Heterobimetallic complexes of palladium and platinum containing a redox-active W[SNS]2 metalloligand.

PubMed

Rosenkoetter, Kyle E; Ziller, Joseph W; Heyduk, Alan F

2017-05-02

Complexes of the general formula W[SNS] 2 M(dppe) (M = Pd, Pt; [SNS]H 3 = bis(2-mercapto-p-tolyl)amine; dppe = 1,2-bis(diphenylphosphino)ethane) were prepared by combining the corresponding (dppe)MCl 2 synthon with W[SNS] 2 under reducing conditions. X-ray diffraction studies revealed the formation of a heterobimetallic complex supported by a single thiolate bridging ligand and a short metal-metal bond between the tungsten and palladium or platinum. Electrochemical and computational results show that the frontier orbitals lie predominantly on the W[SNS] 2 fragment suggesting that it behaves as a redox-active metalloligand in these complexes.

Thiopyridazine-Based Palladium and Platinum Boratrane Complexes.

PubMed

Holler, Stefan; Tüchler, Michael; Steller, Beate G; Belaj, Ferdinand; Veiros, Luis F; Kirchner, Karl; Mösch-Zanetti, Nadia C

2018-06-07

Palladium and platinum boratrane complexes of the type [M{B(Pn Me, tBu ) 3 }(PPh 3 )] (M = Pd 1, Pt 2b) have been prepared via the reaction of the soft scorpionate ligand potassium tris(4-methyl-6- tert-butyl-3-thiopyridazinyl)borate KTn Me, tBu with bis(triphenylphosphine)metal(II) dichloride. While reaction with the Pd precursor allowed direct isolation of a symmetric boratrane complex, the Pt analogue led to the hydrido compound [Pt{B(Pn Me, tBu ) 3 }(PPh 3 )H]Cl (2a), which after reaction with a base gave 2b. Subsequent oxidation with Br 2 and I 2 , respectively, led to the dihalide compounds of the molecular formula [M{B(Pn Me, tBu ) 3 }X 2 ] (3a,b-4a,b). Halide abstraction with Ag(SbF 6 ) further gave interesting cationic compounds of either dimeric [Pd{B(Pn Me, tBu ) 3 }X] 2 (SbF 6 ) 2 (5a,b) or monomeric [Pd{B(Pn Me, tBu ) 3 }(NCMe) 2 ](SbF 6 ) (6) nature. All compounds were spectroscopically and X-ray crystallographically characterized revealing strong metal to boron interactions. DFT calculations of 1, 2a, and 2b confirm the strong M-B interaction and a high positive charge on the metal centers.

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.

Bulk synthesis of nanoporous palladium and platinum powders

DOEpatents

Robinson, David B [Fremont, CA; Fares, Stephen J [Pleasanton, CA; Tran, Kim L [Livermore, CA; Langham, Mary E [Pleasanton, CA

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.

Bulk synthesis of nanoporous palladium and platinum powders

DOEpatents

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.

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.

Synthesis of platinum nanowire networks using a soft template.

PubMed

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

2007-12-01

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

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

DOE PAGES

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

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.

IgE antibody responses to platinum group metals: a large scale refinery survey.

PubMed Central

Murdoch, R D; Pepys, J; Hughes, E G

1986-01-01

All 306 South African platinum refinery workers (116 white, 190 coloured) accepted for employment on grounds of absence of evidence of atopy were investigated using the skin prick test and RAST to detect sensitivity to platinum, palladium, and rhodium salts. RAST studies were made for these, together with HSA and DNP-HSA RAST. Of the 306 workers, 38 had a positive skin prick test to the platinum halide salts; of these, one gave a positive reaction to the palladium salt and six to the rhodium salt. There were no isolated positives to the rhodium and palladium halide salts. Total IgE levels were raised in 24 of the 38 (63%) platinum salt prick test positive workers compared with only 43 of the 268 (16%) prick test negative group (p less than 0.001). Positive RASTs were obtained in 62% of those with positive skin tests to the platinum salts. Four of the six giving positive rhodium salt skin tests gave a positive RAST to rhodium salt. Of these, two gave positive RASTS to HSA and all four to DNP-HSA. The palladium salt RAST was negative in the single skin test reactor. In the platinum salt skin test positive group a raised HSA RAST was obtained in 10.5% compared with only 2.5% in the skin negative group. Twenty one per cent of the platinum salt skin positive group had a raised RAST score to DNP-HSA with only 3.5% (4/116) in the skin test negative group, of whom three also had a raised HSA RAST. The latter findings are suggestive of IgE antibody production to new antigenic determinants in HSA produced by conjugation with the platinum salts. PMID:2936374

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.

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.

Anomalous Nernst and Hall effects in magnetized platinum and palladium

NASA Astrophysics Data System (ADS)

Guo, G. Y.; Niu, Q.; Nagaosa, N.

2014-06-01

We study the anomalous Nernst effect (ANE) and anomalous Hall effect (AHE) in proximity-induced ferromagnetic palladium and platinum which is widely used in spintronics, within the Berry phase formalism based on the relativistic band-structure calculations. We find that both the anomalous Hall (σxyA) and Nernst (αxyA) conductivities can be related to the spin Hall conductivity (σxyS) and band exchange splitting (Δex) by relations σxyA=ΔexeℏσxyS(EF)' and αxyA=-π23kB2TΔexℏσxys(μ )'', respectively. In particular, these relations would predict that the σxyA in the magnetized Pt (Pd) would be positive (negative) since the σxyS(EF)' is positive (negative). Furthermore, both σxyA and αxyA are approximately proportional to the induced spin magnetic moment (ms) because the Δex is a linear function of ms. Using the reported ms in the magnetized Pt and Pd, we predict that the intrinsic anomalous Nernst conductivity (ANC) in the magnetic platinum and palladium would be gigantic, being up to ten times larger than, e.g., iron, while the intrinsic anomalous Hall conductivity (AHC) would also be significant.

MONTANA PALLADIUM RESEARCH INITIATIVE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, John; McCloskey, Jay; Douglas, Trevor

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 highmore » 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

Synthesis, structural characterization, and pro-apoptotic activity of 1-indanone thiosemicarbazone platinum(II) and palladium(II) complexes: potential as antileukemic agents.

PubMed

Gómez, Natalia; Santos, Diego; Vázquez, Ramiro; Suescun, Leopoldo; Mombrú, Alvaro; Vermeulen, Monica; Finkielsztein, Liliana; Shayo, Carina; Moglioni, Albertina; Gambino, Dinorah; Davio, Carlos

2011-08-01

In the search for alternative chemotherapeutic strategies against leukemia, various 1-indanone thiosemicarbazones, as well as eight novel platinum(II) and palladium(II) complexes, with the formula [MCl₂(HL)] and [M(HL)(L)]Cl, derived from two 1-indanone thiosemicarbazones were synthesized and tested for antiproliferative activity against the human leukemia U937 cell line. The crystal structure of [Pt(HL1)(L1)]Cl·2MeOH, where L1=1-indanone thiosemicarbazone, was solved by X-ray diffraction. Free thiosemicarbazone ligands showed no antiproliferative effect, but the corresponding platinum(II) and palladium(II) complexes inhibited cell proliferation and induced apoptosis. Platinum(II) complexes also displayed selective apoptotic activity in U937 cells but not in peripheral blood monocytes or the human hepatocellular carcinoma HepG2 cell line used to screen for potential hepatotoxicity. Present findings show that, in U937 cells, 1-indanone thiosemicarbazones coordinated to palladium(II) were more cytotoxic than those complexed with platinum(II), although the latter were found to be more selective for leukemic cells suggesting that they are promising compounds with potential therapeutic application against hematological malignancies. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Highly Unsaturated Platinum and Palladium Carbenes PtC 3 and PdC 3 Isolated and Characterized in the Gas Phase

DOE PAGES

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

2016-02-16

Carbenes of platinum and palladium, PtC 3 and PdC 3 , 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 PtC 3 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.

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 whether...

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 whether...

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 whether...

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 whether...

Platinum-group elements

USGS Publications Warehouse

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

2017-12-19

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

Exploring the Efficacy of Platinum and Palladium Nanostructures for Organic Molecule Detection via Raman Spectroscopy

PubMed Central

Tran, Minh; Whale, Alison

2018-01-01

Noble transition metals, like palladium (Pd) and platinum (Pt), have been well-known for their excellent catalytic and electrochemical properties. However, they have been considered non-active for surface enhanced Raman spectroscopy (SERS). In this work, we explore the scattering contributions of Pd and Pt for the detection of organic molecules. The Pd and Pt nanostructures were synthesized on silicon substrate using a modified galvanic displacement method. The results show Pt nanoparticles and dendritic Pd nanostructures with controlled density and size. The influence of surfactants, including sodium dodecyl sulfate and cetyltrimethylammonium bromide, on the size and morphology of the nanostructures was investigated. The Pd and Pt nanostructures with a combination of large size and high density were then used to explore their applicability for the detection of 10−5 M Rhodamine 6G and 10−2 M paraoxon. PMID:29316659

Antibacterial activity of microstructured sacrificial anode thin films by combination of silver with platinum group elements (platinum, palladium, iridium).

PubMed

Köller, Manfred; Bellova, Petri; Javid, Siyamak Memar; Motemani, Yahya; Khare, Chinmay; Sengstock, Christina; Tschulik, Kristina; Schildhauer, Thomas A; Ludwig, Alfred

2017-05-01

Five different Ag dots arrays (16 to 400dots/mm 2 ) were fabricated on a continuous platinum, palladium, or iridium thin film and for comparison also on titanium film by sputter deposition and photolithographic patterning. To analyze the antibacterial activity of these microstructured films Staphylococcus aureus (S. aureus) were placed onto the array surfaces and cultivated overnight. To analyze the viability of planktonic as well as surface adherent bacteria, the applied bacterial fluid was subsequently aspirated, plated on blood agar plates and adherent bacteria were detected by fluorescence microscopy. A particular antibacterial effect towards S. aureus was induced by Ag dot arrays on each of the platinum group thin film (sacrificial anode system for Ag) in contrast to Ag dot arrays fabricated on the Ti thin films (non-sacrificial anode system for Ag). Among platinum group elements the Ir-Ag system exerted the highest antibacterial activity which was accompanied by most advanced dissolution of the Ag dots and Ag ion release compared to Ag dots on Pt or Pd. Copyright © 2016 Elsevier B.V. All rights reserved.

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

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.

Poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles-catalyzed hydrolysis of ammonia borane for hydrogen generation

NASA Astrophysics Data System (ADS)

Rakap, Murat

2015-02-01

The catalytic use of highly efficient poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles (4.2 ± 1.9 nm) in the hydrolysis of ammonia-borane is reported. The catalyst is prepared by co-reduction of two metal ions in ethanol/water mixture by an alcohol reduction method and characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and UV-Vis spectroscopy. They are recyclable and highly active for hydrogen generation from the hydrolysis of ammonia-borane even at very low concentrations and temperature, providing a record numbers of average turnover frequency value (125 mol H2/mol cat.min-1) and maximum hydrogen generation rate (3468 L H2 min-1 (mol cat)-1). They also provide activation energy of 51.7 ± 2 kJ/mol for the hydrolysis of ammonia borane.

Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts

NASA Astrophysics Data System (ADS)

Reo, G.; Frank, M. R.; Loocke, M. P.; Macey, C. J.

2017-12-01

Magmatic sulfide ore deposits account for over 80% of the world's platinum group element (PGE) reserves. Layered mafic intrusions (LMIs), a type of magmatic sulfide ore deposit, contain alternating layers of silicate and sulfide mineralization that are thought to have coexisted as an immiscible silicate + sulfide melt pair. Platinum and palladium, the most common PGEs found in LMIs, heavily favor the sulfide melt. Nernst partition coefficients for Pt (D = wt% of Pt in sulfide/wt% of Pt in silicate) range from 102 to 109. This study examined the Pt- and Pd-bearing phases that formed from the quenched sulfide melts to better constrain the PGE-rich sulfide layers of LMIs system. Experiments were conducted with a basalt melt, sulfide melt, and Pt-Pd metal in a vertical tube furnace at 1100°C and 1 atm and with oxygen fugacity buffered to QFM (quartz-fayalite-magnetite). Following the experiments, run products containing both sulfide and silicate glasses (quenched melts) were analyzed by a Shimadzu EPMA-1720HT Electron Probe Microanalyzer. The focus here is on the quenched Fe-rich sulfides whereas data on the partitioning of Pt and Pd between the coexisting silicate and sulfide melts will be presented in the future. The sulfide samples were imaged in back-scattering mode and major and trace element concentrations of separate metal-rich phases in the sulfide matrix were ascertained through wavelength-dispersive x-ray spectroscopy. Three discernable PGE-rich phases were found to have exsolved from the sulfide matrix upon quenching of the sulfide melt. All of these phases had Fe and S of 21-24 and 16-22 wt.%, respectively. An irregularly shaped Pd- and Cu-rich sulfide phase ( 36 and 14 wt.%, respectively) makes up the majority of the exsolution product. A separate Pd- and Ni-rich phase ( 22 and 14 wt%, respectively) can be found as grains or rims adjacent to the exsolved Pd- and Cu-rich phase. A third Pd- and Pt-rich phase ( 26 and 18 wt.%, respectively) exhibits a

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.

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.

LOW-TEMPERATURE HEAT CAPACITIES AND THERMODYNAMIC FUNCTIONS OF SOME PLATINUM AND PALLADIUM GROUP CHALCOGENIDES. I. MONO-CHALCOGENIDES. Pts, PtTe, AND PdTe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Groenvold, F.; Thurmann-Moe, T.; Westrum, E.F. Jr.

1961-11-01

Heat capacities of platinum monosulfide, platinum monotelluride, and palladium monotelluride were measured in the range 5--350 deg K. They show the normal sigmoidal temperature dependence with no evidence of transivions or other anomalies. The derived heat-capacity equations were integrated. Values of heat capacitles, entropy, and enthalpy increments, and of the free-energy function are tabulated for selected temperatures. Av 298,15 deg K, the third-law entroples are 13,16 cal gfw/sup -1/ deg K/sup -1/ for PtS 19.41 cal gfw/sup -1/ deg K/sup - 1/ for PtTe, and 2l.42 cal gfw/sup -1/ deg K/sup -1/ for PdTe. The new dava on PvS weremore » correlaved wlvh exlstlng decomposlvlonpressure data vo evaluate DELTA Hf, DELTA Ff, and DELTA Sf 298.15 deg K. Entropies for other platlnum-metal monochalcogenides were estimated. (auth)« less

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

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.

Platinum, palladium, and rhodium analyses of ultramafic and mafic rocks from the Stillwater Complex, Montana

USGS Publications Warehouse

Page, Norman J; Riley, Leonard Benjamin; Haffty, Joseph

1969-01-01

Analyses by a combination fire- assay-solution-optical-emission spectrographic method of 137 rocks from the Stillwater Complex, Mont., indicate that platinum, palladium, and rhodium are preferentially concentrated in chromitite zones. The A chromitite zone (21 samples) has an average of 988.9 ppb (pans per billion, 10-9) Pt, 2290.2 ppb Pd, and 245.9 ppb Rh and reaches a maximum (to date) of 8,000 ppb Pt, 11,000 ppb Pd, and 1,700 ppb Rh.

Spontaneous incorporation of gold in palladium-based ternary nanoparticles makes durable electrocatalysts for oxygen reduction reaction

PubMed Central

Wang, Deli; Liu, Sufen; Wang, Jie; Lin, Ruoqian; Kawasaki, Masahiro; Rus, Eric; Silberstein, Katharine E.; Lowe, Michael A.; Lin, Feng; Nordlund, Dennis; Liu, Hongfang; Muller, David A.; Xin, Huolin L.; Abruña, Héctor D.

2016-01-01

Replacing platinum by a less precious metal such as palladium, is highly desirable for lowering the cost of fuel-cell electrocatalysts. However, the instability of palladium in the harsh environment of fuel-cell cathodes renders its commercial future bleak. Here we show that by incorporating trace amounts of gold in palladium-based ternary (Pd6CoCu) nanocatalysts, the durability of the catalysts improves markedly. Using aberration-corrected analytical transmission electron microscopy in conjunction with synchrotron X-ray absorption spectroscopy, we show that gold not only galvanically replaces cobalt and copper on the surface, but also penetrates through the Pd–Co–Cu lattice and distributes uniformly within the particles. The uniform incorporation of Au provides a stability boost to the entire host particle, from the surface to the interior. The spontaneous replacement method we have developed is scalable and commercially viable. This work may provide new insight for the large-scale production of non-platinum electrocatalysts for fuel-cell applications. PMID:27336795

Spontaneous incorporation of gold in palladium-based ternary nanoparticles makes durable electrocatalysts for oxygen reduction reaction

DOE PAGES

Wang, Deli; Liu, Sufen; Wang, Jie; ...

2016-06-23

Replacing platinum by a less precious metal such as palladium, is highly desirable for lowering the cost of fuel-cell electrocatalysts. However, the instability of palladium in the harsh environment of fuel-cell cathodes renders its commercial future bleak. Here we show that by incorporating trace amounts of gold in palladium-based ternary (Pd6CoCu) nanocatalysts, the durability of the catalysts improves markedly. Using aberration-corrected analytical transmission electron microscopy in conjunction with synchrotron X-ray absorption spectroscopy, we show that gold not only galvanically replaces cobalt and copper on the surface, but also penetrates through the Pd–Co–Cu lattice and distributes uniformly within the particles. Themore » uniform incorporation of Au provides a stability boost to the entire host particle, from the surface to the interior. The spontaneous replacement method we have developed is scalable and commercially viable. This work may provide new insight for the large-scale production of non-platinum electrocatalysts for fuel-cell applications.« less

Biosorptive recovery of platinum from platinum group metal refining wastewaters by immobilised Saccharomyces cerevisiae.

PubMed

Mack, C L; Wilhelmi, B; Duncan, J R; Burgess, J E

2011-01-01

The process of platinum group metal (PGM) refining can be up to 99.99% efficient at best, and although it may seem small, the amount of valuable metal lost to waste streams is appreciable enough to warrant recovery. The method currently used to remove entrained metal ions from refinery wastewaters, chemical precipitation, is not effective for selective recovery of PGMs. The yeast Saccharomyces cerevisiae has been found capable of sorbing numerous precious and base metals, and is a cheap and abundant source of biomass. In this investigation, S. cerevisiae was immobilised using polyethyleneimine and glutaraldehyde to produce a suitable sorbent, capable of high platinum uptake (150-170 mg/g) at low pH (<2). The sorption mechanism was found to be a chemical reaction, which made effective desorption impossible. When applied to PGM refinery wastewater, two key wastewater characteristics limited the success of the sorption process; high inorganic ion content and complex speciation of the platinum ions. The results proved the concept principle of platinum recovery by immobilised yeast biosorption and indicated that a more detailed understanding of the platinum speciation within the wastewater is required before biosorption can be applied. Overall, the sorption of platinum by the S. cerevisiae sorbent was demonstrated to be highly effective in principle, but the complexity of the wastewater requires that pretreatment steps be taken before the successful application of this process to industrial wastewater.

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

PubMed

Essumang, D K

2010-06-01

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

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)

Variation of M···H-C Interactions in Square-Planar Complexes of Nickel(II), Palladium(II), and Platinum(II) Probed by Luminescence Spectroscopy and X-ray Diffraction at Variable Pressure.

PubMed

Poirier, Stéphanie; Lynn, Hudson; Reber, Christian; Tailleur, Elodie; Marchivie, Mathieu; Guionneau, Philippe; Probert, Michael R

2018-06-12

Luminescence spectra of isoelectronic square-planar d 8 complexes with 3d, 4d, and 5d metal centers show d-d luminescence with an energetic order different from that of the spectrochemical series, indicating that additional structural effects, such as different ligand-metal-ligand angles, are important factors. Variable-pressure luminescence spectra of square-planar nickel(II), palladium(II), and platinum(II) complexes with dimethyldithiocarbamate ({CH 3 } 2 DTC) ligands and their deuterated analogues show unexpected variations of the shifts of their maxima. High-resolution crystal structures and crystal structures at variable pressure for [Pt{(CH 3 ) 2 DTC} 2 ] indicate that intermolecular M···H-C interactions are at the origin of these different shifts.

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, that...

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, that...

Triazole-functionalized N-heterocyclic carbene complexes of palladium and platinum and efficient aqueous Suzuki-Miyaura coupling reaction.

PubMed

Gu, Shaojin; Xu, Hui; Zhang, Na; Chen, Wanzhi

2010-07-05

Imidazolium salts bearing triazole groups are synthesized via a copper catalyzed click reaction, and the silver, palladium, and platinum complexes of their N-heterocyclic carbenes are studied. [Ag(4)(L1)(4)](PF(6))(4), [Pd(L1)Cl](PF(6)), [Pt(L1)Cl](PF(6)) (L1=3-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-1-(pyrimidin-2-yl)-1H-imidazolylidene), [Pd(2)(L2)(2)Cl(2)](PF(6))(2), and [Pd(L2)(2)](PF(6))(2) (L2=1-butyl-3-((1-(pyridin-2-yl)-1H-1,2,3-triazol-4-yl)methyl)imidazolylidene) have been synthesized and fully characterized by NMR, elemental analysis, and X-ray crystallography. The silver complex [Ag(4)(L1)(4)](PF(6))(4) consists of a Ag(4) zigzag chain. The complexes [Pd(L1)Cl](PF(6)) and [Pt(L1)Cl](PF(6)), containing a nonsymmetrical NCN' pincer ligand, are square planar with a chloride trans to the carbene donor. [Pd(2)(L2)(2)Cl(2)](PF(6))(2) consists of two palladium centers with CN(2)Cl coordination mode, whereas the palladium in [Pd(L2)(2)](PF(6))(2) is surrounded by two carbene and two triazole groups with two uncoordinated pyridines. The palladium compounds are highly active for Suzuki-Miyaura cross coupling reactions of aryl bromides and 1,1-dibromo-1-alkenes in neat water under an air atmosphere.

Copper-Based Electrochemical Sensor with Palladium Electrode for Cathodic Stripping Voltammetry of Manganese

PubMed Central

2015-01-01

In this work, we report on the development of a palladium-based, microfabricated point-of-care electrochemical sensor for the determination of manganese using square wave cathodic stripping voltammetry. Heavy metals require careful monitoring, yet current methods are too complex for a point-of-care system. Voltammetry offers an attractive approach to metal detection on the microscale, but traditional carbon, gold, or platinum electrodes are difficult or expensive to microfabricate, preventing widespread use. Our sensor uses palladium working and auxiliary electrodes and integrates them with a copper-based reference electrode for simple fabrication and compatibility with microfabrication and printed circuit board processing, while maintaining competitive performance in electrochemical detection. Copper electrodes were prepared on glass substrate using a combination of microfabrication procedures followed by electrodeposition of palladium. The disposable sensor system was formed by bonding a poly(dimethylsiloxane) (PDMS) well to the glass substrate. Cathodic stripping voltammetry of manganese using our new disposable palladium-based sensors exhibited 334 nM (18.3 ppb) limit of detection in borate buffer. The sensor was used to demonstrate manganese determination in natural water samples from a pond in Burnet Woods, located in Cincinnati, OH, and the Ohio River. PMID:25476591

Copper-based electrochemical sensor with palladium electrode for cathodic stripping voltammetry of manganese.

PubMed

Kang, Wenjing; Pei, Xing; Bange, Adam; Haynes, Erin N; Heineman, William R; Papautsky, Ian

2014-12-16

In this work, we report on the development of a palladium-based, microfabricated point-of-care electrochemical sensor for the determination of manganese using square wave cathodic stripping voltammetry. Heavy metals require careful monitoring, yet current methods are too complex for a point-of-care system. Voltammetry offers an attractive approach to metal detection on the microscale, but traditional carbon, gold, or platinum electrodes are difficult or expensive to microfabricate, preventing widespread use. Our sensor uses palladium working and auxiliary electrodes and integrates them with a copper-based reference electrode for simple fabrication and compatibility with microfabrication and printed circuit board processing, while maintaining competitive performance in electrochemical detection. Copper electrodes were prepared on glass substrate using a combination of microfabrication procedures followed by electrodeposition of palladium. The disposable sensor system was formed by bonding a poly(dimethylsiloxane) (PDMS) well to the glass substrate. Cathodic stripping voltammetry of manganese using our new disposable palladium-based sensors exhibited 334 nM (18.3 ppb) limit of detection in borate buffer. The sensor was used to demonstrate manganese determination in natural water samples from a pond in Burnet Woods, located in Cincinnati, OH, and the Ohio River.

Exhaust system having a gold-platinum group metal catalyst

DOEpatents

Ragle, Christie Susan [Havana, IL; Silver, Ronald G [Peoria, IL; Zemskova, Svetlana Mikhailovna [Edelstein, IL; Eckstein, Colleen J [Metamora, IL

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.

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.

Gold-promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction.

PubMed

Kuttiyiel, Kurian A; Sasaki, Kotaro; Su, Dong; Wu, Lijun; Zhu, Yimei; Adzic, Radoslav R

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here we report on a structurally ordered Au10Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that, at elevated temperatures, palladium cobalt nanoparticles undergo an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets via addition of gold atoms. The superior stability of this catalyst compared with platinum after 10,000 potential cycles in alkaline media is attributed to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matter.

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

Assessment of sublethal endpoints after chronic exposure of the nematode Caenorhabditis elegans to palladium, platinum and rhodium.

PubMed

Schertzinger, Gerhard; Zimmermann, Sonja; Grabner, Daniel; Sures, Bernd

2017-11-01

The aim of this study was to investigate chronic effects of the platinum-group elements (PGE) palladium (Pd), platinum (Pt) and rhodium (Rh) on the nematode Caenorhabditis elegans. Aquatic toxicity testing was carried out according to ISO 10872 by determining 96 h EC 50 values for sublethal endpoints, including growth, fertility and reproduction. Single PGE standard solutions were used as metal source. Based on the EC 50 values for Pt, reproduction (96 h EC 50  = 497 μg/L) was the most sensitive endpoint followed by fertility (96 h EC 50  = 726 μg/L) and growth (96 h EC 50  = 808 μg/L). For Pd, no precise EC 50 values could be calculated due to bell-shaped concentration response curves, but the 96 h EC 50 for reproduction ranged between 10 and 100 μg/L. Pd and Pt had effects on all endpoints. With raising element concentrations reproduction was inhibited first. At a certain concentration, fertility was also affected, which in turn had an additional effect on reproduction. Growth inhibition can also lead to a loss of fertility if the worms do not reach an appropriate body size to become fertile. Rhodium showed no inhibition of any endpoint between concentrations of 100 to 10,000 μg Rh/L. The results of this study allow the following order of PGE with respect to decreasing toxicity to C. elegans: Pd > Pt » Rh. Copyright © 2017 Elsevier Ltd. All rights reserved.

Induction of metallothionein in chick embryos as a mechanism of tolerance to platinum group metal exposure.

PubMed

Gagnon, Zofia E; Patel, Amit

2007-02-15

Recent data show that platinum group metals (PGMs), primarily platinum (Pt), palladium (Pd) and rhodium (Rd), from automobile catalytic converters are being deposited in the environment. We investigated the PGM neurotoxicity and tolerance mechanism by induction of metallothionein (MT) in developing chick embryos. Chick embryos were injected on the 7th and 14th days of incubation with different concentrations of Pt and mixture of Pt, Pd and Rh (PGM mix) solutions. It is documented that induction of MT by zinc (Zn+2) protects against metal and non-metal hepatotoxicity. In this study the MT induction was examined through pretreatment of the two highest Pt(IV) exposure levels with exogenous Zn2+ on the 4th and 11th days of incubation. SDS-PAGE assay and digital image system were used to identify and quantify MT in homogenized brain and liver tissues. Quantitative analysis revealed an increase of MT in the 5 ppm Pt exposure as compared to controls. The 10 ppm Pt treatment was a lethal dose for exposed embryos. There was increased mortality at the 1.0 PGM mix level. The interaction of Pt, Pd and Rh in the mixture seems to favor metal accumulation and MT induction in the liver but not the brain. Pretreatment with exogenous Zn2+ increased chick survival. These results indicate that induction of MT plays a protective role against PGM toxicity. Metal analysis using atomic absorption spectrometer in graphite furnace mode (GFAAS) revealed PGM accumulation in chick embryo liver and brain tissues proportional to exposure concentration. Our results may imply that MT has an important role as a tolerance mechanism against PGM toxicity. The presence of Pt(IV) in brain tissue suggests that the undeveloped blood-brain barrier is permeable to PGMs. This raises concerns regarding the implication of these metals on neural injury.

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.

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

DOE PAGES

Wang, Xue; Choi, Sang-Il; Roling, Luke T.; ...

2015-07-02

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 bemore » 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. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.« less

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.

Process for Making a Noble Metal on Tin Oxide Catalyst

NASA Technical Reports Server (NTRS)

Davis, Patricia; Miller, Irvin; Upchurch, Billy

2010-01-01

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

Antiandrogen and Antimicrobial Aspects of Coordination Compounds of Palladium(II), Platinum(II) and Lead(II)

PubMed Central

Joshi, S. C.; Kulshrestha, Shalini; Nagpal, Pooja; Bansal, Anil

2001-01-01

Synthesis, characterization and antimicrobial activities of an interesting class of biologically potent macrocyclic complexes have been carried out. All the complexes have been evaluated for their antimicrobial effects on different species of pathogenic fungi and bacteria. The testicular sperm density, testicular sperm morphology, sperm motility, density of cauda epididymal spermatozoa and fertility in mating trails and biochemical parameters of reproductive organs have been examined and discussed. The resulting biologically active [M(MaLn)(R2)]Cl2 and [Pb(MaLn)(R2)X2] (where, M = PdII or PtII and X = Cl or NO3) type of complexes have been synthesized by the reactions of macrocyclic ligands (MaLn) with metal salts and different diamines in 1:1:1 molar ratio in methanol. Initially the complexes were characterized by elemental analyses, molecular weight determinations and conductivity measurements. The mode of bonding was established on the basis of IR, 1H NMR, 13C NMR, 195Pt NMR, 207Pb NMR, XRD and electronic spectral studies. The macrocyclic ligand coordinates through the four azomethine nitrogen atoms which are bridged by benzil moieties. IR spectra suggest that the pyridine nitrogen is not coordinating. The palladium and platinum complexes exhibit tetracoordinated square-planar geometry, whereas a hexacoordinated octahedral geometry is suggested for lead complexes. PMID:18475989

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Lulu; Su, Dong; Zhu, Shangqian

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

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

DOE PAGES

Zhang, Lulu; Su, Dong; Zhu, Shangqian; ...

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

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.

Comparative study of hematological responses to platinum group metals, antimony and silver nanoparticles in animal models.

PubMed

Newkirk, Catherine E; Gagnon, Zofia E; Pavel Sizemore, Ioana E

2014-01-01

Research was conducted to examine the hematological effects of heavy metals (platinum (Pt ((IV))), palladium (Pd ((II))), rhodium (Rh ((III))), antimony (Sb ((III)) and Sb ((V))), and silver nanoparticles (AgNPs)) on white blood cells in mammalian (rat) and avian (chick embryo) models. These metals are used in many everyday products and are accumulating in our environment. Six-week old Sprague-Dawley female rats were treated daily by gavage and six-day old, fertile, specific pathogen-free white leghorn strain chick embryos' eggs were injected on days 7 and 14 of incubation with 0.0, 1.0, 5.0 or 10.0 ppm concentrations of Pt ((IV)) and a platinum group metal (PGM) mix of Pt ((IV)), Pd ((II)) and Rh ((III)). Chick embryos were also tested with 1.0 or 5.0 ppm of antimony compounds (Sb ((III)) and Sb ((V))) and 0.0, 15.0, 30.0, 60.0, or 100.0 ppm of silver nanoparticles (AgNPs). After 8 weeks of treatment, blood was obtained from the rats by jugular cut down and from chick embryos on day 20 of incubation by heart puncture. Blood smears were made and stained and a differential white cell count was performed on each. Examination of the smears revealed unconventional dose responses, stimulation of the immune response, and decreases in leukocyte production with various metals and concentrations. Chick embryos responded differently than rats to Pt and the PGM mix; suggesting that species differences and/or stage of development are important components of response to heavy metals. Route of administration of the metals might also influence the response. All of the heavy metals tested affected the immune responses of the tested animals as demonstrated by changes in the types and numbers of leukocytes. Our findings warrant further research to determine the mechanism of these effects and to understand and prevent toxicological effects in humans and other living organisms.

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.

Gold–promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuttiyiel, Kurian A.; Sasaki, Kotaro; Su, Dong

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here, we report on a structurally ordered Au₁₀Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that via addition of gold atoms PdCo nanoparticles undergo at elevated temperatures an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets. The superior stability of this catalyst compared to platinum after 10,000 potential cycles in alkaline media is attributedmore » to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matters.« less

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.

Uniform Pt/Pd Bimetallic Nanocrystals Demonstrate Platinum Effect on Palladium Methane Combustion Activity and Stability

DOE PAGES

Goodman, Emmett D.; Dai, Sheng; Yang, An-Chih; ...

2017-05-18

Bimetallic catalytic materials are in widespread use for numerous reactions, as the properties of a monometallic catalyst are often improved upon addition of a second metal. In studies with bimetallic catalysts, it remains challenging to establish clear structure–property relationships using traditional impregnation techniques, due to the presence of multiple coexisting active phases of different sizes, shapes, and compositions. Here, a convenient approach to prepare small and uniform Pt/Pd bimetallic nanocrystals with tailorable composition is demonstrated, despite the metals being immiscible in the bulk. By depositing this set of controlled nanocrystals onto a high-surface-area alumina support, we systematically investigate the effectmore » of adding platinum to palladium catalysts for methane combustion. At low temperatures and in the absence of steam, all bimetallic catalysts show activity nearly identical with that of Pt/Al 2O 3, with much lower rates in comparison to that of the Pd/Al 2O 3 sample. BUt, unlike Pd/Al 2O 3, which experiences severe low-temperature steam poisoning, all Pt/Pd bimetallic catalysts maintain combustion activity on exposure to excess steam. These features are due to the influence of Pt on the Pd oxidation state, which prevents the formation of a bulk-type PdO phase. Despite lower initial combustion rates, hydrothermal aging of the Pd-rich bimetallic catalyst induces segregation of a PdO phase in close contact to a Pd/Pt alloy phase, forming more active and highly stable sites for methane combustion. Altogether, this work unambiguously clarifies the activity and stability attributes of Pt/Pd phases which often coexist in traditionally synthesized bimetallic catalysts and demonstrates how well-controlled bimetallic catalysts elucidate structure–property relationships.« less

Uniform Pt/Pd Bimetallic Nanocrystals Demonstrate Platinum Effect on Palladium Methane Combustion Activity and Stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goodman, Emmett D.; Dai, Sheng; Yang, An-Chih

Bimetallic catalytic materials are in widespread use for numerous reactions, as the properties of a monometallic catalyst are often improved upon addition of a second metal. In studies with bimetallic catalysts, it remains challenging to establish clear structure–property relationships using traditional impregnation techniques, due to the presence of multiple coexisting active phases of different sizes, shapes, and compositions. Here, a convenient approach to prepare small and uniform Pt/Pd bimetallic nanocrystals with tailorable composition is demonstrated, despite the metals being immiscible in the bulk. By depositing this set of controlled nanocrystals onto a high-surface-area alumina support, we systematically investigate the effectmore » of adding platinum to palladium catalysts for methane combustion. At low temperatures and in the absence of steam, all bimetallic catalysts show activity nearly identical with that of Pt/Al 2O 3, with much lower rates in comparison to that of the Pd/Al 2O 3 sample. BUt, unlike Pd/Al 2O 3, which experiences severe low-temperature steam poisoning, all Pt/Pd bimetallic catalysts maintain combustion activity on exposure to excess steam. These features are due to the influence of Pt on the Pd oxidation state, which prevents the formation of a bulk-type PdO phase. Despite lower initial combustion rates, hydrothermal aging of the Pd-rich bimetallic catalyst induces segregation of a PdO phase in close contact to a Pd/Pt alloy phase, forming more active and highly stable sites for methane combustion. Altogether, this work unambiguously clarifies the activity and stability attributes of Pt/Pd phases which often coexist in traditionally synthesized bimetallic catalysts and demonstrates how well-controlled bimetallic catalysts elucidate structure–property relationships.« less

Interaction of palladium ions with the skin.

PubMed

Santucci, B; Cristaudo, A; Cannistraci, C; Picardo, M

1995-08-01

87 subjects sensitive to both nickel sulfate and palladium-chloride pet., were contemporaneously patch retested to nickel sulfate 5% pet., metallic palladium chloride 1% pet. and to palladium chloride 1% aq. Whilst all subjects reacted to nickel sulfate and palladium chloride pet., only 3 reacted to palladium chloride aq. No positive reactions were found to metallic palladium. The negative results to palladium chloride aq. are probably due to the formation of a new palladium ion (PdCl4)2-, achieved on adding an amount of hydrocloric acid to the aqueous solution of PdCl2. The findings seem to demonstrate that the allergic reaction to palladium depends on the arrangement of the metal electrons. The sensitization to palladium does not seem to be dependent on the element itself but on the complexes formed by the different compounds. The concomitant reactions to nickel and palladium ions could be dependent on the generation of similar complexes between the ions and the skin proteins.

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.

Osmium isotope constraints on ore metal recycling in subduction zones

PubMed

McInnes; McBride; Evans; Lambert; Andrew

1999-10-15

Veined peridotite xenoliths from the mantle beneath the giant Ladolam gold deposit on Lihir Island, Papua New Guinea, are 2 to 800 times more enriched in copper, gold, platinum, and palladium than surrounding depleted arc mantle. Gold ores have osmium isotope compositions similar to those of the underlying subduction-modified mantle peridotite source region, indicating that the primary origin of the metals was the mantle. Because the mantle is relatively depleted in gold, copper, and palladium, tectonic processes that enhance the advective transport and concentration of these fluid soluble metals may be a prerequisite for generating porphyry-epithermal copper-gold deposits.

Noble metals: a toxicological appraisal of potential new environmental contaminants.

PubMed Central

Brubaker, P E; Moran, J P; Bridbord, K; Hueter, F G

1975-01-01

The public health benefits expected by reducing known hazardous emissions from mobile sources should not be compromised by increasing levels of other potentially hazardous unregulated emissions. Catalytic converters are going to be used to meet the statutory requirements on carbon monoxide and hydrocarbon emissions from light duty motor vehicles. Platinum and palladium metals are the catalytic materials to be used in these emission control devices. Preliminary experimental evidence and analysis of the impact of these control devices on the future use and demand for platinum indicates that this metal may appear at detectable levels in the environment by the end of this decade. At the present time, platinum and palladium are not present in the public environment and represent potentially new environmental contaminants as a consequence of use of this new abatement control technology. There is relatively little information available to adequately assess the potential health hazards that may be associated with exposure to these metals and their compounds. Analysis of the environmental problems and concerns associated with possible new environmental contaminants are discussed. Limited estimates are made on community exposure by use of a meteorological dispersion model. Biodegradation potential and attention is also given to the limited toxicological information available. PMID:50939

Cytotoxic properties of a new organometallic platinum(II) complex and its gold(I) heterobimetallic derivatives.

PubMed

Serratrice, Maria; Maiore, Laura; Zucca, Antonio; Stoccoro, Sergio; Landini, Ida; Mini, Enrico; Massai, Lara; Ferraro, Giarita; Merlino, Antonello; Messori, Luigi; Cinellu, Maria Agostina

2016-01-14

A novel platinum(ii) organometallic complex, [Pt(pbi)(Me)(DMSO)], bearing the 2-(2'-pyridyl)-benzimidazole (pbiH) ligand, was synthesized and fully characterized. Interestingly, the reaction of this organometallic platinum(ii) complex with two distinct gold(i) phosphane compounds afforded the corresponding heterobimetallic derivatives with the pbi ligand bridging the two metal centers. The antiproliferative properties in vitro of [Pt(pbi)(Me)(DMSO)] and its gold(i) derivatives as well as those of the known coordination platinum(ii) and palladium(ii) complexes with the same ligand, of the general formula [MCl2(pbiH)], were comparatively evaluated against A2780 cancer cells, either sensitive or resistant to cisplatin. A superior biological activity of the organometallic compound clearly emerged compared to the corresponding platinum(ii) complex; the antiproliferative effects are further enhanced upon attaching the gold(i) triphenylphosphine moiety to the organometallic Pt compound. Remarkably, these novel metal species are able to overcome nearly complete resistance to cisplatin. Significant mechanistic insight into the study compounds was gained after investigating their reactions with a few representative biomolecules by electrospray mass spectrometry and X-ray crystallography. The obtained results are comprehensively discussed.

Synthesis of metal silicide at metal/silicon oxide interface by electronic excitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, J.-G., E-mail: jglee36@kims.re.kr; Nagase, T.; Yasuda, H.

The synthesis of metal silicide at the metal/silicon oxide interface by electronic excitation was investigated using transmission electron microscopy. A platinum silicide, α-Pt{sub 2}Si, was successfully formed at the platinum/silicon oxide interface under 25–200 keV electron irradiation. This is of interest since any platinum silicide was not formed at the platinum/silicon oxide interface by simple thermal annealing under no-electron-irradiation conditions. From the electron energy dependence of the cross section for the initiation of the silicide formation, it is clarified that the silicide formation under electron irradiation was not due to a knock-on atom-displacement process, but a process induced by electronic excitation.more » It is suggested that a mechanism related to the Knotek and Feibelman mechanism may play an important role in silicide formation within the solid. Similar silicide formation was also observed at the palladium/silicon oxide and nickel/silicon oxide interfaces, indicating a wide generality of the silicide formation by electronic excitation.« less

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.

Platinum redispersion on metal oxides in low temperature fuel cells.

PubMed

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

2013-03-07

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

Palladium and Platinum Nanoparticles Attenuate Aging-Like Skin Atrophy via Antioxidant Activity in Mice

PubMed Central

Shibuya, Shuichi; Ozawa, Yusuke; Watanabe, Kenji; Izuo, Naotaka; Toda, Toshihiko; Yokote, Koutaro; Shimizu, Takahiko

2014-01-01

Cu-Zn superoxide dismutase (Sod1) loss causes a redox imbalance as it leads to excess superoxide generation, which results in the appearance of various aging-related phenotypes, including skin atrophy. Noble metal nanoparticles, such as palladium (Pd) and platinum (Pt) nanoparticles, are considered to function as antioxidants due to their strong catalytic activity. In Japan, a mixture of Pd and Pt nanoparticles called PAPLAL has been used to treat chronic diseases over the past 60 years. In the present study, we investigated the protective effects of PAPLAL against aging-related skin pathologies in mice. Transdermal PAPLAL treatment reversed skin thinning associated with increased lipid peroxidation in Sod1 −/− mice. Furthermore, PAPLAL normalized the gene expression levels of Col1a1, Mmp2, Has2, Tnf-α, Il-6, and p53 in the skin of the Sod1 −/− mice. Pt nanoparticles exhibited marked SOD and catalase activity, while Pd nanoparticles only displayed weak SOD and catalase activity in vitro. Although the SOD and catalase activity of the Pt nanoparticles significantly declined after they had been oxidized in air, a mixture of Pd and Pt nanoparticles continued to exhibit SOD and catalase activity after oxidation. Importantly, a mixture of Pd and Pt nanoparticles with a molar ratio of 3 or 4 to 1 continued to exhibit SOD and catalase activity after oxidation, indicating that Pd nanoparticles prevent the oxidative deterioration of Pt nanoparticles. These findings indicate that PAPLAL stably suppresses intrinsic superoxide generation both in vivo and in vitro via SOD and catalase activity. PAPLAL is a potentially powerful tool for the treatment of aging-related skin diseases caused by oxidative damage. PMID:25333617

Palladium and platinum nanoparticles attenuate aging-like skin atrophy via antioxidant activity in mice.

PubMed

Shibuya, Shuichi; Ozawa, Yusuke; Watanabe, Kenji; Izuo, Naotaka; Toda, Toshihiko; Yokote, Koutaro; Shimizu, Takahiko

2014-01-01

Cu-Zn superoxide dismutase (Sod1) loss causes a redox imbalance as it leads to excess superoxide generation, which results in the appearance of various aging-related phenotypes, including skin atrophy. Noble metal nanoparticles, such as palladium (Pd) and platinum (Pt) nanoparticles, are considered to function as antioxidants due to their strong catalytic activity. In Japan, a mixture of Pd and Pt nanoparticles called PAPLAL has been used to treat chronic diseases over the past 60 years. In the present study, we investigated the protective effects of PAPLAL against aging-related skin pathologies in mice. Transdermal PAPLAL treatment reversed skin thinning associated with increased lipid peroxidation in Sod1-/- mice. Furthermore, PAPLAL normalized the gene expression levels of Col1a1, Mmp2, Has2, Tnf-α, Il-6, and p53 in the skin of the Sod1-/- mice. Pt nanoparticles exhibited marked SOD and catalase activity, while Pd nanoparticles only displayed weak SOD and catalase activity in vitro. Although the SOD and catalase activity of the Pt nanoparticles significantly declined after they had been oxidized in air, a mixture of Pd and Pt nanoparticles continued to exhibit SOD and catalase activity after oxidation. Importantly, a mixture of Pd and Pt nanoparticles with a molar ratio of 3 or 4 to 1 continued to exhibit SOD and catalase activity after oxidation, indicating that Pd nanoparticles prevent the oxidative deterioration of Pt nanoparticles. These findings indicate that PAPLAL stably suppresses intrinsic superoxide generation both in vivo and in vitro via SOD and catalase activity. PAPLAL is a potentially powerful tool for the treatment of aging-related skin diseases caused by oxidative damage.

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.

Synthesis of Ultra-Small Palladium Nanoparticles Deposited on CdS Nanorods by Pulsed Laser Ablation in Liquid: Role of Metal Nanocrystal Size in the Photocatalytic Hydrogen Production.

PubMed

Park, Hanbit; Reddy, D Amaranatha; Kim, Yujin; Lee, Seunghee; Ma, Rory; Kim, Tae Kyu

2017-09-21

It is imperative to suppress the rate of recombination of photogenerated carriers to improve the semiconductor-catalyzed solar-driven production of hydrogen. To this end, photocatalysts comprising active sunlight-harvesting photo-absorbers and stable metal co-catalysts have attracted significant attention. However, the size, clean surface, and highly dispersed nature of the metal co-catalysts are crucial factors affecting catalyst performance and reaction rate. Nevertheless, most of the available metal nanocrystals have been synthesized by complex procedures using harmful organic templates and stabilizers, affording high-purity compounds with difficulty and high cost. To overcome these problems, in this study, the pulsed laser ablation in liquid approach was utilized to generate palladium and bimetallic palladium-platinum nanoparticles with an average size and distribution by adjusting the laser wavelength and fluence. A high rate of evolution of hydrogen of 130.33 mmol g -1  h -1 was obtained by using the optimized CdS-PdPt catalyst under simulated sunlight irradiation. This value is 51.31 times greater than that observed for bare CdS nanostructures. Furthermore, the amount of hydrogen evolved was significantly better than that obtained by using several other noble-metal co-catalysts deposited on CdS. This proposed strategy is thought to open new avenues for the design of advanced photocatalytic materials for efficient solar-driven production of hydrogen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biogenic platinum and palladium nanoparticles as new catalysts for the removal of pharmaceutical compounds.

PubMed

Martins, Mónica; Mourato, Cláudia; Sanches, Sandra; Noronha, João Paulo; Crespo, M T Barreto; Pereira, Inês A C

2017-01-01

Pharmaceutical products (PhP) are one of the most alarming emergent pollutants in the environment. Therefore, it is of extreme importance to investigate efficient PhP removal processes. Biologic synthesis of platinum nanoparticles (Bio-Pt) has been reported, but their catalytic activity was never investigated. In this work, we explored the potential of cell-supported platinum (Bio-Pt) and palladium (Bio-Pd) nanoparticles synthesized with Desulfovibrio vulgaris as biocatalysts for removal of four PhP: ciprofloxacin, sulfamethoxazole, ibuprofen and 17β-estradiol. The catalytic activity of the biological nanoparticles was compared with the PhP removal efficiency of D. vulgaris whole-cells. In contrast with Bio-Pd, Bio-Pt has a high catalytic activity in PhP removal, with 94, 85 and 70% removal of 17β-estradiol, sulfamethoxazole and ciprofloxacin, respectively. In addition, the estrogenic activity of 17β-estradiol was strongly reduced after the reaction with Bio-Pt, showing that this biocatalyst produces less toxic effluents. Bio-Pt or Bio-Pd did not act on ibuprofen, but this could be completely removed by D. vulgaris whole-cells, demonstrating that sulfate-reducing bacteria are among the microorganisms capable of biotransformation of ibuprofen in anaerobic environments. This study demonstrates for the first time that Bio-Pt has a high catalytic activity, and is a promising catalyst to be used in water treatment processes for the removal of antibiotics and endocrine disrupting compounds, the most problematic PhP. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Method of synthesizing metal doped diamond-like carbon films

NASA Technical Reports Server (NTRS)

Ueno, Mayumi (Inventor); Sunkara, Mahendra Kumar (Inventor)

2003-01-01

A method of synthesizing metal doped carbon films by placing a substrate in a chamber with a selected amount of a metalorganic compound. An electron cyclotron resonance is applied to the chamber in order to vaporize the metalorganic compound. The resonance is applied to the chamber until a metal doped carbon film is formed. The metalorganic compound is preferably selected from the group consisting of an organic salt of ruthenium, palladium, gold or platinum.

Anthrobiogeochemical platinum, palladium and rhodium cycles of earth: Emerging environmental contamination

NASA Astrophysics Data System (ADS)

Mitra, Arijeet; Sen, Indra Sekhar

2017-11-01

Anthrobiogeochemical cycles have been a subject of scientific research for many decades as they are important for identifying possible sources, sinks, and pathways of an element in the environment. In this study, we quantified global cycles for the platinum group elements (PGE; platinum (Pt), palladium (Pd) and rhodium (Rh)). We quantified the stocks of Pt, Pd, and Rh in Earth's various reservoirs, such as the core, mantle, consolidated crust, biomass, seawater, unconsolidated sediments, and atmosphere, as well as coal and petroleum deposits. We further quantified their fluxes, both natural and anthropogenic, between each reservoir, by identifying the flows across the hydrosphere, geosphere, biosphere, atmosphere and anthroposphere, including from mining activities, fossil fuel and biomass burning, construction activities, soil erosion, human contributions to net primary productivity, riverine transport, aeolian dust movement, primary production, volcanic eruption, sea-salt spray, crustal subduction, crust formation at mid ocean ridges, PGE recovery from recycling processes, and cosmic dust inputs at the Earth's surface. Stocks of PGEs were quantified by multiplying the mass of the reservoir by the average Pt, Pd and Rh concentration in the reservoir, whereas Pt, Pd and Rh fluxes were calculated by multiplying the rate of mass movement across the reservoirs with the Pt, Pd and Rh concentrations of the material. Uncertainties were explicitly incorporated in stock and flow estimations through Monte Carlo simulations. Our calculations reveal that the total surficial anthropogenic Pt, Pd, and Rh mobilizations were greater than their corresponding natural surficial mobilizations. We show that crustal subduction and crustal formation is the most important natural flow and contributes 21-42% of total PGE mobilization. When Earth's surficial processes are considered, soil erosion is the dominant flow for Rh and Pt mobilization, comprising 33% and 13%, respectively, of the

Synthesis, structure, and electrochemistry of di- and zerovalent nickel, palladium, and platinum monomers and dimers derived from an enantiopure (S,S)-tetra(tertiary phosphine).

PubMed

Kitto, Heather J; Rae, A David; Webster, Richard D; Willis, Anthony C; Wild, S Bruce

2007-09-17

The ligand (S,S)-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane, (S,S)-tetraphos, reacts with hexa(aqua)nickel(II) chloride in the presence of trimethylsilyl triflate (TMSOTf) in dichloromethane to give the yellow square-planar complex [Ni{(R,R)-tetraphos}](OTf)2, which has been crystallographically characterized as the square-pyramidal, acetonitrile adduct [Ni(NCMe){(R,R)-tetraphos}]OTf. Cyclic voltammograms of the nickel(II) complex in dichloromethane and acetonitrile at 20 degrees C showed two reduction processes at negative potentials with oxidative (E(p)(ox)) and reductive (E(p)(red)) peak separations similar to those observed for ferrocene/ferrocenium under identical conditions, suggesting two one-electron steps. The cyclic voltammetric data for the divalent nickel complex in acetonitrile at temperatures below -20 degrees C were interpreted according to reversible coordination of acetonitrile to the nickel(I) and nickel(0) complexes. The divalent palladium and platinum complexes [M{(R,R)-tetraphos}](PF6)2 and [M2{(R,R)-tetraphos}2](OTf)4 have been prepared. The reduction potentials for the complexes [M{(R,R)-tetraphos}](PF6)2 increase in the order nickel(II) < palladium(II) < platinum(II). The reaction of (S,S)-tetraphos with bis(cycloocta-1,5-diene)nickel(0) in benzene affords orange [Ni{(R,R)-tetraphos}], which slowly rearranges into the thermodynamically more stable, yellow, double-stranded helicate [Ni2{(R,R)-tetraphos}2]; the crystal structures of both complexes have been determined. The reactions of (S,S)-tetraphos with [M(PPh3)4] in toluene (M = Pd) or benzene (M = Pt) furnish the double-stranded helicates [M2{(R,R)-tetraphos}2]; the palladium complex crystallizes from hot benzene as the 2-benzene solvate and was structurally characterized by X-ray crystallography. In each of the three zerovalent complexes, the coordinated (R,R)-tetraphos stereospecifically generates tetrahedral M(PP)2 stereocenters of M configuration.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khateeb, Siddique; Su, Dong; Guerreo, Sandra

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 cm 2) were assessed under various operating conditions. The core-shell catalyst showed consistently higher performance thanmore » commercial Pt/C 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

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

DOE PAGES

Khateeb, Siddique; Su, Dong; Guerreo, Sandra; ...

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 cm 2) were assessed under various operating conditions. The core-shell catalyst showed consistently higher performance thanmore » commercial Pt/C 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

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. Copyright © 2012 Elsevier B.V. All rights reserved.

Domestic Production Issues in Chromium and Platinum-Group Metals

DTIC Science & Technology

1988-09-01

iridium, and minor amounts of osmium. 12 Uses. Platinum-group metals (PGM) are critical as catalysts in fossil fuel processing and electronic...metals (PGM) were then described as critical in fossil fuel production, and in electronic and electrical components. The international market is...this research process . ii Table of Contents Page Preface.. .............. ii List of Figures ................ vi List of Tables ................ vi

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.

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.

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. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Gold and palladium adsorption from leached electronic scrap using ordered mesoporous carbon nanoscaffolds

DOE Office of Scientific and Technical Information (OSTI.GOV)

McDowell, Rocklan; Dutech, Guy

2014-09-01

Ordered mesoporous carbon (OMC) nanoscaffolds are engineered agglomerates of carbon nanotubes held together by small carbon nanofibers with uniform pore sizes, high pore volume, and high channel permeability. These materials exhibit very high affinity for the adsorption of gold from aqueous acidic mixtures. The efficiency of gold recovery is comparable to those typically accomplished using biopolymer-based adsorbents. The adsorption efficiency for other precious metals such as palladium and platinum is lower. Studies on the precious metal (Au, Pd) adsorption on OMC materials from actual liquors of leached electronics will be presented. Adsorption properties will be compared for several different sorbentsmore » used for the recovery of precious metals. The leach liquor compositions for three different types of electronic scrap materials (personal computer board, cell phone and tv input/output board) will be presented. The sorption efficiencies for Au, Pd, together with a spectrum of competing and non-competing metals, from such leach mixtures will be compared.« less

Synthesis, electronic structure, and reactivity of strained nickel-, palladium-, and platinum-bridged [1]ferrocenophanes.

PubMed

Matas, Inmaculada; Whittell, George R; Partridge, Benjamin M; Holland, Jason P; Haddow, Mairi F; Green, Jennifer C; Manners, Ian

2010-09-29

The group 10 bis(phosphine)metalla[1]ferrocenophanes, [{Fe(η(5)-C(5)H(4))(2)}M(Pn-Bu(3))(2)] [M = Ni (4a), Pd (4b), and Pt (4c)], have been prepared by the reaction of Li(2)[Fe(η(5)-C(5)H(4))(2)]·tmeda (5, tmeda = N,N,N',N'-tetramethylethylenediamine) with trans-[MCl(2)(Pn-Bu(3))(2)] [M = Ni (trans-6a) and Pd (trans-6b)] and cis-[PtCl(2)(Pn-Bu(3))(2)] (cis-6c), respectively. Single crystal X-ray diffraction revealed highly tilted, strained structures as characterized by α angles of 28.4° (4a), 24.5° (4b), and 25.2° (4c) and a distorted square planar environment for the group 10 metal center. UV/visible spectroscopy and cyclic voltammetry indicated that all three compounds had smaller HOMO-LUMO gaps and were more electron-rich in nature than ferrocene and other comparable [1]ferrocenophanes. DFT calculations suggested that these differences were principally due to the electron-releasing nature of the M(Pn-Bu(3))(2) metal-ligand fragments. Attempts to induce thermal or anionic ring-opening polymerization of 4a-c were unsuccessful and were complicated by, for example, competing ligand dissociation processes or unfavorable chain propagation. In contrast, these species all reacted rapidly with acids effecting clean extrusion of the bis(phosphine)metal fragment. Carbon monoxide inserted cleanly into one of the palladium-carbon bonds of 4b to afford the ring-expanded, acylated product [{Fe(η(5)-C(5)H(4))(η(5)-C(5)H(4))(CO)}Pd(Pn-Bu(3))(2)] (10). The nickel analogue 4a, however, afforded [Ni(CO)(2)(Pn-Bu(3))(2)] whereas the platinum-bridged complex 4c was inert. Remarkably, all compounds 4a-c were readily oxidized by elemental sulfur to afford the [5,5']bicyclopentadienylidene (pentafulvalene) complexes [{η(4):η(0)-C(5)H(4)(C(5)H(4))}M(Pn-Bu(3))(2)] [M = Ni (11a)] and [(η(2)-C(10)H(8))M(Pn-Bu(3))(2)] [M = Pd (11b) and Pt (11c)] by a formal 4-electron oxidation of the carbocyclic ligands. Compounds 11b and 11c represent the first examples of [5

Photobiomolecular metallic particles and films

DOEpatents

Hu, Zhong-Cheng

2003-05-06

The method of the invention is based on the unique electron-carrying function of a photocatalytic unit such as the photosynthesis system I (PSI) reaction center of the protein-chlorophyll complex isolated from chloroplasts. The method employs a photo-biomolecular metal deposition technique for precisely controlled nucleation and growth of metallic clusters/particles, e.g., platinum, palladium, and their alloys, etc., as well as for thin-film formation above the surface of a solid substrate. The photochemically mediated technique offers numerous advantages over traditional deposition methods including quantitative atom deposition control, high energy efficiency, and mild operating condition requirements.

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

Electro-architected porous platinum on metallic multijunction nanolayers to optimize their optical properties for infrared sensor application

NASA Astrophysics Data System (ADS)

Stanca, Sarmiza Elena; Hänschke, Frank; Zieger, Gabriel; Dellith, Jan; Dellith, Andrea; Ihring, Andreas; Belkner, Johannes; Meyer, Hans-Georg

2018-03-01

Tailoring the physicochemical properties of the metallic multijunction nanolayers is a prerequisite for the development of microelectronics. From this perspective, a desired lower reflectance of infrared radiation was achieved by an electrochemical deposition of porous platinum in nonaqueous media on silver mirror supported nickel-chrome and nickel-titanium metallic films with incremental decreasing thicknesses from 80-10 nm. The electro-assembled architectures were examined by means of scanning electron microscopy and Fourier transform infrared spectroscopy and it was observed that the layer and sublayer thicknesses and resistivities have a substantial effect upon the porous platinum morphology and its optical properties. It is here reported that the augmentation of the metallic layer electrical conductivity determines the electroformation of more compact platinum nanolayers. Moreover, the platinum black coating of metallic nanolayers causes a considerable decrease of the reflectance in the region from 1000-8000 cm-1.

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Secondary Precious Metals...

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.

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.

Maximum-valence radii of transition metals

PubMed Central

Pauling, Linus

1975-01-01

In many of their compounds the transition metals have covalence 9, forming nine bonds with use of nine hybrid spd bond orbitals. A set of maximum-valence single-bond radii is formulated for use in these compounds. These radii are in reasonably good agreement with observed bond lengths. Quadruple bonds between two transition metal atoms are about 50 pm (iron-group atoms) or 55 pm (palladium and platinum-group atoms) shorter than single bonds. This amount of shortening corresponds to four bent single bonds with the best set of bond angles, 79.24° and 128.8°. PMID:16578730

Processing precious metals in a top-blown rotary converter

NASA Astrophysics Data System (ADS)

Whellock, John G.; Matousek, Jan W.

1990-09-01

Copper-nickel/platinum-palladium flotation concentrates produced by the Stillwater Mining Company were smelted and refined in an integrated pilot plant consisting of a submerged-arc electric furnace and top-blown rotary converter. The conversion of high-iron electric furnace mattes was achieved with apparent oxygen efficiencies in excess of 100 percent. Platinum and palladium recoveries averaged 99 percent, and copper and nickel recoveries were 94 percent.

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

Photobiomolecular deposition of metallic particles and films

DOEpatents

Hu, Zhong-Cheng

2005-02-08

The method of the invention is based on the unique electron-carrying function of a photocatalytic unit such as the photosynthesis system I (PSI) reaction center of the protein-chlorophyll complex isolated from chloroplasts. The method employs a photo-biomolecular metal deposition technique for precisely controlled nucleation and growth of metallic clusters/particles, e.g., platinum, palladium, and their alloys, etc., as well as for thin-film formation above the surface of a solid substrate. The photochemically mediated technique offers numerous advantages over traditional deposition methods including quantitative atom deposition control, high energy efficiency, and mild operating condition requirements.

Exploring the palladium- and platinum-bis(pyridine) complex motif by NMR spectroscopy, X-ray crystallography, (tandem) mass spectrometry, and isothermal titration calorimetry: do substituent effects follow chemical intuition?

PubMed

Weilandt, Torsten; Löw, Nora L; Schnakenburg, Gregor; Daniels, Jörg; Nieger, Martin; Schalley, Christoph A; Lützen, Arne

2012-12-21

A series of ten palladium-bis(pyridine) complexes, as well as their corresponding platinum complexes, have been synthesized. The pyridine ligands in each series carried different σ-donor and/or π-acceptor/donor substituents at the para-position of their pyridine rings. These complexes were analysed by NMR spectroscopy, X-ray crystallography, (tandem) MS, and isothermal titration calorimetry (ITC) to validate whether these methods allowed us to obtain a concise and systematic picture of the relative and absolute thermodynamic stabilities of the complexes, as determined by the electronic effects of the substituents. Interestingly, the NMR spectroscopic data hardly correlated with the expected substituent effects but the heteronuclear platinum-phosphorus coupling constants did. Crystallographic data were found to be blurred by packing effects. Instead, tandem MS and ITC data were in line with each other and followed the expected trends. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of forming supported doped palladium containing oxidation catalysts

DOEpatents

Mohajeri, Nahid

2014-04-22

A method of forming a supported oxidation catalyst includes providing a support comprising a metal oxide or a metal salt, and depositing first palladium compound particles and second precious metal group (PMG) metal particles on the support while in a liquid phase including at least one solvent to form mixed metal comprising particles on the support. The PMG metal is not palladium. The mixed metal particles on the support are separated from the liquid phase to provide the supported oxidation catalyst.

Traceable Measurements of Seebeck Coefficients of Thermoelectric Materials by Using Noble Metal Thermocouples

NASA Astrophysics Data System (ADS)

Haupt, Sebastian; Edler, Frank

2018-06-01

The characterization of thermoelectric materials as reference materials for Seebeck coefficients at the Physikalisch-Technische Bundesanstalt (PTB) is based on the usage of gold/platinum differential thermocouples. In the case of thermoelectric materials containing silicon, the gold/platinum thermocouples are insufficient due to reactions with the silicon when the samples are at higher temperatures. To overcome this limitation and to expand the temperature range for the certification process, platinum/palladium thermocouples were incorporated in the measurement setup. This paper discusses the influence of the different differential thermocouples used for the measurement of the Seebeck coefficients. Results of a comparative investigation of Seebeck coefficient measurements of a metallic and two semiconducting reference materials in the temperature range from 300 K to 870 K are presented.

Ni-BaTiO3-Based Base-Metal Electrode (BME) Ceramic Capacitors for Space Applications

NASA Technical Reports Server (NTRS)

Liu, Donhang; Fetter, Lula; Meinhold, Bruce

2015-01-01

A multi-layer ceramic capacitor (MLCC) is a high-temperature (1350C typical) co-fired ceramic monolithic that is composed of many layers of alternately stacked oxide-based dielectric and internal metal electrodes. To make the dielectric layers insulating and the metal electrode layers conducting, only highly oxidation-resistant precious metals, such as platinum, palladium, and silver, can be used for the co-firing of insulating MLCCs in a regular air atmosphere. MLCCs made with precious metals as internal electrodes and terminations are called precious-metal electrode (PME) capacitors. Currently, all military and space-level applications only address the use of PME capacitors.

Concentrations of platinum group elements in 122 U.S. coal samples

USGS Publications Warehouse

Oman, C.L.; Finkelman, R.B.; Tewalt, S.J.

1997-01-01

Analysis of more than 13,000 coal samples by semi-quantitative optical emission spectroscopy (OES) indicates that concentrations of the platinum group elements (iridium, palladium, platinum, osmium, rhodium, and ruthenium) are less than 1 ppm in the ash, the limit of detection for this method of analysis. In order to accurately determine the concentration of the platinum group elements (PGE) in coal, additional data were obtained by inductively coupled plasma mass spectroscopy, an analytical method having part-per-billion (ppb) detection limits for these elements. These data indicate that the PGE in coal occur in concentrations on the order of 1 ppb or less.

Platinum, palladium, gold and ruthenium complexes as anticancer agents: Current clinical uses, cytotoxicity studies and future perspectives.

PubMed

Lazarević, Tatjana; Rilak, Ana; Bugarčić, Živadin D

2017-12-15

Metallodrugs offer potential for unique mechanism of drug action based on the choice of the metal, its oxidation state, the types and number of coordinated ligands and the coordination geometry. This review illustrates notable recent progress in the field of medicinal bioinorganic chemistry as many new approaches to the design of innovative metal-based anticancer drugs are emerging. Current research addressing the problems associated with platinum drugs has focused on other metal-based therapeutics that have different modes of action and on prodrug and targeting strategies in an effort to diminish the side-effects of cisplatin chemotherapy. Examples of metal compounds and chelating agents currently in clinical use, clinical trials or preclinical development are highlighted. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Biosorption of precious metals.

PubMed

Mack, C; Wilhelmi, B; Duncan, J R; Burgess, J E

2007-01-01

Biosorption has emerged as a low-cost and often low-tech option for removal or recovery of base metals from aqueous wastes. The conditions under which precious metals such as gold, platinum and palladium are sorbed by biomass are often very different to those under which base metals are sorbed. This, coupled with the increasingly high demand for precious metals, drives the increase in research into efficient recovery of precious metal ions from all waste material, especially refining wastewaters. Common biosorbents for precious metal ions include various derivatives of chitosan, as well as other compounds with relatively high surface amine functional group content. This is generally due to the ability of the positively charged amine groups to attract anionic precious metal ions at low pH. Recent research regarding the biosorption of some precious metals is reviewed here, with emphasis on the effects of the biosorption environment and the biosorption mechanisms identified.

High-pressure/high-temperature synthesis and characterization of the first palladium or platinum containing lithium transition-metal sulfides Li2M3S4 (M=Pd, Pt)

NASA Astrophysics Data System (ADS)

Heymann, Gunter; Niehaus, Oliver; Krüger, Hannes; Selter, Philipp; Brunklaus, Gunther; Pöttgen, Rainer

2016-10-01

The new lithium transition-metal sulfides Li2M3S4 (M=Pd, Pt) were obtained via multianvil high-pressure/high-temperature syntheses at 8 GPa and 1150 °C starting from a stoichiometric mixture of lithium nitride, sulfur, and palladium or platinum. Single crystal structure analyses indicated the space group P21/c (no. 14) with the following lattice parameters and refinement results: a=492.9(1), b=1005.9(2), c=614.9(2) pm, β=110.9 (1)°, R1=0.0165, wR2=0.0308 (all data) for Li2Pd3S4 and a=498.2(1), b=1005.5(2), c=613.0(2) pm, β=110.8(1)°, R1=0.0215, wR2=0.0450 (all data) for Li2Pt3S4. The crystal structures are built up from two distinct Pd/Pt sites, one of which is a special position (0,0,0), two sulfur sites, and one lithium site. The atoms Pd2/Pt2 form isolated square planar PdS4/PtS4 units, whereas the Pd1/Pt1 atoms form pairs of square planar PdS4/PtS4 units, which are connected via a common edge. These two structural motives built up a three-dimensional network structure by linking through common corners. The lithium atoms are positioned inside of the so formed channels. Li2M3S4 (M=Pd, Pt) are isostructural to the minerals jaguéite, Cu2Pd3Se4 and chrisstanleyite, Ag2Pd3Se4, which are up to now the only representatives of this structure type. Both compounds were studied with respect to their magnetic properties and can be classified as Pauli paramagnetic or diamagnetic. Regarding the possibility of lithium mobility inside the channels, of the structure, solid state 7Li NMR and high-temperature single crystal investigations revealed localization of the lithium atoms on their crystallographic sites.

Nanostructuring of Palladium with Low-Temperature Helium Plasma

PubMed Central

Fiflis, P.; Christenson, M.P.; Connolly, N.; Ruzic, D.N.

2015-01-01

Impingement of high fluxes of helium ions upon metals at elevated temperatures has given rise to the growth of nanostructured layers on the surface of several metals, such as tungsten and molybdenum. These nanostructured layers grow from the bulk material and have greatly increased surface area over that of a not nanostructured surface. They are also superior to deposited nanostructures due to a lack of worries over adhesion and differences in material properties. Several palladium samples of varying thickness were biased and exposed to a helium helicon plasma. The nanostructures were characterized as a function of the thickness of the palladium layer and of temperature. Bubbles of ~100 nm in diameter appear to be integral to the nanostructuring process. Nanostructured palladium is also shown to have better catalytic activity than not nanostructured palladium. PMID:28347109

Nanostructuring of Palladium with Low-Temperature Helium Plasma.

PubMed

Fiflis, P; Christenson, M P; Connolly, N; Ruzic, D N

2015-11-25

Impingement of high fluxes of helium ions upon metals at elevated temperatures has given rise to the growth of nanostructured layers on the surface of several metals, such as tungsten and molybdenum. These nanostructured layers grow from the bulk material and have greatly increased surface area over that of a not nanostructured surface. They are also superior to deposited nanostructures due to a lack of worries over adhesion and differences in material properties. Several palladium samples of varying thickness were biased and exposed to a helium helicon plasma. The nanostructures were characterized as a function of the thickness of the palladium layer and of temperature. Bubbles of ~100 nm in diameter appear to be integral to the nanostructuring process. Nanostructured palladium is also shown to have better catalytic activity than not nanostructured palladium.

Geological structure and prospects of noble metal ore mineralization of the Khayrkhan gabbroid massif (Western Mongolia)

NASA Astrophysics Data System (ADS)

Kurumshieva, K. R.; Gertner, I. F.; Tishin, P. A.

2017-12-01

An analysis of the distribution of noble metals in zones of sulfide mineralization makes it possible to justify the isolation of four ore-bearing horizons with a specific geochemical zonation. A rise in the gold content relative to palladium and platinum is observed from the bottom upwards along the section of the stratified series of gabbroids. The study of the mineral phases of sulphides and the noble minerals itself indicates the evolution of hydrothermal solutions, which determines the different activity and mobility of the fluid (mercury, tellurium, sulfur) and ore (copper, nickel, iron, platinum, gold and silver) components.

Low platinum catalyst and method of preparation

DOEpatents

Liu, Di-Jia; Chong, Lina

2017-11-21

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

Effects of soldering methods on tensile strength of a gold-palladium metal ceramic alloy.

PubMed

Ghadhanfari, Husain A; Khajah, Hasan M; Monaco, Edward A; Kim, Hyeongil

2014-10-01

The tensile strength obtained by conventional postceramic application soldering and laser postceramic welding may require more energy than microwave postceramic soldering, which could provide similar tensile strength values. The purpose of the study was to compare the tensile strength obtained by microwave postceramic soldering, conventional postceramic soldering, and laser postceramic welding. A gold-palladium metal ceramic alloy and gold-based solder were used in this study. Twenty-seven wax specimens were cast in gold-palladium noble metal and divided into 4 groups: laser welding with a specific postfiller noble metal, microwave soldering with a postceramic solder, conventional soldering with the same postceramic solder used in the microwave soldering group, and a nonsectioned control group. All the specimens were heat treated to simulate a normal porcelain sintering sequence. An Instron Universal Testing Machine was used to measure the tensile strength for the 4 groups. The means were analyzed statistically with 1-way ANOVA. The surface and fracture sites of the specimens were subjectively evaluated for fracture type and porosities by using a scanning electron microscope. The mean (standard deviation) ultimate tensile strength values were as follows: nonsectioned control 818 ±30 MPa, microwave 516 ±34 MPa, conventional 454 ±37 MPa, and laser weld 191 ±39 MPa. A 1-way ANOVA showed a significant difference in ultimate tensile strength among the groups (F3,23=334.5; P<.001). Follow-up multiple comparisons showed a significant difference among all the groups. Microwave soldering resulted in a higher tensile strength for gold and palladium noble metals than either conventional soldering or laser welding. Conventional soldering resulted in a higher tensile strength than laser welding. Under the experimental conditions described, either microwave or conventional postceramic soldering would appear to satisfy clinical requirements related to tensile strength

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…

Palladium and platinum based solid and hollow nanoparticles: An ab-initio study of structural and electronic properties

NASA Astrophysics Data System (ADS)

Yildizhan, Gulsum; Caliskan, Serkan; Ozturk, Ramazan

2018-04-01

Nanoparticles composed of palladium and platinum are particularly interesting for catalytic purposes, for instance, selective hydrogenation and alcohol oxidation. The reactivity and selectivity of nanostructures are mostly based on the size and shape of the nanocrystals in catalytic reactions. In this work, we studied the structural stabilities of Pd and Pt based nanocubes and nanocages and adsorption strength of chemisorbed species on these nanostructures to investigate their structure dependent catalytic activities. Solid cubic and hollow cage like nanostructures of different sizes were designed with Pd and Pt atoms. The volume of the crystal cavity in nanocage structures was tuned by removing of atoms from solid cubic structure. The effect of size and shape on the formation energies and HOMO-LUMO energy gap of nanostructures were elucidated and correlated to structural stabilities, hardness-softness, electronegativity and electrophilicity index. The relationship between size and chemical reactivity clearly showed that increasing the number of atoms participating in a catalyst enhances the activity. For further understanding of the catalytic activity we employed 4-nitro thiophenol, as an S-donor representative molecule, to evaluate the adsorption characteristics of the nanostructures.

Biomonitoring of traffic police officers exposed to airborne platinum

PubMed Central

Iavicoli, I; Bocca, B; Petrucci, F; Senofonte, O; Carelli, G; Alimonti, A; Caroli, S

2004-01-01

Background: Over the past two decades there has been a substantial increase in environmental levels of palladium, platinum, and rhodium, the platinum group elements (PGEs), due to the widespread use of catalytic converters for automotive traction. Aim: To evaluate urinary platinum levels in occupationally exposed subjects. Methods: A total of 161 employees from the Rome City Police Force were studied; 103 were traffic police involved in controlling streets with an average flow of vehicles, while the remaining 58 were control subjects engaged only in office work. Platinum quantification in the urine samples of these subjects was carried out by sector field inductively coupled plasma mass spectrometry. Results: There were no statistically significant differences between platinum levels in the group of subjects engaged in traffic control and the control group (4.45 (2.42) ng/l v 4.56 (2.84) ng/l, respectively). Conclusions: Urinary levels were found to be higher than those reported for other urban populations, thus showing a progressive increase in human exposure to Pt. PMID:15208381

Vapor deposition of thin films

DOEpatents

Smith, David C.; Pattillo, Stevan G.; Laia, Jr., Joseph R.; Sattelberger, Alfred P.

1992-01-01

A highly pure thin metal film having a nanocrystalline structure and a process of preparing such highly pure thin metal films of, e.g., rhodium, iridium, molybdenum, tungsten, rhenium, platinum, or palladium by plasma assisted chemical vapor deposition of, e.g., rhodium(allyl).sub.3, iridium(allyl).sub.3, molybdenum(allyl).sub.4, tungsten(allyl).sub.4, rhenium(allyl).sub.4, platinum(allyl).sub.2, or palladium(allyl).sub.2 are disclosed. Additionally, a general process of reducing the carbon content of a metallic film prepared from one or more organometallic precursor compounds by plasma assisted chemical vapor deposition is disclosed.

Request for Correction 11001 Toxicological Review of Halogenated Platinum Salts and Platinum Compounds

EPA Pesticide Factsheets

Request for Correction by the International Platinum Group Metals Association seeking the correction of information disseminated in the draft EPA document Toxicological Review of Halogenated Platinum Salts and Platinum Compounds: In Support of Summary Information on the Integrated Risk Information System (IRIS).

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

NASA Astrophysics Data System (ADS)

Maksoed, Wh-

2016-11-01

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

Thermally Deposited Palladium-Tungsten Carbide and Platinum-Tungsten Carbide Counter Electrodes for a High Performance Dye-Sensitized Solar Cell Based on Organic T-/T₂ Electrolyte.

PubMed

Towannang, Madsakorn; Thiangkaew, Anongnad; Maiaugree, Wasan; Ratchaphonsaenwong, Kunthaya; Jarernboon, Wirat; Pimanpang, Samuk; Amornkitbamrung, Vittaya

2018-02-01

Tungsten carbide (WC) particles (~1 μm) were dispersed in DI water and dropped onto conductive glass. The resulting WC films were used as dye-sensitized solar cell (DSSC) counter electrodes. The performance of the WC DSSC based on the organic thiolate/disulfide (T-/T2) electrolyte was ~0.78%. The cell efficiency was greatly improved after decorating palladium (Pd) or platinum (Pt) nanoparticles on WC particles with a promising efficiency of ~2.15% for Pd-WC DSSC and ~4.62% for Pt-WC DSSC. The efficiency improvement of the composited (Pd-WC and Pt-WC) cells is attributed to co-functioning catalysts, the large electrode interfacial area and a low charge-transfer resistance at the electrolyte/counter electrode interface.

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

PubMed

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

2014-01-01

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

Ceramic-metal composite article and joining method

DOEpatents

Kang, Shinhoo; Selverian, John H.; Kim, Hans J.; Dunn, Edmund M.; Kim, Kyung S.

1992-01-01

A ceramic-metal article including a ceramic rod, a metal rod, and a braze joining the ceramic and metal rods at a braze area of a coaxial bore in the metal rod. The bore gradually decreases in diameter, having an inward seat area sized for close sliding fit about the ceramic, a larger brazing area near the joint end, and a void area intermediate the braze and seat areas. The ceramic is seated without brazing in the bore seat area. The side wall between the brazing area and the metal outer surface is about 0.030-0.080 inch. The braze includes an inner braze layer, an outer braze layer, and an interlayer about 0.030-0.090 inch thick. A shoulder between the brazing and void areas supports the interlayer during bonding while preventing bonding between the void area and the ceramic member, leaving a void space between the void area and the ceramic member. A venting orifice extends generally radially through the metal member from the outer surface to the void space. The braze layers are palladium, platinum, gold, silver, copper, nickel, indium, chromium, molybdenum, niobium, iron, aluminum, or alloys thereof. Preferred is a gold-palladium-nickel brazing alloy. The interlayer is nickel, molybdenum, copper, tantalum, tungsten, niobium, aluminum, cobalt, iron, or an alloy thereof.

Ceramic-metal composite article and joining method

DOEpatents

Kang, S.; Selverian, J.H.; Kim, H.J.; Dunn, E.M.; Kim, K.S.

1992-04-28

A ceramic-metal article including a ceramic rod, a metal rod, and a braze joining the ceramic and metal rods at a braze area of a coaxial bore in the metal rod is described. The bore gradually decreases in diameter, having an inward seat area sized for close sliding fit about the ceramic, a larger brazing area near the joint end, and a void area intermediate the braze and seat areas. The ceramic is seated without brazing in the bore seat area. The side wall between the brazing area and the metal outer surface is about 0.030-0.080 inch. The braze includes an inner braze layer, an outer braze layer, and an interlayer about 0.030-0.090 inch thick. A shoulder between the brazing and void areas supports the interlayer during bonding while preventing bonding between the void area and the ceramic member, leaving a void space between the void area and the ceramic member. A venting orifice extends generally radially through the metal member from the outer surface to the void space. The braze layers are palladium, platinum, gold, silver, copper, nickel, indium, chromium, molybdenum, niobium, iron, aluminum, or alloys thereof. Preferred is a gold-palladium-nickel brazing alloy. The interlayer is nickel, molybdenum, copper, tantalum, tungsten, niobium, aluminum, cobalt, iron, or an alloy thereof. 4 figs.

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Hochmuth, J.; Pagliaro, P.

1981-01-01

A number of electrocatalyst combinations were prepared and characterized. These electrocatalysts were formulated to contain platinum combined with transition metal carbide forming elements (W, Mo, V) for cathodes and platinum combined with palladium for anodes. High resolution electron microscopy was used to determine the crystallite size and dispersion of platinum-palladium alloy electrocatalysts in order to provide analytical support for the electrochemical determinations of the particle dispersions. An equation was derived which correlates palladium crystallite size with electrochemical hydrogen adsorption. Based on comparisons of electrocatalyst performances in the presence of pure hydrogen and hydrogen containing carbon monoxide, it was shown that the apparent poisoning of the electrocatalyst by carbon monoxide is influenced by the electrode structure.

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

2015-10-07

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.

Palladium coated porous anodic alumina membranes for gas reforming processes

NASA Astrophysics Data System (ADS)

Wu, Jeremy P.; Brown, Ian W. M.; Bowden, Mark E.; Kemmitt, Timothy

2010-11-01

Nanostructured ceramic membranes with ultrathin coatings of palladium metal have been demonstrated to separate hydrogen gas from a gas mixture containing nitrogen with 10% carbon dioxide and 10% hydrogen at temperatures up to 550 °C. The mechanically robust and thermally durable membranes were fabricated using a combination of conventional and high-efficiency anodisation processes on high purity aluminium foils. A pH-neutral plating solution has also been developed to enable electroless deposition of palladium metal on templates which were normally prone to chemical corrosion in strong acid or base environment. Activation and thus seeding of palladium nuclei on the surface of the template were essential to ensure uniform and fast deposition, and the thickness of the metal film was controlled by time of deposition. The palladium coated membranes showed improved hydrogen selectivity with increased temperature as well as after prolonged exposure to hydrogen, demonstrating excellent potential for gas separation technologies.

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.

Method for forming porous platinum films

DOEpatents

Maya, Leon

2000-01-01

A method for forming a platinum film includes providing a substrate, sputtering a crystalline platinum oxide layer over at least a portion of the substrate, and reducing the crystalline platinum oxide layer to form the platinum film. A device includes a non-conductive substrate and a platinum layer having a density of between about 2 and 5 g/cm.sup.3 formed over at least a portion of the non-conductive substrate. The platinum films produced in accordance with the present invention provide porous films suitable for use as electrodes, yet require few processing steps. Thus, such films are less costly. Such films may be formed on both conductive and non-conductive substrates. While the invention has been illustrated with platinum, other metals, such as noble metals, that form a low density oxide when reactively sputtered may also be used.

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

DOE PAGES

St. John, Samuel; Atkinson, Robert W.; Unocic, Kinga A.; ...

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 Ru 0.90Pt 0.10 display a surface-specific activity (2.4 mA/cm 2) 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/cm 2). The surface-segregated structure also confers dramatically increased Pt utilization efficiency. We find a platinum-mass-specificmore » 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.« less

l-Glutamic acid assisted eco-friendly one-pot synthesis of sheet-assembled platinum-palladium alloy networks for methanol oxidation and oxygen reduction reactions.

PubMed

Shi, Ya-Cheng; Mei, Li-Ping; Wang, Ai-Jun; Yuan, Tao; Chen, Sai-Sai; Feng, Jiu-Ju

2017-10-15

In this work, bimetallic platinum-palladium sheet-assembled alloy networks (PtPd SAANs) were facilely synthesized by an eco-friendly one-pot aqueous approach under the guidance of l-glutamic acid at room temperature, without any additive, seed, toxic or organic solvent involved. l-Glutamic acid was served as the green shape-director and weak-stabilizing agent. A series of characterization techniques were employed to examine the morphology, structure and formation mechanism of the product. The architectures exhibited improved electrocatalytic activity and durable ability toward methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in contrast with commercial Pt black and Pd black catalysts. This is ascribed to the unique structures of the obtained PtPd SAANs and the synergistic effects of the bimetals. These results demonstrate the potential application of the prepared catalyst in fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Separation of metallic residues from the dissolution of a high-burnup BWR fuel using nitrogen trifluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

McNamara, Bruce K.; Buck, Edgar C.; Soderquist, Chuck Z.

2014-03-23

Nitrogen trifluoride (NF 3) was used to fluorinate the metallic residue from the dissolution of a high burnup, boiling water reactor fuel (~70 MWd/kgU). The metallic residue included the noble metal phase (containing ruthenium, rhodium, palladium, technetium, and molybdenum), and smaller amounts of zirconium, selenium, tellurium, and silver. Exposing the noble metal phase to 10% NF 3 in argon between 400 and 550°C, removed molybdenum and technetium near 400°C as their volatile fluorides, and ruthenium near 500C as its volatile fluoride. The events were thermally and temporally distinct and the conditions specified are a recipe to separate these transition metalsmore » from each other and from the noble metal phase nonvolatile residue. Depletion of the volatile fluorides resulted in substantial exothermicity. Thermal excursion behavior was recorded under non-adiabatic, isothermal conditions that typically minimize heat release. Physical characterization of the metallic noble phase and its thermal behavior are consistent with high kinetic velocity reactions encouraged by the nanoparticulate phase or perhaps catalytic influences of the mixed platinum metals with nearly pure phase structure. Post-fluorination, only two phases were present in the residual nonvolatile fraction. These were identified as a nano-crystalline, metallic palladium cubic phase and a hexagonal rhodium trifluoride (RhF 3) phase. The two phases were distinct as the sub-µm crystallites of metallic palladium were in contrast to the RhF 3 phase, which grew from the parent nano-crystalline noble-metal phase during fluorination, to acicular crystals exceeding 20-µm in length.« less

Preparation of metal/zeolite catalysts: Formation of palladium aquocomplexes in the precursor of palladium-mordenite catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1993-09-01

Previous research has revealed that the catalytic performance of metal/zeolite catalysts can be significantly modified by exposing the catalyst precursor to H[sub 2]O vapor during the period after calcination, but before reduction. For bimetallic PdCo/NaY catalysts used for CO hydrogenation, the selectivity was changed from predominant production of oxygenates to predominant production of higher hydrocarbons. For Pt/H-mordenite catalysts, this water treatment has been reported to improve the alkane isomerization activity. Although it is certain that Lewis sites are transformed to Bronsted sites by reaction with H[sub 2]O, the activity of the catalyst is affected most when the water is addedmore » after calcination, when the noble metal is present as ligand-free ions. This observation led to the hypothesis that complexation of transition metal ions with water might be instrumental for the observed effects. In zeolites containing cages, such as Y, the formation of metal-ligand complex ions appears to incite their migration from small to large cages. In cageless zeolites such as mordenite, however, it is not clear, a priori, whether hydration of transition metal ions will increase or decrease their reducibility and whether it will ultimately result in higher or lower metal dispersion. The authors have therefore undertaken research to clarify these issues. Palladium supported in H-mordenite (Pd/HMor) or Na-mordenite (Pd/Na-Mor) has been tested using methylcyclopentane as a probe reaction; temperature-programmed reduction (TPR), desorption (TPD), and extended X-ray absorption fine structure (EXAFS) spectroscopy have been used to characterize the effects of water treatment on the samples.« less

Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian

2012-05-04

A new type of electrocatalyst with a core–shell structure that consists of a platinum monolayer shell placed on an iridium–rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium–rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of Pt ML/Pd ML/Ir 2Re 1,more » Pt ML/Pd 2layers/Ir 2Re 1, and Pt ML/Pd 2layers/Ir 7Re 3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O 2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. Finally, the results with the Pt ML/Pd ML/Ir 2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.« less

Platinum-group elements: so many excellent properties

USGS Publications Warehouse

Zientek, Michael L.; Loferski, Patricia J.

2014-01-01

The platinum-group elements (PGE) include platinum, palladium, rhodium, ruthenium, iridium, and osmium. These metals have similar physical and chemical properties and occur together in nature. The properties of PGE, such as high melting points, corrosion resistance, and catalytic qualities, make them indispensable to many industrial applications. PGE are strategic and critical materials for many nations because they are essential for important industrial applications but are mined in a limited number of places and have no adequate substitutes. Exploration and mining companies have found approximately 104,000 metric tons of PGE (with minor gold) in mineral deposits around the world that could be developed. For PGE, almost all known production and resources are associated with three geologic features: the Bushveld Complex, a layered mafic-to-ultramafic intrusion in South Africa; the Great Dyke, a layered mafic-to-ultramafic intrusion in Zimbabwe; and sill-like intrusions associated with flood basalts in the Noril’sk-Talnakh area, Russia. To help predict where PGE supplies might be located, USGS scientists study how and where PGE resources are concentrated in the Earth's crust and use that knowledge to assess the likelihood that undiscovered PGE deposits may exist. Techniques used for assessing mineral resources were developed by the USGS to support the stewardship of Federal lands and evaluate mineral resource availability in a global context. The USGS also compiles statistics and information on the worldwide supply, demand, and flow of PGE. These data are all used to inform U.S. national policymakers.

Graphenes in the absence of metals as carbocatalysts for selective acetylene hydrogenation and alkene hydrogenation

NASA Astrophysics Data System (ADS)

Primo, Ana; Neatu, Florentina; Florea, Mihaela; Parvulescu, Vasile; Garcia, Hermenegildo

2014-10-01

Catalysis makes possible a chemical reaction by increasing the transformation rate. Hydrogenation of carbon-carbon multiple bonds is one of the most important examples of catalytic reactions. Currently, this type of reaction is carried out in petrochemistry at very large scale, using noble metals such as platinum and palladium or first row transition metals such as nickel. Catalysis is dominated by metals and in many cases by precious ones. Here we report that graphene (a single layer of one-atom-thick carbon atoms) can replace metals for hydrogenation of carbon-carbon multiple bonds. Besides alkene hydrogenation, we have shown that graphenes also exhibit high selectivity for the hydrogenation of acetylene in the presence of a large excess of ethylene.

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

Correlation between the Knight shift of chemisorbed CO and the Fermi level local density of states at clean platinum catalyst surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tong, Y.Y.; Rice, C.; Godbout, N.

1999-04-07

Due to its fundamental importance in heterogeneous catalysis, as well as in electrocatalysis, the chemisorption and reaction of CO on transition metal surfaces has been an important focus of modern surface science. Here, the NMR spectroscopy of {sup 13}CO adsorbed onto transition metal surfaces has been shown to be a very powerful probe of molecular structure and dynamics of CO itself, as well as a probe of the electronic properties of the transition metal surfaces onto which it is adsorbed. The authors have investigated the {sup 195}Pt and {sup 13}C nuclear magnetic resonance (NMR) spectroscopy of clean-surface platinum catalysts andmore » of CO chemisorbed onto Pt catalysts surfaces. They use Knight shift, relaxation, and J-coupling data to deduce information about the Fermi level local density of states (E{sub f}-LDOS) at catalyst surfaces. There is a linear correlation between the Knight shifts of chemisorbed CO and the clean surface E{sub f}-LDOS of platinum onto which the CO is bound, as determined by {sup 13}C and {sup 195}Pt NMR. The correlation amounts to {approximately} 12 ppm/Ry{sup {minus}1} {center_dot} atom{sup {minus}1}, the same as that which can be deduced for CO on palladium, as well as from the electrode potential dependence of {sup 13}C Knight shifts and infrared vibrational frequencies, {nu}{sub CO}, and the relationship between {nu}{sub CO} and the E{sub f}-LDOS at clean platinum surfaces. The ability to now directly relate meal and adsorbate electronic properties opens up new avenues for investigating metal-ligand interactions in heterogeneous catalysis and electrocatalysis.« less

Freestanding palladium nanosheets with plasmonic and catalytic properties

NASA Astrophysics Data System (ADS)

Huang, Xiaoqing; Tang, Shaoheng; Mu, Xiaoliang; Dai, Yan; Chen, Guangxu; Zhou, Zhiyou; Ruan, Fangxiong; Yang, Zhilin; Zheng, Nanfeng

2011-01-01

Ultrathin metal films can exhibit quantum size and surface effects that give rise to unique physical and chemical properties. Metal films containing just a few layers of atoms can be fabricated on substrates using deposition techniques, but the production of freestanding ultrathin structures remains a significant challenge. Here we report the facile synthesis of freestanding hexagonal palladium nanosheets that are less than 10 atomic layers thick, using carbon monoxide as a surface confining agent. The as-prepared nanosheets are blue in colour and exhibit a well-defined but tunable surface plasmon resonance peak in the near-infrared region. The combination of photothermal stability and biocompatibility makes palladium nanosheets promising candidates for photothermal therapy. The nanosheets also exhibit electrocatalytic activity for the oxidation of formic acid that is 2.5 times greater than that of commercial palladium black catalyst.

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

PubMed

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

2012-06-01

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

Evaluation of cytotoxicity of new trans-palladium(II) complex in human cells in vitro.

PubMed

Kontek, Renata; Matławska-Wasowska, Ksenia; Kalinowska-Lis, Urszula; Kontek, Bogdan; Ochocki, Justyn

2011-01-01

Studies of cytotoxicity allow to elucidate the mechanisms by which chemical compounds influence cells and tissues. On the basis of the structural analogy between platinum(II) and palladium(II) complexes, a variety of studies on palladium(II) compounds as potential anticancer drugs have been carried out (1, 2). The cytotoxicity was evaluated by MTT assay. Abilities of trans-palladium(II) complex containing diethyl (pyridin-2-ylmethyl)phosphates as non-leaving ligands (trans-[PdCl2(2-pmOpe 2)]) to induce apoptosis and necrosis in normal lymphocytes, A549 cells and HT29 cell lines were performed by use of fluorochrome staining. The obtained results revealed, that the new trans-palladium(II) complex was more cytotoxic against A549 and HT29 tumor cells than on the normal lymphocytes in vitro. The novel complex induces apoptosis in all tested cells, but in lymphocytes to a lesser degree. The compound tested also induced significant amounts of necrotic cells, which exceeded the level of apoptotic cell fractions. The results demonstrate that the trans-Pd(II) complex showed substantial cytotoxic activity against A549 and HT29 tumor cells and indicate that the new trans-palladium(II) complex effectively inhibited cancer cells growth.

Transition metal sensing by Toll-like receptor-4: next to nickel, cobalt and palladium are potent human dendritic cell stimulators.

PubMed

Rachmawati, Dessy; Bontkes, Hetty J; Verstege, Marleen I; Muris, Joris; von Blomberg, B Mary E; Scheper, Rik J; van Hoogstraten, Ingrid M W

2013-06-01

Nickel was recently identified as a potent activator of dendritic cells through ligating with human Toll-like receptor (TLR)-4. Here, we studied an extended panel of transition metals neighbouring nickel in the periodic table of elements, for their capacity to activate human monocyte-derived dendritic cells (MoDCs). The panel included chromium, cobalt, and palladium, all of which are known to be frequent clinical sensitizers. MoDC activation was monitored by assessment of release of the pro-inflammatory mediator interleukin (IL)-8, a major downstream result of TLR ligation. Results The data obtained in the present study show that cobalt and palladium also have potent MoDC-activating capacities, whereas copper and zinc, but not iron and chromium, have low but distinct MoDC-activating potential. Involvement of endotoxin contamination in MoDC activation was excluded by Limulus assays and consistent stimulation in the presence of polymyxin B. The critical role of TLR4 in nickel-induced, cobalt-induced and palladium-induced activation was confirmed by essentially similar stimulatory patterns obtained in an HEK293 TLR4/MD2 transfectant cell line. Given the adjuvant role of costimulatory danger signals, the development of contact allergies to the stimulatory metals may be facilitated by signals from direct TLR4 ligation, whereas other metal sensitizers, such as chromium, may rather depend on microbial or tissue-derived cofactors to induce clinical sensitization. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

In-situ surface science studies of the interaction between sulfur dioxide and two-dimensional palladium loaded-cerium/zirconium mixed metal oxide model catalysts

NASA Astrophysics Data System (ADS)

Romano, Esteban Javier

2005-07-01

Cerium and zirconium oxides are important materials in industrial catalysis. Particularly, the great advances attained in the past 30 years in controlling levels of gaseous pollutants released from internal combustion engines can be attributed to the development of catalysts employing these materials. Unfortunately, oxides of sulfur are known threats to the longevity of many catalytic systems by irreversibly interacting with catalytic materials. In this work, polycrystalline cerium-zirconium mixed-metal-oxide (MMO) solid solutions were synthesized. High resolution x-ray photoelectron spectroscopy (XPS) spectral data was collected and examined for revelation of the surface species that form on these metal oxides after in-situ exposures to sulfur dioxide. The model catalysts were exposed to sulfur dioxide using a custom modified in-situ reaction cell and platen heater. The results of this study demonstrate the formation of sulfate and sulfite surface sulfur species. Temperature and compositional dependencies were displayed, with higher temperatures and ceria molar ratios displaying a larger propensity for forming surface sulfur species. In addition to analysis of sulfur photoemission, the photoemission regions of oxygen, zirconium, and cerium were examined for the materials used in this study before and after the aforementioned treatments with sulfur dioxide. The presence of surface hydroxyl groups was observed and metal oxidation state changes were probed to further enhance the understanding of sulfur dioxide adsorption on the synthesized materials. Palladium loaded mixed-metal oxides were synthesized using a unique solid-state methodology to probe the effect of palladium addition on sulfur dioxide adsorption. The addition of palladium to this model system is shown to have a strong effect on the magnitude of adsorption for sulfur dioxide on some material/exposure condition combinations. Ceria/zirconia sulfite and sulfate species are identified on the palladium

Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential.

PubMed

Wang, Jun; Yu, Liang; Hu, Lin; Chen, Gang; Xin, Hongliang; Feng, Xiaofeng

2018-05-15

Electrochemical reduction of N 2 to NH 3 provides an alternative to the Haber-Bosch process for sustainable, distributed production of NH 3 when powered by renewable electricity. However, the development of such process has been impeded by the lack of efficient electrocatalysts for N 2 reduction. Here we report efficient electroreduction of N 2 to NH 3 on palladium nanoparticles in phosphate buffer solution under ambient conditions, which exhibits high activity and selectivity with an NH 3 yield rate of ~4.5 μg mg -1 Pd h -1 and a Faradaic efficiency of 8.2% at 0.1 V vs. the reversible hydrogen electrode (corresponding to a low overpotential of 56 mV), outperforming other catalysts including gold and platinum. Density functional theory calculations suggest that the unique activity of palladium originates from its balanced hydrogen evolution activity and the Grotthuss-like hydride transfer mechanism on α-palladium hydride that lowers the free energy barrier of N 2 hydrogenation to *N 2 H, the rate-limiting step for NH 3 electrosynthesis.

Comparison of the metal-to-ceramic bond strengths of four noble alloys with press-on-metal and conventional porcelain layering techniques.

PubMed

Khmaj, Mofida R; Khmaj, Abdulfatah B; Brantley, William A; Johnston, William M; Dasgupta, Tridib

2014-11-01

New noble alloys for metal ceramic restorations introduced by manufacturers are generally lower-cost alternatives to traditional higher-gold alloys. Information about the metal-to-ceramic bond strength for these alloys, which is needed for rational clinical selection, is often lacking. The purpose of this study was to evaluate the bond strength of 4 recently introduced noble alloys by using 2 techniques for porcelain application. Aquarius Hard (high-gold: 86.1 gold, 8.5 platinum, 2.6 palladium, 1.4 indium; values in wt. %), Evolution Lite (reduced-gold: 40.3 gold, 39.3 palladium, 9.3 indium, 9.2 silver, 1.8 gallium), Callisto 75 Pd (palladium-silver containing gold: 75.2 palladium, 7.1 silver, 2.5 gold, 9.3 tin, 1.0 indium), and Aries, (conventional palladium-silver: 63.7 palladium, 26.0 silver, 7.0 tin, 1.8 gallium, 1.5 indium) were selected for bonding to leucite-containing veneering porcelains. Ten metal ceramic specimens that met dimensional requirements for International Organization for Standardization (ISO) Standard 9693 were prepared for each alloy by using conventional porcelain layering and press-on-metal methods. The 3-point bending test in ISO Standard 9693 was used to determine bond strength. Values were compared with 2-way ANOVA (maximum likelihood analysis, SAS Mixed Procedure) and the Tukey test (α=.05). Means (standard deviations) for bond strength with conventional porcelain layering were as follows: Aquarius Hard (50.7 ±5.5 MPa), Evolution Lite (40.2 ±3.3 MPa), Callisto 75 Pd (37.2 ±3.9 MPa), and Aries (34.0 ±4.9 MPa). For the press-on-metal technique, bond strength results were as follows: Aquarius Hard (33.7 ±11.5 MPa), Evolution Lite (34.9 ±4.5 MPa), Callisto 75 Pd (37.2 ±11.9 MPa), and Aries (30.7 ±10.8 MPa). From statistical analyses, the following 3 significant differences were found for metal-to-ceramic bond strength: the bond strength for Aquarius Hard was significantly higher for conventional porcelain layers compared with

Organometallic Palladium Reagents for Cysteine Bioconjugation

PubMed Central

Vinogradova, Ekaterina V.; Zhang, Chi; Spokoyny, Alexander M.; Pentelute, Bradley L.; Buchwald, Stephen L.

2015-01-01

Transition-metal based reactions have found wide use in organic synthesis and are used frequently to functionalize small molecules.1,2 However, there are very few reports of using transition-metal based reactions to modify complex biomolecules3,4, which is due to the need for stringent reaction conditions (for example, aqueous media, low temperature, and mild pH) and the existence of multiple, reactive functional groups found in biopolymers. Here we report that palladium(II) complexes can be used for efficient and highly selective cysteine conjugation reactions. The bioconjugation reaction is rapid and robust under a range of biocompatible reaction conditions. The straightforward synthesis of the palladium reagents from diverse and easily accessible aryl halide and trifluoromethanesulfonate precursors makes the method highly practical, providing access to a large structural space for protein modification. The resulting aryl bioconjugates are stable towards acids, bases, oxidants, and external thiol nucleophiles. The broad utility of the new bioconjugation platform was further corroborated by the synthesis of new classes of stapled peptides and antibody-drug conjugates. These palladium complexes show potential as a new set of benchtop reagents for diverse bioconjugation applications. PMID:26511579

Metal oxide nanorod arrays on monolithic substrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

Greenland snow evidence of large scale atmospheric contamination for platinum, palladium, and rhodium.

PubMed

Barbante, C; Veysseyre, A; Ferrari, C; van de Velde, K; Morel, C; Capodaglio, G; Cescon, P; Scarponi, G; Boutron, C

2001-03-01

Since 1976 in the United States, Canada, and Japan, and later in other countries, the exhaust system of gasoline powered cars has been equipped with catalytic converters containing Pt and/or Pd and/or Rh. This has resulted in a very significant decrease in urban air pollution for various chemical species such as NOx, CO, and hydrocarbons. There has however been concern that their ever increasing use might lead to Platinum Group Metals (PGMs) becoming widely dispersed in the environment. From the analysis of Pt, Pd, and Rh in central Greenland recent snow and ancient ice using the ultrasensitive inductively coupled plasma sector field mass spectrometry technique, we show here that the concentrations of these metals in snow dated from the mid 1990s are indeed approximately 40-120 times higher than in ice dated from 7000 years ago. The fact that such an increase is observed far away from populated areas at a high altitude location indicates there is now a large scale contamination of the troposphere of the Northern Hemisphere for PGMs. Pt/Rh mass ratio in the most recent snow samples is close to the same ratio documented for catalytic converter exhausts in a recent study, which suggests that a large fraction of the recent increase for Pt and Rh might originate from automobile catalytic converters.

Synthesis and properties of a novel catalyst for the combustion of methane. Final report, January 1986-December 1989

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hicks, R.F.

1990-10-17

The objective of the research, which was funded by the Physical Sciences Department of the Gas Research Institute, was to understand how to design precious metal catalysts for methane combustion. These catalyst must be stable in the combustion environment and exhibit high rates of oxidation. The authors have found that palladium on alumina does not lose active surface area in air below 900C. Whereas, platinum vaporizes above 600C. The rate of methane oxidation per exposed metal atom depends on the metal used, platinum or palladium, and whether the metal is completely oxidized or covered with adsorbed oxygen during reaction. Themore » percentage of metal oxidized depends on the size, morphology and crystallinity of the metal particles. The relative rates of methane oxidation are: dispersed PtO2: dispersed PdO: crystalline Pt: crystalline Pd = 1:6:16:100.« less

Palladium-metalated porous organic polymers as recyclable catalysts for chemoselective decarbonylation of aldehydes.

PubMed

Li, Wen-Hao; Li, Cun-Yao; Li, Yan; Tang, Hai-Tao; Wang, Heng-Shan; Pan, Ying-Ming; Ding, Yun-Jie

2018-06-07

A novel palladium nanoparticle (NP)-metalated porous organic ligand (Pd NPs/POL-xantphos) has been prepared for the chemoselective decarbonylation of aldehydes. This heterogenous catalyst not only has excellent catalytic activity and chemoselectivity, but also holds high activity after 10 runs of reuse. The effective usage of this method is demonstrated through the synthesis of biofuels such as furfuryl alcohol (FFA) via the highly chemoselective decarbonylation of biomass-derived 5-hydroxy-methylfurfural (HMF) with a TON up to 1540. More importantly, 9-fluorenone could be obtained in one step through the decarbonylation of 2-bromobenzaldehyde by using this heterogeneous catalyst.

Recommended values of clean metal surface work functions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Derry, Gregory N., E-mail: gderry@loyola.edu; Kern, Megan E.; Worth, Eli H.

2015-11-15

A critical review of the experimental literature for measurements of the work functions of clean metal surfaces of single-crystals is presented. The tables presented include all results found for low-index crystal faces except cases that were known to be contaminated surfaces. These results are used to construct a recommended value of the work function for each surface examined, along with an uncertainty estimate for that value. The uncertainties are based in part on the error distribution for all measured work functions in the literature, which is included here. The metals included in this review are silver (Ag), aluminum (Al), goldmore » (Au), copper (Cu), iron (Fe), iridium (Ir), molybdenum (Mo), niobium (Nb), nickel (Ni), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), tantalum (Ta), and tungsten (W)« less

Stylized facts of intraday precious metals

PubMed Central

Batten, Jonathan; McGroarty, Frank; Peat, Maurice; Urquhart, Andrew

2017-01-01

This paper examines the stylized facts, correlation and interaction between volatility and returns at the 5-minute frequency for gold, silver, platinum and palladium from May 2000 to April 2015. We study the full sample period, as well as three subsamples to determine how high-frequency data of precious metals have developed over time. We find that over the full sample, the number of trades has increased substantially over time for each precious metal, while the bid-ask spread has narrowed over time, indicating an increase in liquidity and price efficiency. We also find strong evidence of periodicity in returns, volatility, volume and bid-ask spread. Returns and volume both experience strong intraday periodicity linked to the opening and closing of major markets around the world while the bid-ask spread is at its lowest when European markets are open. We also show a bilateral Granger causality between returns and volatility of each precious metal, which holds for the vast majority subsamples. PMID:28448492

Stylized facts of intraday precious metals.

PubMed

Batten, Jonathan; Lucey, Brian; McGroarty, Frank; Peat, Maurice; Urquhart, Andrew

2017-01-01

This paper examines the stylized facts, correlation and interaction between volatility and returns at the 5-minute frequency for gold, silver, platinum and palladium from May 2000 to April 2015. We study the full sample period, as well as three subsamples to determine how high-frequency data of precious metals have developed over time. We find that over the full sample, the number of trades has increased substantially over time for each precious metal, while the bid-ask spread has narrowed over time, indicating an increase in liquidity and price efficiency. We also find strong evidence of periodicity in returns, volatility, volume and bid-ask spread. Returns and volume both experience strong intraday periodicity linked to the opening and closing of major markets around the world while the bid-ask spread is at its lowest when European markets are open. We also show a bilateral Granger causality between returns and volatility of each precious metal, which holds for the vast majority subsamples.

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.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Stabilizing platinum in phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Remick, R. J.

1981-01-01

The cathode of the phosphoric acid fuel cell uses a high surface area platinum catalyst supported on a carbon substrate. During operation, the small platinum crystallites sinter, causing loss in cell performance. A support was developed that stabilizes platinum in the high surface area condition by retarding or preventing the sintering process. The approach is to form etch pits in the carbon by oxidizing the carbon in the presence of a metal oxide catalyst, remove the metal oxide by an acid wash, and then deposit platinum in these pits. Results confirm the formation of etch pits in each of the three supports chosen for investigation: Vulcan XC-72R, Vulcan XC-72 that was graphized at 2500 C, and Shawinigan Acetylene Black.

Synthesis of platinum nanowheels using a bicellar template.

PubMed

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

2008-09-24

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

Ozone sensing based on palladium decorated carbon nanotubes.

PubMed

Colindres, Selene Capula; Aguir, Khalifa; Cervantes Sodi, Felipe; Vargas, Luis Villa; Salazar, José Moncayo; Febles, Vicente Garibay

2014-04-14

Multiwall carbon nanotubes (MWCNTs) were easily and efficiently decorated with Pd nanoparticles through a vapor-phase impregnation-decomposition method starting from palladium acetylacetonates. The sensor device consisted on a film of sensitive material (MWCNTs-Pd) deposited by drop coating on platinum interdigitated electrodes on a SiO₂ substrate. The sensor exhibited a resistance change to ozone (O₃) with a response time of 60 s at different temperatures and the capability of detecting concentrations up to 20 ppb. The sensor shows the best response when exposed to O3 at 120 °C. The device shows a very reproducible sensor performance, with high repeatability, full recovery and efficient response.

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

PubMed

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

2018-01-22

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

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

PubMed

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

2011-03-01

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

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

PubMed

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

2010-03-14

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

High-pressure/high-temperature synthesis and characterization of the first palladium or platinum containing lithium transition-metal sulfides Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heymann, Gunter, E-mail: Gunter.Heymann@uibk.ac.at; Niehaus, Oliver; Krüger, Hannes

The new lithium transition-metal sulfides Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) were obtained via multianvil high-pressure/high-temperature syntheses at 8 GPa and 1150 °C starting from a stoichiometric mixture of lithium nitride, sulfur, and palladium or platinum. Single crystal structure analyses indicated the space group P2{sub 1}/c (no. 14) with the following lattice parameters and refinement results: a=492.9(1), b=1005.9(2), c=614.9(2) pm, β=110.9 (1)°, R1=0.0165, wR2=0.0308 (all data) for Li{sub 2}Pd{sub 3}S{sub 4} and a=498.2(1), b=1005.5(2), c=613.0(2) pm, β=110.8(1)°, R1=0.0215, wR2=0.0450 (all data) for Li{sub 2}Pt{sub 3}S{sub 4}. The crystal structures are built up from two distinct Pd/Pt sites, one of whichmore » is a special position (0,0,0), two sulfur sites, and one lithium site. The atoms Pd2/Pt2 form isolated square planar PdS{sub 4}/PtS{sub 4} units, whereas the Pd1/Pt1 atoms form pairs of square planar PdS{sub 4}/PtS{sub 4} units, which are connected via a common edge. These two structural motives built up a three-dimensional network structure by linking through common corners. The lithium atoms are positioned inside of the so formed channels. Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) are isostructural to the minerals jaguéite, Cu{sub 2}Pd{sub 3}Se{sub 4} and chrisstanleyite, Ag{sub 2}Pd{sub 3}Se{sub 4}, which are up to now the only representatives of this structure type. Both compounds were studied with respect to their magnetic properties and can be classified as Pauli paramagnetic or diamagnetic. Regarding the possibility of lithium mobility inside the channels, of the structure, solid state {sup 7}Li NMR and high-temperature single crystal investigations revealed localization of the lithium atoms on their crystallographic sites. - Graphical abstract: The ternary lithium transition-metal sulfides Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) were prepared via multianvil high-pressure/high-temperature syntheses. They are built up from square planar Pt

Metal nanoparticles (other than gold or silver) prepared using plant extracts for medical applications

NASA Astrophysics Data System (ADS)

Pasca, Roxana-Diana; Santa, Szabolcs; Racz, Levente Zsolt; Racz, Csaba Pal

2016-12-01

There are many modalities to prepare metal nanoparticles, but the reducing of the metal ions with plant extracts is one of the most promising because it is considerate less toxic for the environment, suitable for the use of those nanoparticles in vivo and not very expensive. Various metal ions have been already studied such as: cobalt, copper, iron, platinum, palladium, zinc, indium, manganese and mercury and the number of plant extracts used is continuously increasing. The prepared systems were characterized afterwards with a great number of methods of investigation: both spectroscopic (especially UV-Vis spectroscopy) and microscopic (in principal, electron microscopy-TEM) methods. The applications of the metal nanoparticles obtained are diverse and not completely known, but the medical applications of such nanoparticles occupy a central place, due to their nontoxic components, but some diverse industrial applications do not have to be forgotten.

Electro-catalytic activity of multiwall carbon nanotube-metal (Pt or Pd) nanohybrid materials synthesized using microwave-induced reactions and their possible use in fuel cells.

PubMed

V, Lakshman Kumar; Ntim, Susana Addo; Sae-Khow, Ornthida; Janardhana, Chelli; Lakshminarayanan, V; Mitra, Somenath

2012-11-30

Microwave induced reactions for immobilizing platinum and palladium nanoparticles on multiwall carbon nanotubes are presented. The resulting hybrid materials were used as catalysts for direct methanol, ethanol and formic acid oxidation in acidic as well as alkaline media. The electrodes are formed by simply mixing the hybrids with graphite paste, thus using a relatively small quantity of the precious metal. We report Tafel slopes and apparent activation energies at different potentials and temperatures. Ethanol electro-oxidation with the palladium hybrid showed an activation energy of 7.64 kJmol(-1) which is lower than those observed for other systems. This system is economically attractive because Pd is significantly less expensive than Pt and ethanol is fast evolving as a commercial biofuel.

Electro-catalytic activity of multiwall carbon nanotube-metal (Pt or Pd) nanohybrid materials synthesized using microwave-induced reactions and their possible use in fuel cells

PubMed Central

V, Lakshman Kumar; Ntim, Susana Addo; Sae-Khow, Ornthida; Janardhana, Chelli; Lakshminarayanan, V.; Mitra, Somenath

2012-01-01

Microwave induced reactions for immobilizing platinum and palladium nanoparticles on multiwall carbon nanotubes are presented. The resulting hybrid materials were used as catalysts for direct methanol, ethanol and formic acid oxidation in acidic as well as alkaline media. The electrodes are formed by simply mixing the hybrids with graphite paste, thus using a relatively small quantity of the precious metal. We report Tafel slopes and apparent activation energies at different potentials and temperatures. Ethanol electro-oxidation with the palladium hybrid showed an activation energy of 7.64 kJmol−1 which is lower than those observed for other systems. This system is economically attractive because Pd is significantly less expensive than Pt and ethanol is fast evolving as a commercial biofuel. PMID:23118490

Polymer Nanocomposite Film with Metal Rich Surface Prepared by In Situ Single-Step Formation of Palladium Nanoparticles: An Interesting Way to Combine Specific Functional Properties.

PubMed

Thompson, David; Kranbuehl, David; Espuche, Eliane

2016-10-18

This paper presents a continuous single-step route that permits preparation of a thermostable polymer/metal nanocomposite film and to combine different functional properties in a unique material. More precisely, palladium nanoparticles are in situ generated in a polyimide matrix thanks to a designed curing cycle which is applied to a polyamic acid/metal precursor solution cast on a glass plate. A metal-rich surface layer which is strongly bonded to the bulk film is formed in addition to homogeneously dispersed metal nanoparticles. This specific morphology leads to obtaining an optically reflective film. The metal nanoparticles act as gas diffusion barriers for helium, oxygen, and carbon dioxide; they induce a tortuosity effect which allows dividing the gas permeation coefficients by a factor near to 2 with respect to the neat polyimide matrix. Moreover, the ability of the in situ synthesized palladium nanoparticles to entrap hydrogen is evidenced. The nanocomposite film properties can be modulated as a function of the location of the film metal-rich surface with respect to the hydrogen feed. The synthesized nanocomposite could represent a major interest for a wide variety of applications, from specific coatings for aerospace or automotive industry, to catalysis applications or sensors.

Recovery of Elemental Palladium by Shewanella putrefaciens

NASA Astrophysics Data System (ADS)

Akasaka, S.; Xia, X.; Sawada, K.; Enokida, Y.; Yamamoto, I.; Ohnuki, T.

2006-12-01

Microbial reduction of metals plays an important role in environmental behavior and provides a technique for the recovery of metals from industrial wastewater. Recently, demand for platinum group metals (PGMs) increases by their catalytic properties. The extreme rarity of PGMs have led to a growing interest in their recovery. Palladium, one of PGMs, has different oxidation states of Pd(II) and Pd(0). The oxidized form of Pd(II) is soluble, while the reduced form of Pd(0) is insoluble. In this study, microbial reduction of palladium by Fe(III)- reducing bacterium, Shewanella putrefaceins was conducted. This bacterium is known to be capable of reducing metals, such as Mn(IV), U(VI), or Tc(VII) with organic C or H2 as an electron donor. In order to investigate the potential of S. putrefaciens to reduce Pd(II) in solution, resting cells or heat-killed cells were suspended under anaerobic conditions with lactate or H2 as an electron donor. The cells of S. putrefaciens (NBRC3908) were grown in aerobic medium, harvested by centrifugation, and then washed with 25 mmol/dm3 HEPES and 100 mmol/dm3 NaCl (HEPES-NaCl) solution (pH 7.0). The heat-killed cells were autoclaved for 20 min at 121 degrees C. The cell suspension (21.5 mg in dry weight) was resuspended in the HEPES-NaCl solution which contained 1.0 mmol/dm3 Na2PdCl4 (Wako Pure chemical Industries, Ltd). The suspensions were bubbled with N2 for 15 min before 10 mmol/dm3 lactate or 4.8 v/v% H2 was added. The suspensions were then incubated at 30 degrees C. Redox potential (Eh) and pH of the solutions were measured in an inert glove box with Ar gas. Concentration of Pd(II) was measured by Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES). Deposited Pd and cells were analyzed by X-ray powder diffraction (XRD) and Scanning Electron Microscope (SEM) with Energy-Dispersive Spectroscopy (EDS). Approximately 86% of Pd(II) of the initial concentration was removed from solution by the resting cells within 24 h when

Thin metal bilayer for surface plasmon resonance sensors in a multimode plastic optical fiber: the case of palladium and gold metal films

NASA Astrophysics Data System (ADS)

Cennamo, Nunzio; Zuppella, Paola; Bacco, Davide; Corso, Alain J.; Pelizzo, Maria G.; Pesavento, Maria; Zeni, Luigi

2016-05-01

A novel sensing platform based on thin metal bilayer for surface plasmon resonance (SPR) in a D-shaped plastic optical fiber (POF) has been designed, implemented and tested. The experimental results are congruent with the numerical studies. This platform has been properly optimized to work in the 1.38 -1.42 refractive index range and it exhibits excellent sensitivity. This refractive index range is very interesting for bio-chemical applications, where the polymer layer are used as receptors (e.g. molecularly imprinted polymer) or to immobilize the bio-receptor on the metal surface. The proposed metallic bilayer is based on palladium and gold films and replaces the traditional gold by exhibiting higher performances. Furthermore, the deposition of the thin bilayer is a single process and no further manufacturing step is required. In fact, in this case the photoresist buffer layer between the POF core and the metal layer, usually required to increase the refractive index range, is no longer necessary.

High-Valent Organometallic Copper and Palladium in Catalysis

PubMed Central

Hickman, Amanda J.; Sanford, Melanie S.

2015-01-01

Preface Copper and palladium catalysts are critically important for numerous commercial chemical processes. Improvements in the activity, selectivity, and scope of these catalysts have the potential to dramatically reduce the environmental impact and increase the sustainability of chemical reactions. One rapidly emerging strategy to achieve these goals is to exploit “high-valent” copper and palladium intermediates in catalysis. This review describes exciting recent advances involving both the fundamental chemistry and the applications of these high-valent metal complexes in numerous synthetically useful catalytic transformations. PMID:22498623

Porous platinum-based catalysts for oxygen reduction

DOEpatents

Erlebacher, Jonah D; Snyder, Joshua D

2014-11-25

A porous metal that comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A fuel cell includes a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte arranged between the first and the second electrodes. At least one of the first and second electrodes is coated with a porous metal catalyst for oxygen reduction, and the porous metal catalyst comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A method of producing a porous metal according to an embodiment of the current invention includes producing an alloy consisting essentially of platinum and nickel according to the formula Pt.sub.xNi.sub.1-x, where x is at least 0.01 and less than 0.3; and dealloying the alloy in a substantially pH neutral solution to reduce an amount of nickel in the alloy to produce the porous metal.

Partial oxidation of step-bound water leads to anomalous pH effects on metal electrode step-edges

DOE PAGES

Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan; ...

2016-05-26

The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet understood, limiting systematic improvement. In this paper, we analyze the change in charge and free energies upon adsorptionmore » using density-functional theory (DFT) to establish that water adsorbs on platinum step edges across a wide voltage range, including the double-layer region, with a loss of approximately 0.2 electrons upon adsorption. We show how this as-yet unreported change in net surface charge due to this water explains the anomalous pH variations of the hydrogen underpotential deposition (H upd) and the potentials of zero total charge (PZTC) observed in published experimental data. This partial oxidation of water is not limited to platinum metal step edges, and we report the charge of the water on metal step edges of commonly used catalytic metals, including copper, silver, iridium, and palladium, illustrating that this partial oxidation of water broadly influences the reactivity of metal electrodes.« less

Ultrafast studies of gold, nickel, and palladium nanorods

NASA Astrophysics Data System (ADS)

Sando, Gerald M.; Berry, Alan D.; Owrutsky, Jeffrey C.

2007-08-01

Steady state and ultrafast transient absorption studies have been carried out for gold, nickel, and palladium high aspect ratio nanorods. For each metal, nanorods were fabricated by electrochemical deposition into ˜6μm thick polycarbonate templates. Two nominal pore diameters(10 and 30nm, resulting in nanorod diameters of about 40 and 60nm, respectively) were used, yielding nanorods with high aspect ratios (>25). Static spectra of nanorods of all three metals reveal both a longitudinal surface plasmon resonance (SPRL) band in the mid-infrared as well as a transverse band in the visible for the gold and larger diameter nickel and palladium nanorods. The appearance of SPRL bands in the infrared for high aspect ratio metal nanorods and the trends in their maxima for the different aspect ratios and metals are consistent with calculations based on the Gans theory. For the gold and nickel samples, time resolved studies were performed with a subpicosecond resolution using 400nm excitation and a wide range of probe wavelengths from the visible to the mid-IR as well as for infrared excitation (near 2000cm-1) probed at 800nm. The dynamics observed for nanorods of both metals and both diameters include transients due to electron-phonon coupling and impulsively excited coherent acoustic breathing mode oscillations, which are similar to those previously reported for spherical and smaller rod-shaped gold nanoparticles. The dynamics we observe are the same within the experimental uncertainty for 400nm and infrared (5μm) excitation probed at 800nm. The transient absorption using 400nm excitation and 800nm probe pulses of the palladium nanorods also reveal coherent acoustic oscillations. The results demonstrate that the dynamics for high aspect ratio metal nanorods are similar to those for smaller nanoparticles.

Ozone Sensing Based on Palladium Decorated Carbon Nanotubes

PubMed Central

Colindres, Selene Capula; Aguir, Khalifa; Sodi, Felipe Cervantes; Vargas, Luis Villa; Moncayo Salazar, José A.; Febles, Vicente Garibay

2014-01-01

Multiwall carbon nanotubes (MWCNTs) were easily and efficiently decorated with Pd nanoparticles through a vapor-phase impregnation-decomposition method starting from palladium acetylacetonates. The sensor device consisted on a film of sensitive material (MWCNTs-Pd) deposited by drop coating on platinum interdigitated electrodes on a SiO2 substrate. The sensor exhibited a resistance change to ozone (O3) with a response time of 60 s at different temperatures and the capability of detecting concentrations up to 20 ppb. The sensor shows the best response when exposed to O3 at 120 °C. The device shows a very reproducible sensor performance, with high repeatability, full recovery and efficient response. PMID:24736133

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

DOEpatents

Wilcoxon, Jess P.

1992-01-01

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

Platinum(II)-Oligonucleotide Coordination Based Aptasensor for Simple and Selective Detection of Platinum Compounds.

PubMed

Cai, Sheng; Tian, Xueke; Sun, Lianli; Hu, Haihong; Zheng, Shirui; Jiang, Huidi; Yu, Lushan; Zeng, Su

2015-10-20

Wide use of platinum-based chemotherapeutic regimens for the treatment for carcinoma calls for a simple and selective detection of platinum compound in biological samples. On the basis of the platinum(II)-base pair coordination, a novel type of aptameric platform for platinum detection has been introduced. This chemiluminescence (CL) aptasensor consists of a designed streptavidin (SA) aptamer sequence in which several base pairs were replaced by G-G mismatches. Only in the presence of platinum, coordination occurs between the platinum and G-G base pairs as opposed to the hydrogen-bonded G-C base pairs, which leads to SA aptamer sequence activation, resulting in their binding to SA coated magnetic beads. These Pt-DNA coordination events were monitored by a simple and direct luminol-peroxide CL reaction through horseradish peroxidase (HRP) catalysis with a strong chemiluminescence emission. The validated ranges of quantification were 0.12-240 μM with a limit of detection of 60 nM and selectivity over other metal ions. This assay was also successfully used in urine sample determination. It will be a promising candidate for the detection of platinum in biomedical and environmental samples.

Palladium-bacterial cellulose membranes for fuel cells.

PubMed

Evans, Barbara R; O'Neill, Hugh M; Malyvanh, Valerie P; Lee, Ida; Woodward, Jonathan

2003-07-01

Bacterial cellulose is a versatile renewable biomaterial that can be used as a hydrophilic matrix for the incorporation of metals into thin, flexible, thermally stable membranes. In contrast to plant cellulose, we found it catalyzed the deposition of metals within its structure to generate a finely divided homogeneous catalyst layer. Experimental data suggested that bacterial cellulose possessed reducing groups capable of initiating the precipitation of palladium, gold, and silver from aqueous solution. Since the bacterial cellulose contained water equivalent to at least 200 times the dry weight of the cellulose, it was dried to a thin membranous structure suitable for the construction of membrane electrode assemblies (MEAs). Results of our study with palladium-cellulose showed that it was capable of catalyzing the generation of hydrogen when incubated with sodium dithionite and generated an electrical current from hydrogen in an MEA containing native cellulose as the polyelectrolyte membrane (PEM). Advantages of using native and metallized bacterial cellulose membranes in an MEA over other PEMs such as Nafion 117 include its higher thermal stability to 130 degrees C and lower gas crossover.

Platinum Monolayer Shell on Non-Noble Metal Core Electrocatalysts for the Hydrogen Oxidation Reaction

NASA Astrophysics Data System (ADS)

Teeluck, Krishani Malini

According to the United States Environmental Protection Agency, as of 2015, transportation accounted for 32% of the carbon dioxide emissions in the United States (and all carbon dioxide emissions in the U.S. accounted for 82.2% of all greenhouse gases from human activity). A hydrogen fuel cell is a device that efficiently produces electrical energy directly from a chemical reaction, with zero carbon emissions, and therefore holds great promise in alleviating our dependence on harmful use of energy sources. Due to their clean emissions and high efficiencies, there has been focus on the hydrogen fuel cell for vehicle applications using proton exchange membrane and alkaline fuel cells. Although the proton exchange membrane fuel cell is currently being used in vehicles, their high cost limits their feasibility in the market. This has inspired the development of the alkaline fuel cell whose efficiency and simplicity suggest the possibility of manufacturing high power fuel cell vehicles at a low cost, since the electrocatalysts in the alkaline fuel cell can be made from non-noble metals. Although the hydrogen oxidation reaction is one of the fastest electrochemical reactions in acidic media, it is two orders of magnitude slower in alkaline media, which hinders the overall efficiency of the alkaline fuel cell. Pure platinum is currently the best catalyst for the hydrogen oxidation reaction, but platinum’s high cost and rarity yields economic issues, rendering the technology futile if it cannot be commercialized. Furthermore, platinum’s hydrogen binding energy is slightly stronger than the optimal hydrogen binding energy. As the hydrogen oxidation reaction happens only on the surface of the catalyst, there is no need for platinum content beyond the exterior. Since tungsten and nickel are cheap, as well as abundant, they are ideal elements to replace the core of the catalyst with, while leaving a platinum shell surrounding this core. The activity of the hydrogen

Electrodeposition of platinum and silver into chemically modified microporous silicon electrodes

PubMed Central

2012-01-01

Electrodeposition of platinum and silver into hydrophobic and hydrophilic microporous silicon layers was investigated using chemically modified microporous silicon electrodes. Hydrophobic microporous silicon enhanced the electrodeposition of platinum in the porous layer. Meanwhile, hydrophilic one showed that platinum was hardly deposited within the porous layer, and a film of platinum on the top of the porous layer was observed. On the other hand, the electrodeposition of silver showed similar deposition behavior between these two chemically modified electrodes. It was also found that the electrodeposition of silver started at the pore opening and grew toward the pore bottom, while a uniform deposition from the pore bottom was observed in platinum electrodeposition. These electrodeposition behaviors are explained on the basis of the both effects, the difference in overpotential for metal deposition on silicon and on the deposited metal, and displacement deposition rate of metal. PMID:22720690

Formation of palladium(0) nanoparticles at microbial surfaces.

PubMed

Bunge, Michael; Søbjerg, Lina S; Rotaru, Amelia-Elena; Gauthier, Delphine; Lindhardt, Anders T; Hause, Gerd; Finster, Kai; Kingshott, Peter; Skrydstrup, Troels; Meyer, Rikke L

2010-10-01

The increasing demand and limited natural resources for industrially important platinum-group metal (PGM) catalysts render the recovery from secondary sources such as industrial waste economically interesting. In the process of palladium (Pd) recovery, microorganisms have revealed a strong potential. Hitherto, bacteria with the property of dissimilatory metal reduction have been in focus, although the biochemical reactions linking enzymatic Pd(II) reduction and Pd(0) deposition have not yet been identified. In this study we investigated Pd(II) reduction with formate as the electron donor in the presence of Gram-negative bacteria with no documented capacity for reducing metals for energy production: Cupriavidus necator, Pseudomonas putida, and Paracoccus denitrificans. Only large and close-packed Pd(0) aggregates were formed in cell-free buffer solutions. Pd(II) reduction in the presence of bacteria resulted in smaller, well-suspended Pd(0) particles that were associated with the cells (called "bioPd(0)" in the following). Nanosize Pd(0) particles (3-30 nm) were only observed in the presence of bacteria, and particles in this size range were located in the periplasmic space. Pd(0) nanoparticles were still deposited on autoclaved cells of C. necator that had no hydrogenase activity, suggesting a hydrogenase-independent formation mechanism. The catalytic properties of Pd(0) and bioPd(0) were determined by the amount of hydrogen released in a reaction with hypophosphite. Generally, bioPd(0) demonstrated a lower level of activity than the Pd(0) control, possibly due to the inaccessibility of the Pd(0) fraction embedded in the cell envelope. Our results demonstrate the suitability of bacterial cells for the recovery of Pd(0), and formation and immobilization of Pd(0) nanoparticles inside the cell envelope. However, procedures to make periplasmic Pd(0) catalytically accessible need to be developed for future nanobiotechnological applications.

Method of making sulfur-resistant composite metal membranes

DOEpatents

Way, J Douglas [Boulder, CO; Lusk, Mark [Golden, CO; Thoen, Paul [Littleton, CO

2012-01-24

The invention provides thin, hydrogen-permeable, sulfur-resistant membranes formed from palladium or palladium-alloy coatings on porous, ceramic or metal supports. Also disclosed are methods of making these membranes via sequential electroless plating techniques, wherein the method of making the membrane includes decomposing any organic ligands present on the substrate, reducing the palladium crystallites on the substrate to reduced palladium crystallites, depositing a film of palladium metal on the substrate and then depositing a second, gold film on the palladium film. These two metal films are then annealed at a temperature between about 200.degree. C. and about 1200.degree. C. to form a sulfur-resistant, composite PdAu alloy membrane.

Artificial crystals with 3d metal and palladium particles subjected to high-temperature heat treatment

NASA Astrophysics Data System (ADS)

Rinkevich, A. B.; Nemytova, O. V.; Perov, D. V.; Samoylovich, M. I.; Kuznetsov, E. A.

2018-04-01

High-temperature heat treatment has valuable impact on the structure and physical properties of artificial crystals with 3d metal and palladium particles. Artificial crystals are obtained by means of introduction of particles into the interspherical voids of opal matrices. The magnetic properties are studied at the temperatures ranging from 2 to 300 K and in fields up to 350 kOe. Microwave properties are investigated in the millimeter frequency range. The complex dielectric permittivity of several nanocomposites is measured. The influence of heat treatment up to 960 °C on the structure of artificial crystals is clarified.

Synthesis of ferromagnetic nanoparticles, formic acid oxidation catalyst nanocomposites, and late-transition metal-boride intermetallics by unique synthetic methods and single-source precursors

NASA Astrophysics Data System (ADS)

Wellons, Matthew S.

The design, synthesis, and characterization of magnetic alloy nanoparticles, supported formic acid oxidation catalysts, and superhard intermetallic composites are presented. Ferromagnetic equatomic alloy nanoparticles of FePt, FePd, and CoPt were synthesized utilizing single-source heteronuclear organometallic precursors supported on an inert water-soluble matrix. Direct conversion of the precursor-support composite to supported ferromagnetic nanoparticles occurs under elevated temperatures and reducing conditions with metal-ion reduction and minimal nanoparticle coalescence. Nanoparticles were easily extracted from the support by addition of water and characterized in structure and magnetic properties. Palladium and platinum based nanoparticles were synthesized with microwave-based and chemical metal-ion reduction strategies, respectively, and tested for catalytic performance in a direct formic acid fuel cell (DFAFC). A study of palladium carbide nanocomposites with various carbonaceous supports was conducted and demonstrated strong activity comparable to commercially available palladium black, but poor catalytic longevity. Platinum-lead alloy nanocomposites synthesized with chemical reduction and supported on Vulcan carbon demonstrated strong activity, excellent catalytic longevity, and were subsequently incorporated into a prototype DFAFC. A new method for the synthesis of superhard ceramics on polymer substrates called Confined Plasma Chemical Deposition (CPCD) was developed. The CPCD method utilizes a tuned Free Electron Laser to selectively decompose the single-source precursor, Re(CO)4(B3H8), in a plasma-like state resulting in the superhard intermetallic ReB2 deposited on polymer substrates. Extension of this method to the synthesis of other hard of superhard ceramics; WB4, RuB2, and B4C was demonstrated. These three areas of research show new synthetic methods and novel materials of technological importance, resulting in a substantial advance in their

Forging Unsupported Metal-Boryl Bonds with Icosahedral Carboranes.

PubMed

Saleh, Liban M A; Dziedzic, Rafal M; Khan, Saeed I; Spokoyny, Alexander M

2016-06-13

In contrast to the plethora of metal-catalyzed cross-coupling methods available for the installation of functional groups on aromatic hydrocarbons, a comparable variety of methods are currently not available for icosahedral carboranes, which are boron-rich three-dimensional aromatic analogues of aryl groups. Part of this is due to the limited understanding of the elementary steps for cross-coupling involving carboranes. Here, we report our efforts in isolating metal-boryl complexes to further our understanding of one of these elementary steps, oxidative addition. Structurally characterized examples of group 10 M-B bonds featuring icosahedral carboranes are completely unknown. Use of mercurocarboranes as a reagent to deliver M-B bonds saw divergent reactivity for platinum and palladium, with a Pt-B bond being isolated for the former, and a rare Pd-Hg bond being formed for the latter. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of platinum(II) and palladium(II) complexes with 9,9-dihexyl-4,5-diazafluorene and their in vivo antitumour activity against Hep3B xenografted mice.

PubMed

Wang, Q-W; Lam, P-L; Wong, R S-M; Cheng, G Y-M; Lam, K-H; Bian, Z-X; Ho, C-L; Feng, Y-H; Gambari, R; Lo, Y-H; Wong, W-Y; Chui, C-H

2016-11-29

Two complexes dichloro(9,9-dihexyl-4,5-diazafluorene)platinum(II) (Pt-DHF) and dichloro(9,9-dihexyl-4,5-diazafluorene)palladium(II) (Pd-DHF) were synthesized and their in vivo antitumour activity was investigated using an athymic nude mice model xenografted with human Hep3B carcinoma cells. Pt-DHF- and Pd-DHF-treated groups showed significant tumour growth inhibition (with about 9-fold and 3-fold tumour growth retardation) when compared with the vehicle control group. The liver toxicology effects on the animals of the two compounds were investigated. Pt-DHF and Pd-DHF-treated groups had a lower alanine transaminase and aspartate transaminase values than those of the vehicle treated group as the animals from the vehicle control group had very heavy hepatoma burden. We assume that both complexes could be further investigated as effective antitumour agents and it is worthwhile to study their underlying working mechanism. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Platinum recycling in the United States in 1998

USGS Publications Warehouse

Hilliard, Henry E.

2001-01-01

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

Failure mechanism characterization of platinum alloy

NASA Technical Reports Server (NTRS)

Rosen, J. M.; Mcfarlen, W. T.

1986-01-01

This article describes procedures and results of testing performed on a platinum/10-percent rhodium, thin-wall tubular product. The purpose of the testing was to develop exemplar SEM fractographs to be used to characterize failures under various environmental conditions. Conditions evaluated for the platinum alloys included high temperature, hydrogen environment, braze metal contamination, and cyclic loading.

Developments in platinum anticancer drugs

NASA Astrophysics Data System (ADS)

Tylkowski, Bartosz; Jastrząb, Renata; Odani, Akira

2018-01-01

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

First find of platinum group metals in the ore of Kirganik copper-porphyry deposit (Kamchatka)

NASA Astrophysics Data System (ADS)

Sidorov, E. G.; Ignatyev, E. K.; Chubarov, V. M.

2017-08-01

The Kirganik copper-porphyry deposit is situated in the central part of the Sredinnyi Mountain Range of Kamchatka and is confined to fields of development of potassic orthoclase metasomatite and hypabyssal intrusions of shonkinite. Platinum group metals (PGMs), such as merenskyite, kotulskite, keithconnite, and temagamite, were discovered in the chalcopyrite-bornite and chalcopyrite-bornite-chalcosine ore of the deposit for the first time.

Palladium nanoparticles formed on titanium silicate ETS-10.

PubMed

Lin, Christopher C H; Danaie, Mohsen; Mitlin, David; Kuznicki, Steven M

2011-03-01

We report that surface templated and supported palladium nanoparticles self assemble on ETS-10 type molecular sieve surfaces by simple exchange and activation procedures in the absence of a reductant. This procedure is similar to the one previously reported for silver nanoparticle self assembly on ETS-10. We observed a bimodal distribution with particle sizes ranging from 2-5 and 15-30 nm. This simple, economical method generates high concentrations (approximately 12 wt% of total composite) of uniform, metallic palladium nanoparticles that are multiply twinned and thermally stable making them potentially unique for advanced catalytic and electronic applications.

Method for high temperature mercury capture from gas streams

DOEpatents

Granite, Evan J [Wexford, PA; Pennline, Henry W [Bethel Park, PA

2006-04-25

A process to facilitate mercury extraction from high temperature flue/fuel gas via the use of metal sorbents which capture mercury at ambient and high temperatures. The spent sorbents can be regenerated after exposure to mercury. The metal sorbents can be used as pure metals (or combinations of metals) or dispersed on an inert support to increase surface area per gram of metal sorbent. Iridium and ruthenium are effective for mercury removal from flue and smelter gases. Palladium and platinum are effective for mercury removal from fuel gas (syngas). An iridium-platinum alloy is suitable for metal capture in many industrial effluent gas streams including highly corrosive gas streams.

Chlorodifluoromethane-triggered formation of difluoromethylated arenes catalysed by palladium

NASA Astrophysics Data System (ADS)

Feng, Zhang; Min, Qiao-Qiao; Fu, Xia-Ping; An, Lun; Zhang, Xingang

2017-09-01

Difluoromethylated aromatic compounds are of increasing importance in pharmaceuticals, agrochemicals and materials. Chlorodifluoromethane (ClCF2H), an inexpensive, abundant and widely used industrial raw material, represents the ideal and most straightforward difluoromethylating reagent, but introduction of the difluoromethyl group (CF2H) from ClCF2H into aromatics has not been reported. Here, we describe a direct palladium-catalysed difluoromethylation method for coupling ClCF2H with arylboronic acids and esters to generate difluoromethylated arenes with high efficiency. The reaction exhibits a remarkably broad substrate scope, including heteroarylboronic acids, and was used for difluoromethylation of a range of pharmaceuticals and biologically active compounds. Preliminary mechanistic studies revealed that a palladium difluorocarbene intermediate is involved in the reaction. Although numerous metal-difluorocarbene complexes have been prepared, the catalytic synthesis of difluoromethylated or difluoromethylenated compounds involving metal-difluorocarbene complexes has not received much attention. This new reaction therefore also opens the door to understand metal-difluorocarbene complex catalysed reactions.

Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates

DOEpatents

Adzic, Radoslav; Zhang, Junliang; Vukmirovic, Miomir

2012-11-13

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen.

Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates

DOEpatents

Adzic, Radoslav [East Setauket, NY; Zhang, Junliang [Stony Brook, NY; Vukmirovic, Miomir [Port Jefferson Station, NY

2011-11-22

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen.

Toxicity, Spectroscopic Characterization and Electrochemical Behaviour of New Macrocclic Complexes of Lead(II) and Palladium(II) Metals

PubMed Central

Bansal, Anil; Singh, Randhir

2000-01-01

Tetraazamacrocyclie complexes of lead and palladium have been synthesized by the template process using the bis(benzil)ethylenediamine precursor. The tetradentate macrocycle (maL) reacts with PbCl2, PdCl2 and different diamines in a 1:1:1 molar ratio in methanol to give several solid complexes of the types [Pb(maL)(R)Cl2] and [Pd(maL)(R)]Cl2 (where R = 2,6-diaminopyridine or 1,2-phenylenediamine). The macrocycle and its metal complexes have been characterized by elemental analysis, molecular weight determinations, molar conductivity, IR, 1H NMR, 13C NMR, electronic, mass and electrochemical studies. The macrocyclic ligand coordinates through the four azomethine nitrogen atoms which are bridged by benzil moieties. IR spectra suggest that the pyridine nitrogen is not coordinating. The palladium complexes exhibit tetracoordinated square-planar geometry, whereas a hexacoordinated octahedral geometry is suggested for lead complexes. The macrocycle along with its complexes have been screened in vitro against a number of pathogenic fungi and bacteria to assess their growth inhibiting potential. PMID:18475947

Rational Design of Porous Conjugated Polymers and Roles of Residual Palladium for Photocatalytic Hydrogen Production.

PubMed

Li, Lianwei; Cai, Zhengxu; Wu, Qinghe; Lo, Wai-Yip; Zhang, Na; Chen, Lin X; Yu, Luping

2016-06-22

Developing highly efficient photocatalyts for water splitting is one of the grand challenges in solar energy conversion. Here, we report the rational design and synthesis of porous conjugated polymer (PCP) that photocatalytically generates hydrogen from water splitting. The design mimics natural photosynthetics systems with conjugated polymer component to harvest photons and the transition metal part to facilitate catalytic activities. A series of PCPs have been synthesized with different light harvesting chromophores and transition metal binding bipyridyl (bpy) sites. The photocatalytic activity of these bpy-containing PCPs can be greatly enhanced due to the improved light absorption, better wettability, local ordering structure, and the improved charge separation process. The PCP made of strong and fully conjugated donor chromophore DBD (M4) shows the highest hydrogen production rate at ∼33 μmol/h. The results indicate that copolymerization between a strong electron donor and weak electron acceptor into the same polymer chain is a useful strategy for developing efficient photocatalysts. This study also reveals that the residual palladium in the PCP networks plays a key role for the catalytic performance. The hydrogen generation activity of PCP photocatalyst can be further enhanced to 164 μmol/h with an apparent quantum yield of 1.8% at 350 nm by loading 2 wt % of extra platinum cocatalyst.

Characterization of the Sukinda and Nausahi ultramafic complexes, Orissa, India by platinum-group element geochemistry

USGS Publications Warehouse

Page, N.J.; Banerji, P.K.; Haffty, J.

1985-01-01

Samples of 20 chromitite, 14 ultramafic and mafic rock, and 9 laterite and soil samples from the Precambrian Sukinda and Nausahi ultramafic complexes, Orissa, India were analyzed for platinum-group elements (PGE). The maximum concentrations are: palladium, 13 parts per billion (ppb); platinum, 120 ppb; rhodium, 21 ppb; iridium, 210 ppb; and ruthenium, 630 ppb. Comparison of chondrite-normalized ratios of PGE for the chromitite samples of lower Proterozoic to Archean age with similar data from Paleozoic and Mesozoic ophiolite complexes strongly implies that these complexes represent Precambrian analogs of ophiolite complexes. This finding is consistent with the geology and petrology of the Indian complexes and suggests that plate-tectonic and ocean basin developement models probably apply to some parts of Precambrian shield areas. ?? 1985.

Oxidation of methane over palladium catalysts: effect of the support.

PubMed

Escandón, Lara S; Ordóñez, Salvador; Vega, Aurelio; Díez, Fernando V

2005-01-01

This work is focused on the deep catalytic oxidation of methane over supported palladium catalysts. The influences of the metal loading, oxidation state of palladium, nature of supports, presence of promoters in the supports (for zirconia-based supports), and thermal stability have been studied experimentally. Catalysts were prepared by incipient wetness of commercially available supports with aqueous solutions of palladium nitrate. For gamma-alumina support, it was observed that the optimal amount of palladium is between 0.5% and 2%, with higher amounts leading to a loss in specific activity. Concerning the oxidation state of the catalyst, it is concluded that for all the supports tested in the present work, a reduction of the catalyst is not needed, yielding the same conversion at steady state catalysts reduced and oxidised. The thermal stability of various supported catalysts were also studied, zirconia supports being the most active. These supports, specially Y-modified zirconia support, do not suffer appreciable deactivation below 500 degrees C.

Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Hockmuth, J.; Pagliaro, P.

1984-01-01

The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

Evaluation of cellular influences of platinum nanoparticles by stable medium dispersion.

PubMed

Horie, Masanori; Kato, Haruhisa; Endoh, Shigehisa; Fujita, Katsuhide; Nishio, Keiko; Komaba, Lilian Kaede; Fukui, Hiroko; Nakamura, Ayako; Miyauchi, Arisa; Nakazato, Tetsuya; Kinugasa, Shinichi; Yoshida, Yasukazu; Hagihara, Yoshihisa; Morimoto, Yasuo; Iwahashi, Hitoshi

2011-11-01

Platinum nanoparticles have industrial application, for example in catalysis, and are used in consumer products such as cosmetics and supplements. Therefore, among the many nanoparticles, platinum is one of the more accessible nanoparticles for consumers. Most platinum nanoparticles that are used in cosmetics and supplements which have an anti-oxidant activity are modified particles. However, the cellular influences of pristine platinum nanoparticles are still unclear, although it has been reported that platinum nanoparticles induce oxidative stress. In this study, we investigated the cellular influences induced by pure pristine platinum nanoparticles. Platinum nanoparticles of 100% purity were dispersed in a cell culture medium and stable medium dispersion was obtained. The platinum nanoparticle medium dispersion was applied to two kinds of cultured cells, A549 and HaCaT cells, and the cellular influences were examined. Cell viability (MTT assay), cell proliferation (clonogenic assay), apoptosis induction (caspase-3 activity), intracellular ROS level (DCFH assay), and lipid peroxidation level (DPPP assay) were measured as markers of cellular influences. Transmission electron microscope observation showed cellular uptake of platinum nanoparticles. However, the platinum nanoparticles did not drive any markers. It is known that some metal oxide nanoparticles such as NiO and CuO show severe cytotoxicity via metal ion release. Compared with these toxic nanoparticles, the platinum nanoparticles used in this study did not release platinum ions into the culture media. These results suggest that the physically and chemically inactive cellular influences of platinum nanoparticles are small.

The Role of Near-Earth Asteroids in Long-Term Platinum Supply

NASA Astrophysics Data System (ADS)

Blair, B. R.

2000-01-01

High-grade platinum-group metal concentrations have been identified in an abundant class of near-Earth asteroids known as LL Chondrites. The potential existence of a high-value asteroid-derived mineral product is examined from an economic perspective to assess the possible impacts on long-term precious metal supply. It is hypothesized that extraterrestrial sources of platinum group metals will become available in the global marketplace in a 20-year time frame, based on current trends of growth in technology and increasing levels of human activities in near-Earth space. Current and projected trends in platinum supply and demand are cited from the relevant literature to provide an economic context and provide an example for evaluating the economic potential of future asteroid-derived precious and strategic metals.

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.

Are scarce metals in cars functionally recycled?

PubMed

Andersson, Magnus; Ljunggren Söderman, Maria; Sandén, Björn A

2017-02-01

Improved recycling of end-of-life vehicles (ELVs) may serve as an important strategy to address resource security risks related to increased global demand for scarce metals. However, in-depth knowledge of the magnitude and fate of such metals entering ELV recycling is lacking. This paper quantifies input of 25 scarce metals to Swedish ELV recycling, and estimates the extent to which they are recycled to material streams where their metal properties are utilised, i.e. are functionally recycled. Methodologically, scarce metals are mapped to main types of applications within newly produced Swedish car models and subsequently, material flow analysis of ELV waste streams is used as basis for identifying pathways of these applications and assessing whether contained metals are functionally recycled. Results indicate that, of the scarce metals, only platinum may be functionally recycled in its main application. Cobalt, gold, manganese, molybdenum, palladium, rhodium and silver may be functionally recycled depending on application and pathways taken. For remaining 17 metals, functional recycling is absent. Consequently, despite high overall ELV recycling rates of materials in general, there is considerable risk of losing ELV scarce metals to carrier metals, construction materials, backfilling materials and landfills. Given differences in the application of metals and identified pathways, prospects for increasing functional recycling are discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Platinum and associated elements at the New Rambler mine and vicinity, Albany and Carbon Counties, Wyoming

USGS Publications Warehouse

Theobald, P.K.; Thompson, Charles Emmet

1968-01-01

Platinum-group metals in the Medicine Bow Mountains were first identified by W. C. Knight in 1901. In the Medicine Bow Mountains, these metals are commonly associated with copper, silver, or gold in shear zones that cut a series of mafic igneous and metamorphic rocks. At the New Rambler mine, where the initial discovery was made, about 50,000 tons of mine and mill waste contain an average of 0.3 percent copper, 7 ppm (parts per million) silver, 1 ppm platinum plus palladium, and 0.7 ppm gold. This material is believed to be from a low-grade envelope around the high-grade pod of complex ore that was mined selectively in the old workings. Soil samples in the vicinity of the New Rambler mine exhibit a wide range of content of several elements associated with the ore. Most of the variation can be attributed to contamination, from the mine workings. Even though soil samples identify a low-level copper anomaly that persists to the limit of the area sampled, soils do not offer a promising medium for tracing mineralization owing to the blanket of transported overburden. Stream sediments, if preconcentrated for analysis, do reveal anomalies not only in the contaminated stream below the New Rambler mine, but in adjacent drainage and on Dave Creek. Examination of a spectrum of elements in heavy-mineral concentrates from stream sediment may contribute to knowledge of the nature of the mineralization and of the basic geology of the environment. The sampling of bedrock exposures is not particularly fruitful because outcrops are sparse and the exposed rocks are the least altered and mineralized. Bedrock sampling does, however, provide information on the large size and provincial nature of the platinum-rich area. We feel that a properly integrated program of geological, geophysical, and geochemical exploration in the Medicine Bow Mountains and probably in the Sierra Madre to the west has a reasonable probability of successfully locating a complex ore body.

Synthesis and characterization of new complexes of nickel (II), palladium (II) and platinum(II) with derived sulfonamide ligand: Structure, DFT study, antibacterial and cytotoxicity activities

NASA Astrophysics Data System (ADS)

Bouchoucha, Afaf; Zaater, Sihem; Bouacida, Sofiane; Merazig, Hocine; Djabbar, Safia

2018-06-01

The synthesis, characterization and biological study of new nickel (II), palladium (II), and platinum (II) complexes with sulfamethoxazole ligand used in pharmaceutical field, were reported. [MLCl2].nH2O is the general formula obtained for Pd(II) and Pt(II) complexes. These complexes have been prepared and characterized by elemental analysis, FTIR, 1HNMR spectral, magnetic measurements, UV-Visible spectra, and conductivity. The DFT calculation was applied to optimize the geometric structure of the Pd(II) and Pt(II) complexes. A new single-crystal X-ray structure of the Ni(II) complex has been determined. It crystallized in monoclinic system with P 21/c space group and Z = 8. The invitro antibacterial activity of ligand and complexes against Escherichia coli, P. aeruginosa, Klebsiella pneumoniae, S. aureus, Bacillus subtilis species has been carried out and compared using agar-diffusion method. The Pd(II) and Pt(II) complexes showed a remarkable inhibition against bacteria tested. The invitro cytotoxicity assay of the complexes against three cell lines chronic myelogenous leukaemia (K562), human colon adenocarcinoma (HT-29) and breast cancer (MCF-7) was also reported.

Trace metals in occupationally and nonoccupationally exposed individuals.

PubMed Central

Johnson, D E; Tillery, J B; Prevost, R J

1975-01-01

An epidemiological survey was conducted in Houston, Texas on five trace metals in policemen, parking garage attendants, women living near freeways and three control groups of subjects. The controls were matched with the exposed groups for covariate information such as age, sex, smoking habits, ethnic background, socioeconomic status, hair color, and education. Each subject was sampled four times for blood, urine, hair, and feces, and these samples were analyzed for lead, cadmium, zinc, manganese, and copper. Lead and cadmium were correlated with airborne exposures but zinc, manganese and copper were not. The second part of this paper deals with a market study of platinum and palladium markets and a design of an epidemiology survey of individuals occupationally and nonoccupationally exposed to these two metals. The market survey shows that although the catalytic muffler will have a major impact on the market, it is predicted that producers can meet these demands. PMID:1157784

Metal-support interactions during the adsorption of CO on thin layers and islands of epitaxial palladium

NASA Technical Reports Server (NTRS)

Park, C.; Poppa, H.; Soria, F.

1984-01-01

Islands and continuous layers of palladium were grown in an ultrahigh vacuum on substrates of Mo(110)c(14 x 7)-O, designated MoO(x), and of clean Mo(110). It was found that as-deposited islands and layers exhibited bulk palladium adsorption properties for CO when deposited at room temperature and for palladium thicknesses in excess of about 3 monolayers. CO adsorption was drastically reduced, however, on annealing. For islands, annealing temperatures of as low as 400 K led to some reduction in CO adsorption whereas more severe reductions were found to occur at 600 K for islands and at 800 K for continuous multilayers. The deactivation depended on the palladium thickness, the substrate species and the extent of thermal treatments. Auger electron spectroscopy, temperature-programmed desorption and Delta-Phi measurements were combined to interpret the deactivation behavior in terms of substrate-support interactions involving the diffusion of substrate species towards the palladium surface.

Platinum group metals as flux pinning additions in screen printed superconducting YBa 2Cu 3O 7-δ thick films

NASA Astrophysics Data System (ADS)

Langhorn, J.; Bi, Y. J.; Abell, J. S.

1996-02-01

Platinum group metal additions made to thick films of YBCO have induced significant improvements in the superconducting properties, in particular critical current densities ( Jc). Values in excess of 7 × 10 3 A cm -2 at 77 K and zero applied field have been measured. Optical and transmission electron microscopy have shown a homogeneous distribution of sub-micron sized, and larger highly anisotropic 211, believed to result from a reaction between Pt and YBCO to create nucleation sites for 211 precipitates. Indirect supporting thermal analysis evidence for this reaction is presented. An increased density of dislocations associated with the {123}/{211} interface suggests that refined 211 precipitates may act as heterogeneous nucleation sites for flux pinning defects. Similar effects have been observed for additions of other platinum group metals (Rh, Pd).

Size control and catalytic activity of bio-supported palladium nanoparticles.

PubMed

Søbjerg, Lina Sveidal; Lindhardt, Anders T; Skrydstrup, Troels; Finster, Kai; Meyer, Rikke Louise

2011-07-01

The development of nanoparticles has greatly improved the catalytic properties of metals due to the higher surface to volume ratio of smaller particles. The production of nanoparticles is most commonly based on abiotic processes, but in the search for alternative protocols, bacterial cells have been identified as excellent scaffolds of nanoparticle nucleation, and bacteria have been successfully employed to recover and regenerate platinum group metals from industrial waste. We report on the formation of bio-supported palladium (Pd) nanoparticles on the surface of two bacterial species with distinctly different surfaces: the gram positive Staphylococcus sciuri and the gram negative Cupriavidus necator. We investigated how the type of bacterium and the amount of biomass affected the size and catalytic properties of the nanoparticles formed. By increasing the biomass:Pd ratio, we could produce bio-supported Pd nanoparticles smaller than 10nm in diameter, whereas lower biomass:Pd ratios resulted in particles ranging from few to hundreds of nm. The bio-supported Pd nanoparticle catalytic properties were investigated towards the Suzuki-Miyaura cross coupling reaction and hydrogenation reactions. Surprisingly, the smallest nanoparticles obtained at the highest biomass:Pd ratio showed no reactivity towards the test reactions. The lack of reactivity appears to be caused by thiol groups, which poison the catalyst by binding strongly to Pd. Different treatments intended to liberate particles from the biomass, such as burning or rinsing in acetone, did not re-establish their catalytic activity. Sulphur-free biomaterials should therefore be explored as more suitable scaffolds for Pd(0) nanoparticle formation. Copyright © 2011 Elsevier B.V. All rights reserved.

Fuel cell with Pt/Pd electrocatalyst electrode

DOEpatents

Stonehart, Paul

1983-01-01

An electrode for use in a phosphoric acid fuel cell comprising a graphitized or partially graphitized carbon support having a platinum/palladium electrocatalyst thereon. Preferably, the platinum/palladium catalyst comprises 20 to 65 weight percent palladium.

Platinum particle size and support effects in NO(x) mediated carbon oxidation over platinum catalysts.

PubMed

Villani, Kenneth; Vermandel, Walter; Smets, Koen; Liang, Duoduo; van Tendeloo, Gustaaf; Martens, Johan A

2006-04-15

Platinum metal was dispersed on microporous, mesoporous, and nonporous support materials including the zeolites Na-Y, Ba-Y, Ferrierite, ZSM-22, ETS-10, and AIPO-11, alumina, and titania. The oxidation of carbon black loosely mixed with catalyst powder was monitored gravimetrically in a gas stream containing nitric oxide, oxygen, and water. The carbon oxidation activity of the catalysts was found to be uniquely related to the Pt dispersion and little influenced by support type. The optimum dispersion is around 3-4% corresponding to relatively large Pt particle sizes of 20-40 nm. The carbon oxidation activity reflects the NO oxidation activity of the platinum catalyst, which reaches an optimum in the 20-40 nm Pt particle size range. The lowest carbon oxidation temperatures were achieved with platinum loaded ZSM-22 and AIPO-11 zeolite crystallites bearing platinum of optimum dispersion on their external surfaces.

MICROWAVE-ASSISTED SYNTHESIS OF NOBLE NANOSTRUCTURES

EPA Science Inventory

Microwave-assisted (MW) spontaneous reduction of noble metal salts, silver (Ag), gold (Au), platinum (Pt) and palladium (Pd) is reported using sugar solutions such as -D glucose, sucrose and maltose, etc. to generate nanomaterials. These MW-assisted reactions, conducted in aqueo...

Metal Complexes for Organic Optoelectronic Applications

NASA Astrophysics Data System (ADS)

Huang, Liang

Organic optoelectronic devices have drawn extensive attention by over the past two decades. Two major applications for Organic optoelectronic devices are efficient organic photovoltaic devices(OPV) and organic light emitting diodes (OLED). Organic Solar cell has been proven to be compatible with the low cost, large area bulk processing technology and processed high absorption efficiencies compared to inorganic solar cells. Organic light emitting diodes are a promising approach for display and solid state lighting applications. To improve the efficiency, stability, and materials variety for organic optoelectronic devices, several emissive materials, absorber-type materials, and charge transporting materials were developed and employed in various device settings. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. In this thesis, Chapter 1 provides an introduction to the background knowledge of OPV and OLED research fields presented. Chapter 2 discusses new porphyrin derivatives- azatetrabenzylporphyrins for OPV and near infrared OLED applications. A modified synthetic method is utilized to increase the reaction yield of the azatetrabenzylporphyrin materials and their photophysical properties, electrochemical properties are studied. OPV devices are also fabricated using Zinc azatetrabenzylporphyrin as donor materials. Pt(II) azatetrabenzylporphyrin were also synthesized and used in near infra-red OLED to achieve an emission over 800 nm with reasonable external quantum efficiencies. Chapter 3, discusses the synthesis, characterization, and device evaluation of a series of tetradentate platinum and palladium complexesfor single doped white OLED applications and RGB white OLED applications. Devices employing some of the developed emitters demonstrated impressively high external quantum efficiencies within the range of 22%-27% for various emitter concentrations. And the palladium complex, i

Preparation of Supported Palladium Catalysts using Deep Eutectic Solvents.

PubMed

Iwanow, Melanie; Finkelmeyer, Jasmin; Söldner, Anika; Kaiser, Manuela; Gärtner, Tobias; Sieber, Volker; König, Burkhard

2017-09-12

Deep eutectic solvents (DESs) dissolve metal salts or oxides and are used as solvent and carbon source for the preparation of supported palladium catalysts. After dissolving of the palladium salt in the DES, the pyrolysis of the mixture under nitrogen atmosphere yields catalytically active palladium on supporting material composed of carbon, nitrogen and oxygen (CNO) by a simple single step preparation method without further activation. The catalysts were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and CHNS/O elementary analysis. The amount of functional groups on the surface of the supporting material was determined by Boehm titrations. Moreover, the activity of the prepared catalysts was evaluated in the hydrogenation of linear alkenes and compared with a commercial Pd/C catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Platinum transfer from hCTR1 to Atox1 is dependent on the type of platinum complex.

PubMed

Wu, Xuelei; Yuan, Siming; Wang, Erqiong; Tong, Yang; Ma, Guolin; Wei, Kaiju; Liu, Yangzhong

2017-05-24

In spite of their wide application, the cellular uptake of platinum based anticancer drugs is still unclear. The copper transport protein, hCTR1, is proposed to facilitate the cellular uptake of cisplatin, whereas organic cation transport (OCT) is more important for oxaliplatin. It has been reported that both N-terminal and C-terminal metal binding motifs of hCTR1 are highly reactive to cisplatin, which is the initial step of protein assisted cellular uptake of cisplatin. It is still unknown how the platinum drugs in hCTR1 transfer to cytoplasmic media, and whether various platinum complexes possess different activities in this process. Herein, we investigated the reaction of the platinated C-terminal metal binding motif of hCTR1 (C8) with the down-stream protein Atox1. Results show that Atox1 is highly reactive to the platinated C8 adducts of cisplatin and transplatin, whereas the oxaliplatin/C8 adduct is much less reactive. The platinum transfer from C8 to Atox1 occurs in the reaction, which results in the protein unfolding of Atox1. These results demonstrated that the platinated intracellular-domain of hCTR1 is reactive to Atox1, and the reactivity is dependent on the ligand and the coordination structure of platinum complexes. The different reactivity is consistent with the hypothesis that hCTR1 is more significant in the transport of cisplatin than that of oxaliplatin.

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.

Metal allergens of growing significance: epidemiology, immunotoxicology, strategies for testing and prevention.

PubMed

Forte, Giovanni; Petrucci, Francesco; Bocca, Beatrice

2008-09-01

Metal-induced allergic contact dermatitis (ACD) is expressed in a wide range of cutaneous reactions following dermal and systemic exposure to products such as cosmetics and tattoos, detergents, jewellery and piercing, leather tanning, articular prostheses and dental implants. Apart from the well known significance of nickel in developing ACD, other metals such as aluminium, beryllium, chromium, cobalt, copper, gold, iridium, mercury, palladium, platinum, rhodium and titanium represented emerging causes of skin hypersensitivity. Despite the European Union directives that limit the total nickel content in jewellery alloys, the water soluble chromium (VI) in cement, and metals banned in cosmetics, the diffusion of metal-induced ACD remained quite high. On this basis, a review on the epidemiology of metal allergens, the types of exposure, the skin penetration, the immune response, and the protein interaction is motivated. Moreover, in vivo and in vitro tests for the identification and potency of skin-sensitizing metals are here reviewed in a risk assessment framework for the protection of consumer's health. Avenues for ACD prevention and therapy such as observance of maximum allowable metal levels, optimization of metallurgic characteristics, efficacy of chelating agents and personal protection are also discussed.

Metallization of Large Silicon Wafers

NASA Technical Reports Server (NTRS)

Pryor, R. A.

1978-01-01

A metallization scheme was developed which allows selective plating of silicon solar cell surfaces. The system is comprised of three layers. Palladium, through the formation of palladium silicide at 300 C in nitrogen, makes ohmic contact to the silicon surface. Nickel, plated on top of the palladium silicide layer, forms a solderable interface. Lead-tin solder on the nickel provides conductivity and allows a convenient means for interconnection of cells. To apply this metallization, three chemical plating baths are employed.

Alkali metal-refractory metal biphase electrode for AMTEC

NASA Technical Reports Server (NTRS)

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

1989-01-01

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

Metal/ceramic composites with high hydrogen permeability

DOEpatents

Dorris, Stephen E.; Lee, Tae H.; Balachandran, Uthamalingam

2003-05-27

A membrane for separating hydrogen from fluids is provided comprising a sintered homogenous mixture of a ceramic composition and a metal. The metal may be palladium, niobium, tantalum, vanadium, or zirconium or a binary mixture of palladium with another metal such as niobium, silver, tantalum, vanadium, or zirconium.

In vitro permeation of platinum and rhodium through Caucasian skin.

PubMed

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

2014-12-01

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

Low-cost method for fabricating palladium and palladium-alloy thin films on porous supports

DOEpatents

Lee, Tae H; Park, Chan Young; Lu, Yunxiang; Dorris, Stephen E; Balachandran, Uthamalingham

2013-11-19

A process for forming a palladium or palladium alloy membrane on a ceramic surface by forming a pre-colloid mixture comprising a powder palladium source, carrier fluid, dispersant and a pore former and a binder. Ultrasonically agitating the precolloid mixture and applying to a substrate with an ultrasonic nozzle and heat curing the coating form a palladium-based membrane.

Methods of producing porous platinum-based catalysts for oxygen reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erlebacher, Jonah D.; Snyder, Joshua D.

A porous metal that comprises platinum and has a specific surface area that is greater than 5 m 2/g and less than 75 m 2/g. A fuel cell includes a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte arranged between the first and the second electrodes. At least one of the first and second electrodes is coated with a porous metal catalyst for oxygen reduction, and the porous metal catalyst comprises platinum and has a specific surface area that is greater than 5 m 2/g and less than 75 m 2/g. A method ofmore » producing a porous metal according to an embodiment of the current invention includes producing an alloy consisting essentially of platinum and nickel according to the formula Pt xNi 1-x, where x is at least 0.01 and less than 0.3; and dealloying the alloy in a substantially pH neutral solution to reduce an amount of nickel in the alloy to produce the porous metal.« less

40 CFR 421.263 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... Ammonia (as N) 599.900 263.700 (b) Raw material granulation. BAT Limitations for the Secondary Precious....051 Zinc 0.653 0.269 Combined metals 0.192 Palladium 0.064 Platinum 0.064 Ammonia (as N) 85.310 37.500... Combined metals 0.300 Ammonia (as N) 133.300 58.600 (d) Spent cyanide stripping solutions. BAT Limitations...

40 CFR 421.263 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... Ammonia (as N) 599.900 263.700 (b) Raw material granulation. BAT Limitations for the Secondary Precious....051 Zinc 0.653 0.269 Combined metals 0.192 Palladium 0.064 Platinum 0.064 Ammonia (as N) 85.310 37.500... Combined metals 0.300 Ammonia (as N) 133.300 58.600 (d) Spent cyanide stripping solutions. BAT Limitations...

40 CFR 421.263 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... Ammonia (as N) 599.900 263.700 (b) Raw material granulation. BAT Limitations for the Secondary Precious....051 Zinc 0.653 0.269 Combined metals 0.192 Palladium 0.064 Platinum 0.064 Ammonia (as N) 85.310 37.500... Combined metals 0.300 Ammonia (as N) 133.300 58.600 (d) Spent cyanide stripping solutions. BAT Limitations...

40 CFR 421.263 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... Ammonia (as N) 599.900 263.700 (b) Raw material granulation. BAT Limitations for the Secondary Precious....051 Zinc 0.653 0.269 Combined metals 0.192 Palladium 0.064 Platinum 0.064 Ammonia (as N) 85.310 37.500... Combined metals 0.300 Ammonia (as N) 133.300 58.600 (d) Spent cyanide stripping solutions. BAT Limitations...

Device for hydrogen separation and method

DOEpatents

Paglieri, Stephen N [White Rock, NM; Anderson, Iver E [Ames, IA; Terpstra, Robert L [Ames, IA

2009-11-03

A device for hydrogen separation has a porous support and hydrogen separation material on the support. The support is prepared by heat treatment of metal microparticles, preferably of iron-based or nickel-based alloys that also include aluminum and/or yttrium. The hydrogen separation material is then deposited on the support. Preferred hydrogen separation materials include metals such as palladium, alloys, platinum, refractory metals, and alloys.

Phosphorus adlayers on Platinum (110)

NASA Astrophysics Data System (ADS)

Heikkinen, Olli; Riihimäki, Ari; Sainio, Jani; Lahtinen, Jouko

2017-10-01

Platinum is a metal utilized in many applications. Its catalytic activity can be decreased due to chemical poisoning caused e.g. by phosphorus. To gain more understanding of its poisoning, we present a study of phosphorus adsorption on a platinum (110) single crystal surface. Using X-ray photoelectron spectroscopy, we have found that the adsorbate coverage saturates at around 3 monolayers. Annealing the phosphorus-covered platinum surface at 750 °C gives rise to three different ordered adlayer structures, with symmetries of 2 × 3, 11 × 4 and √{ 2} × 1 , from the lowest to the highest coverage, detected with low-energy electron diffraction. We have studied the sample topography with scanning tunnelling microscopy. We also present a tentative model for the observed structures and their evolution.

SELECTIVE OXIDATION IN SUPERCRITICAL CARBON DIOXIDE USING CLEAN OXIDANTS

EPA Science Inventory

We have systematically investigated heterogeneous catalytic oxidation of different substrates in supercritical carbon dioxide (SC-CO2). Three types of catagysts: a metal complex, 0.5% platinum g-alumina and 0.5% palladium g-alumina were used at a pressure of 200 bar, temperatures...

Recovery of fission product palladium from acidic high level waste solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rizvi, G.H.; Mathur, J.N.; Murali, M.S.

1996-07-01

The recovery of palladium from a synthetic pressurized heavy water reactor high level waste (PHWR-HLW) solution has been carried out, and the best reagents to use for the actual HLW solutions are discussed. The extraction of palladium from nitric acid solutions has been carried out using Cyanex-471X (triisobutylphosphine sulfide, TIPS) as the extractant. The metal ion could be quantitatively extracted from solutions with nitric acid concentrations between 2.0 and 6.0 M. The species extracted into the organic phase was found to be Pd(NO{sub 3}){sub 2}{center_dot}TIPS. Nitric acid in the range of 2.0 to 5.0 M had no effect on TIPSmore » for at least 71 hours. A systematic study of gamma irradiation on loading and stripping of palladium from loaded organic phases using several potential extractants, TIPS, alpha benzoin oxime, dioctylsulfide, and dioctylsulfoxide has been made. A flow sheet for the recovery of palladium from actual HLW solutions using TIPS is proposed.« less

Geochemical behaviour of palladium in soils and Pd/PdO model substances in the presence of the organic complexing agents L-methionine and citric acid.

PubMed

Zereini, Fathi; Wiseman, Clare L S; Vang, My; Albers, Peter; Schneider, Wolfgang; Schindl, Roland; Leopold, Kerstin

2016-01-01

Risk assessments of platinum group metal (PGE) emissions, notably those of platinum (Pt), palladium (Pd) and rhodium (Rh), have been mostly based on data regarding the metallic forms used in vehicular exhaust converters, known to be virtually biologically inert and immobile. To adequately assess the potential impacts of PGE, however, data on the chemical behaviour of these metals under ambient conditions post-emission is needed. Complexing agents with a high affinity for metals in the environment are hypothesized to contribute to an increased bioaccessibility of PGE. The purpose of this study is to examine the modulating effects of the organic complexing agents, L-methionine and citric acid, on the geochemical behavior of Pd in soils and model substances (Pd black and PdO). Batch experimental tests were conducted with soils and model substances to examine the impacts of the concentration of complexing agents, pH and length of extraction period on Pd solubility and its chemical transformation. Particle surface chemistry was examined using X-ray photoelectron spectroscopy (XPS) on samples treated with solutions under various conditions, including low and high O2 levels. Pd was observed to be more soluble in the presence of organic complexing agents, compared to Pt and Rh. Pd in soils was more readily solubilized with organic complexing agents compared to the model substances. After 7 days of extraction, L-methionine (0.1 M) treated soil and Pd black samples, for instance, had mean soluble Pd fractions of 12.4 ± 5.9% and 0.554 ± 0.024%, respectively. Surface chemistry analyses (XPS) confirmed the oxidation of metallic Pd surfaces when treated with organic complexing agents. The type of organic complexing agent used for experimental purposes was observed to be the most important factor influencing solubility, followed by solution pH and time of extraction. The results demonstrate that metallic Pd can be transformed into more bioaccessible species in the presence of

Effect of barrier height on friction behavior of the semiconductors silicon and gallium arsenide in contact with pure metals

NASA Technical Reports Server (NTRS)

Mishina, H.; Buckley, D. H.

1984-01-01

Friction experiments were conducted for the semiconductors silicon and gallium arsenide in contact with pure metals. Polycrystalline titanium, tantalum, nickel, palladium, and platinum were made to contact a single crystal silicon (111) surface. Indium, nickel, copper, and silver were made to contact a single crystal gallium arsenide (100) surface. Sliding was conducted both in room air and in a vacuum of 10 to the minus 9th power torr. The friction of semiconductors in contact with metals depended on a Schottky barrier height formed at the metal semiconductor interface. Metals with a higher barrier height on semiconductors gave lower friction. The effect of the barrier height on friction behavior for argon sputtered cleaned surfaces in vacuum was more specific than that for the surfaces containing films in room air. With a silicon surface sliding on titanium, many silicon particles back transferred. In contrast, a large quantity of indium transferred to the gallium arsenide surface.

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

PubMed

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

2015-02-17

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

Laccases as palladium oxidases.

PubMed

Mekmouche, Yasmina; Schneider, Ludovic; Rousselot-Pailley, Pierre; Faure, Bruno; Simaan, A Jalila; Bochot, Constance; Réglier, Marius; Tron, Thierry

2015-02-01

The first example of a coupled catalytic system involving an enzyme and a palladium(ii) catalyst competent for the aerobic oxidation of alcohol in mild conditions is described. In the absence of dioxygen, the fungal laccase LAC3 is reduced by a palladium(0) species as evidenced by the UV/VIS and ESR spectra of the enzyme. During the oxidation of veratryl alcohol performed in water, at room temperature and atmospheric pressure, LAC3 regenerates the palladium catalyst, is reduced and catalyzes the four-electron reduction of dioxygen into water with no loss of enzyme activity. The association of a laccase with a water-soluble palladium complex results in a 7-fold increase in the catalytic efficiency of the complex. This is the first step in the design of a family of renewable palladium catalysts for aerobic oxidation.

Platinum recycling going green via induced surface potential alteration enabling fast and efficient dissolution

PubMed Central

Hodnik, Nejc; Baldizzone, Claudio; Polymeros, George; Geiger, Simon; Grote, Jan-Philipp; Cherevko, Serhiy; Mingers, Andrea; Zeradjanin, Aleksandar; Mayrhofer, Karl J. J.

2016-01-01

The recycling of precious metals, for example, platinum, is an essential aspect of sustainability for the modern industry and energy sectors. However, due to its resistance to corrosion, platinum-leaching techniques rely on high reagent consumption and hazardous processes, for example, boiling aqua regia; a mixture of concentrated nitric and hydrochloric acid. Here we demonstrate that complete dissolution of metallic platinum can be achieved by induced surface potential alteration, an ‘electrode-less' process utilizing alternatively oxidative and reductive gases. This concept for platinum recycling exploits the so-called transient dissolution mechanism, triggered by a repetitive change in platinum surface oxidation state, without using any external electric current or electrodes. The effective performance in non-toxic low-concentrated acid and at room temperature is a strong benefit of this approach, potentially rendering recycling of industrial catalysts, including but not limited to platinum-based systems, more sustainable. PMID:27767178

Ester versus polyketone formation in the palladium-diphosphine catalyzed carbonylation of ethene.

PubMed

Zuidema, Erik; Bo, Carles; van Leeuwen, Piet W N M

2007-04-04

The origin of the chemoselectivity of palladium catalysts containing bidentate phosphine ligands toward either methoxycarbonylation of ethene or the copolymerization of ethene and carbon monoxide was investigated using density functional theory based calculations. For a palladium catalyst containing the electron-donating bis(dimethylphosphino)ethane (dmpe) ligand, the rate determining step for chain propagation is shown to be the insertion of ethene into the metal-acyl bond. The high barrier for chain propagation is attributed to the low stability of the ethene intermediate, (dmpe)Pd(ethene)(C(O)CH3). For the competing methanolysis process, the most likely pathway involves the formation of (dmpe)Pd(CH3OH)(C(O)CH3) via dissociative ligand exchange, followed by a solvent mediated proton-transfer/reductive- elimination process. The overall barrier for this process is higher than the barrier for ethene insertion into the palladium-acetyl bond, in line with the experimentally observed preference of this type of catalyst toward the formation of polyketone. Electronic bite angle effects on the rates of ethene insertion and ethanoyl methanolysis were evaluated using four electronically and sterically related ligands (Me)2P(CH2)nP(Me)2 (n = 1-4). Steric effects were studied for larger tert-butyl substituted ligands using a QM/MM methodology. The results show that ethene coordination to the metal center and subsequent insertion into the palladium-ethanoyl bond are disfavored by the addition of steric bulk around the metal center. Key intermediates in the methanolysis mechanism, on the other hand, are stabilized because of electronic effects caused by increasing the bite angle of the diphosphine ligand. The combined effects explain successfully which ligands give polymer and which ones give methyl propionate as the major products of the reaction.

FAST TRACK COMMUNICATION: Poly(methyl methacrylate)-palladium clusters nanocomposite formation by supersonic cluster beam deposition: a method for microstructured metallization of polymer surfaces

NASA Astrophysics Data System (ADS)

Ravagnan, Luca; Divitini, Giorgio; Rebasti, Sara; Marelli, Mattia; Piseri, Paolo; Milani, Paolo

2009-04-01

Nanocomposite films were fabricated by supersonic cluster beam deposition (SCBD) of palladium clusters on poly(methyl methacrylate) (PMMA) surfaces. The evolution of the electrical conductance with cluster coverage and microscopy analysis show that Pd clusters are implanted in the polymer and form a continuous layer extending for several tens of nanometres beneath the polymer surface. This allows the deposition, using stencil masks, of cluster-assembled Pd microstructures on PMMA showing a remarkably high adhesion compared with metallic films obtained by thermal evaporation. These results suggest that SCBD is a promising tool for the fabrication of metallic microstructures on flexible polymeric substrates.

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.

Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores.

PubMed

El-Safty, Sherif A; Shenashen, Mohamed A; Sakai, Masaru; Elshehy, Emad; Halada, Kohmei

2015-12-06

Developing low-cost, efficient processes for recovering and recycling palladium, gold and cobalt metals from urban mine remains a significant challenge in industrialized countries. Here, the development of optical mesosensors/adsorbents (MSAs) for efficient recognition and selective recovery of Pd(II), Au(III), and Co(II) from urban mine was achieved. A simple, general method for preparing MSAs based on using high-order mesoporous monolithic scaffolds was described. Hierarchical cubic Ia3d wagon-wheel-shaped MSAs were fabricated by anchoring chelating agents (colorants) into three-dimensional pores and micrometric particle surfaces of the mesoporous monolithic scaffolds. Findings show, for the first time, evidence of controlled optical recognition of Pd(II), Au(III), and Co(II) ions and a highly selective system for recovery of Pd(II) ions (up to ~95%) in ores and industrial wastes. Furthermore, the controlled assessment processes described herein involve evaluation of intrinsic properties (e.g., visual signal change, long-term stability, adsorption efficiency, extraordinary sensitivity, selectivity, and reusability); thus, expensive, sophisticated instruments are not required. Results show evidence that MSAs will attract worldwide attention as a promising technological means of recovering and recycling palladium, gold and cobalt metals.

Deposition of platinum nanoparticles on carbon nanotubes by supercritical fluid method.

PubMed

Yen, Clive H; Cui, Xiaoli; Pan, Horng-Bin; Wang, Shaofen; Lin, Yuehe; Wai, Chien M

2005-11-01

Carbon nanotube-supported platinum nanoparticles with a 5-15 nm diameter size range can be synthesized by hydrogen reduction of platinum(ll) acetylacetonate in methanol modified supercritical carbon dioxide. X-ray photoelectron spectroscopy and X-ray diffraction spectra indicate that the carbon nanotubes contain zero-valent platinum metal and high-resolution transmission electron microscopy images show that the visible lattice fringes of platinum nanoparticles are crystallites. Carbon nanotubes synthesized with 25% by weight of platinum nanoparticles exhibit a higher activity for hydrogenation of benzene compared with a commercial carbon black platinum catalyst. The carbon nanotube-supported platinum nanocatalyst can be reused at least six times for the hydrogenation reaction without losing activity. The carbon nanotube-supported platinum nanoparticles are also highly active for electrochemical oxidation of methanol and for reduction of oxygen suggesting their potential use as a new electrocatalyst for proton exchange membrane fuel cell applications.

Platinum blue staining of cells grown in electrospun scaffolds.

PubMed

Yusuf, Mohammed; Millas, Ana Luiza G; Estandarte, Ana Katrina C; Bhella, Gurdeep K; McKean, Robert; Bittencourt, Edison; Robinson, Ian K

2014-01-01

Fibroblast cells grown in electrospun polymer scaffolds were stained with platinum blue, a heavy metal stain, and imaged using scanning electron microscopy. Good contrast on the cells was achieved compared with samples that were gold sputter coated. The cell morphology could be clearly observed, and the cells could be distinguished from the scaffold fibers. Here we optimized the required concentration of platinum blue for imaging cells grown in scaffolds and show that a higher concentration causes platinum aggregation. Overall, platinum blue is a useful stain for imaging cells because of its enhanced contrast using scanning electron microscopy (SEM). In the future it would be useful to investigate cell growth and morphology using three-dimensional imaging methods.

The RSC Faraday prize lecture of 1989 on platinum.

PubMed

Thomas, John Meurig

2017-08-25

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

Preparation of low-sulfur platinum and platinum aluminide layers in thermal barrier coatings

NASA Technical Reports Server (NTRS)

Spitsberg, Irene T. (Inventor); Walston, William S. (Inventor); Schaeffer, Jon C. (Inventor)

2003-01-01

A method for preparing a coated nickel-base superalloy article reduces the sulfur content of the surface region of the metallic coating layers to low levels, thereby improving the adhesion of the coating layers to the article. The method includes depositing a first layer of platinum overlying the surface of a substrate, depositing a second layer of aluminum over the platinum, and final desulfurizing the article by heating the article to elevated temperature, preferably in hydrogen, and removing a small amount of material from the surface that was exposed during the step of heating. A ceramic layer may be deposited over the desulfurized article. The article may also be similarly desulfurized at other points in the fabrication procedure.

Access to the meta position of arenes through transition metal catalysed C-H bond functionalisation: a focus on metals other than palladium.

PubMed

Mihai, Madalina T; Genov, Georgi R; Phipps, Robert J

2018-01-02

The elaboration of simple arenes in order to access more complex substitution patterns is a crucial endeavor for synthetic chemists, given the central role that aromatic rings play in all manner of important molecules. Classical methods are now routinely used alongside stoichiometric organometallic approaches and, most recently, transition metal catalysis in the range of methodologies that are available to elaborate arene C-H bonds. Regioselectivity is an important consideration when selecting a method and, of all those available, it is arguably those that target the meta position that are fewest in number. The rapid development of transition metal-catalysed C-H bond functionalisation over the last few decades has opened new possibilities for meta-selective C-H functionalisation through the diverse reactivity of transition metals and their compatibility with a wide range of directing groups. The pace of discovery of such processes has grown rapidly in the last five years in particular and it is the purpose of this review to examine these but in doing so to place the focus on metals other than palladium, the specific contributions of which have been very recently reviewed elsewhere. It is hoped this will serve to highlight to the reader the breadth of current strategies and mechanisms that have been used to tackle this challenge, which may inspire further progress in the field.

Prefunctionalized Porous Organic Polymers: Effective Supports of Surface Palladium Nanoparticles for the Enhancement of Catalytic Performances in Dehalogenation.

PubMed

Zhong, Hong; Liu, Caiping; Zhou, Hanghui; Wang, Yangxin; Wang, Ruihu

2016-08-22

Three porous organic polymers (POPs) containing H, COOMe, and COO(-) groups at 2,6-bis(1,2,3-triazol-4-yl)pyridyl (BTP) units (i.e., POP-1, POP-2, and POP-3, respectively) were prepared for the immobilization of metal nanoparticles (NPs). The ultrafine palladium NPs are uniformly encapsulated in the interior pores of POP-1, whereas uniform- and dual-distributed palladium NPs are located on the external surface of POP-2 and POP-3, respectively. The presence of carboxylate groups not only endows POP-3 an outstanding dispersibility in H2 O/EtOH, but also enables the palladium NPs at the surface to show the highest catalytic activity, stability, and recyclability in dehalogenation reactions of chlorobenzene at 25 °C. The palladium NPs on the external surface are effectively stabilized by the functionalized POPs containing BTP units and carboxylate groups, which provides a new insight for highly efficient catalytic systems based on surface metal NPs of porous materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Comparative Life Cycle Assessment of Recycling the Platinum Group Metals from Automobile Catalytic Converter: An Australian Perspective

NASA Astrophysics Data System (ADS)

Ghodrat, Maryam; Rhamdhani, M. Akbar; Sharafi, Pezhman; Samali, Bijan

2017-12-01

This study provides a comparison between environmental impacts of the recovery of platinum group metals (PGMs) from the end-of-life catalytic converters by hydrometallurgical and pyrometallurgical methods. A gate to grave life cycle assessment of a typical three-way catalytic converter manufactured for an Australian passenger car was carried out using GaBi professional environmental package. Recovery rates, as well as qualities, quantities, losses, and fugitive emissions for all materials and elements used in both methods were calculated based on the developed flowsheets. A life cycle impact assessment was then made by carrying out a mass balance calculation. Inventory data show that the hydrometallurgical route for recycling of the platinum group metals out of catalytic converter scrap has lower impacts on the environment compared with the pyrometallurgical method. In terms of emission effects, the hydrometallurgical process was found to be highly advantageous since it causes insignificant emissions to air, sea water, and fresh water. It is also found that the hydrometallurgical route performs comparatively superior in terms of acidification, eutrophication, fossil depletion, and human toxicity. The obtained results are applicable only to the Australian setting.

Synthesis of metal-metal oxide catalysts and electrocatalysts using a metal cation adsorption/reduction and adatom replacement by more noble ones

DOEpatents

Adzic, Radoslav; Vukmirovic, Miomir; Sasaki, Kotaro

2010-04-27

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen. The invention also relates to methods of making the metal-metal oxide composites.

Experimental partitioning of Zr, Ti, and Nb between silicate liquid and a complex noble metal alloy and the partitioning of Ti between perovskite and platinum metal

NASA Technical Reports Server (NTRS)

Jurewicz, Stephen R.; Jones, John H.

1993-01-01

El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.

Potentiodynamic polarization study of the in vitro corrosion behavior of 3 high-palladium alloys and a gold-palladium alloy in 5 media.

PubMed

Sun, Desheng; Monaghan, Peter; Brantley, William A; Johnston, William M

2002-01-01

Corrosion of cast alloy restorations may lead to their failure or adversely affect their biocompatibility. Although some documentation of the corrosion behavior of the high-palladium dental alloys exists, questions remain about their corrosion resistance and mechanisms. This study compared the in vitro corrosion characteristics of 3 high-palladium alloys and 1 gold-palladium alloy in simulated body fluid and oral environments. Two Pd-Cu-Ga alloys and 1 Pd-Ga alloy were selected; an Au-Pd alloy served as the control. The corrosion behavior for the as-cast and simulated porcelain-firing (heat-treated) conditions of each alloy (N = 5) was evaluated in 0.9% NaCl, 0.09% NaCl, and Fusayama solutions. Heat-treated specimens of each alloy (N = 5) were also tested in N(2)-deaerated 0.09% NaCl and Fusayama solutions (pH 4). After immersion in the electrolyte for 24 hours, the open-circuit potential (OCP) was measured, and linear polarization was performed from -20 mV to +20 mV (vs. OCP) at a scanning rate of 0.125 mV/s. Cyclic polarization was performed from -300 mV to +1000 mV and back to -300 mV (vs. OCP) at a scanning rate of 1 mV/s. Data were evaluated with analysis of variance and the Ryan-Einot-Gabriel-Welsch multiple-range test (alpha=.05). The OCP of each alloy varied with the condition (as-cast or heat-treated) and electrolyte used. Corrosion resistance was similar for the 4 alloys tested. For cyclic polarization, all alloys showed active-passive or spontaneous passive behavior in nearly all electrolytes. During some reverse scans, the 3 high-palladium alloys displayed 3 or 5 anodic peaks. No positive hysteresis was observed for any of the alloy/electrolyte combinations evaluated. The corrosion resistances of the 3 high-palladium alloys in simulated body fluid and oral environments were comparable to that of the gold-palladium alloy. The similar corrosion resistance for the 3 high-palladium alloys was attributed to their high noble metal content and theorized stable

Platinum stable isotopes in ferromanganese crust and nodules

NASA Astrophysics Data System (ADS)

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

2015-04-01

Hydrogenetic ferromanganese (Fe-Mn) crust and nodules are slow-growing chemical sediments that form by direct precipitation from seawater, resulting in a record of changing seawater chemistry. These sediments are the primary sink for platinum in the modern oxic marine environment, hosting well-documented enrichments over other platinum-group elements (PGEs): the Pt anomaly [1]. Platinum is a non-bio-essential, highly siderophile, transition metal with six stable isotopes (190Pt, 192Pt, 194Pt, 195Pt, 196Pt, and 198Pt) with several oxidation states (Pt0, Pt2+ and Pt4+). Platinum is generally considered to exist in the hydrosphere as Pt2+ although its behaviour in the marine environment is poorly constrained, and Pt4+may also be present. Variations in ocean redox state, together with changes in source fluxes to the oceans, may therefore lead to small variations (< ±1) in the stable isotopic composition of marine platinum, raising the potential of adding platinum to the growing arsenal of paleoceanographic tracers. A method has been developed to measure the platinum isotopic composition using double spike MC-ICPMS analysis [2]and applied to a global suite of modern Fe-Mn crust and nodules. Combining synchrotron XAFS analyses of platinum adsorbed onto Fe-Mn oxide and oxyhydroxide surfaces to determine oxidation state and bonding environment, with platinum stable isotopic measurements allowing us to evaluate both platinum incorporation onto these sediments and the associated degree of platinum isotopic fractionation. Leaching experiments conducted on platinum rich terrestrial materials underwent platinum stable isotopic measurement as an analogue for the Pt isotopic fractionation associated with continental weathering. [1] Hodge, V.F. et al. (1985) Earth and Planetary Science Letters, 72, 158-162. [2] Creech, J. et al. (2013) Journal of Analytical Atomic Spectrometry, 28. 853-865.

Addition of platinum and silver nanoparticles to toughen dental porcelain.

PubMed

Fujieda, Tokushi; Uno, Mitsunori; Ishigami, Hajime; Kurachi, Masakazu; Wakamatsu, Nobukazu; Doi, Yutaka

2012-01-01

Several studies have investigated toughening porcelain that is layered over a frame or a core. The introduction of residual compressive stress to the surface of porcelain has been shown to be effective to strengthen it. In the present study, nanoparticles of precious metals of silver and platinum (rather than non-precious metals) were used to evaluate if they could increase the fracture resistance of porcelain. The addition of silver and platinum nanoparticles was found to improve the mechanical properties of porcelain since it increased both the Young's modulus and the fracture toughness of commercial porcelain.

Fabrication of rippled surfaces for diffraction gratings by plastic deformation of platinum foils and metallic glasses

NASA Astrophysics Data System (ADS)

Korsukov, V. E.; Malygin, G. A.; Korsukova, M. M.; Nyapshaev, I. A.; Obidov, B. A.

2015-12-01

Thin platinum foils and metallic glass ribbons with a fractal surface consisting of different-scale unidirectionally oriented ripples have been fabricated using special thermoplastic processing. The general fractal dimension of the rippled surface and dimensions along and across the ripples have been measured. The optical spectra of a PRK-4 lamp using rippled Pt(111) foils as reflective diffraction gratings have been determined. A model describing the mechanism of the formation of surface unidirectional fractal structures during deformation has been proposed.

Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin

PubMed Central

Wilson, Justin J.

2012-01-01

Oxidation of the acetate-bridged half-lantern platinum(II) complex, cis-[PtII(NH3)2(µ-OAc)2PtII(NH3)2](NO3)2, [1](NO3)2, with iodobenzene dichloride or bromine generates the halide-capped platinum(III) species, cis-[XPtIII(NH3)2(µ-OAc)2PtIII(NH3)2X](NO3)2, where X is Cl in [2](NO3)2, or Br in [3](NO3)2, respectively. These three complexes, characterized structurally by X-ray crystallography, feature short (≈ 2.6 Å) Pt–Pt separations, consistent with formation of a formal metal-metal bond upon oxidation. Elongated axial Pt–X distances occur, reflecting the strong trans influence of the metal-metal bond. The three structures are compared to those of other known dinuclear platinum complexes. A combination of 1H, 13C, 14N, and 195Pt NMR spectroscopy was used to characterize [1]2+–[3]2+ in solution. All resonances shift downfield upon oxidation of [1]2+ to [2]2+ and [3]2+. For the platinum(III) complexes, the 14N and 195Pt resonances exhibit decreased linewidths by comparison to those of [1]2+. Density functional theory (DFT) calculations suggest that the decrease in 14N linewidth arises from a diminished electric field gradient (EFG) at the 14N nuclei in the higher valent compounds. The oxidation of [1](NO3)2 with the alternative oxidizing agent, bis(trifluoroacetoxy) iodobenzene, affords the novel tetranuclear complex, cis-[(O2CCF3)PtIII(NH3)2(µ-OAc)2PtIII(NH3)(µ-NH2)]2(NO3)4, [4](NO3)4, also characterized structurally by X-ray crystallography. In solution, this complex exists as a mixture of species, the identities of which are proposed. PMID:22946515

Correlation between theoretical descriptor and catalytic oxygen reduction activity of graphene supported palladium and palladium alloy electrocatalysts

NASA Astrophysics Data System (ADS)

Seo, Min Ho; Choi, Sung Mook; Lee, Dong Un; Kim, Won Bae; Chen, Zhongwei

2015-12-01

The oxygen reduction reaction, ORR, performances of graphene-supported palladium (Pd) and palladium alloys (Pd3X: X = Ag, Co and Fe) catalysts with highly dispersed catalyst particles are investigated in acidic and alkaline conditions using a rotating disk electrode, RDE. Graphene nanosheet, GNS, supported Pd based catalysts are fabricated without surfactant through the impregnation of Pd and 2nd metal precursors on GNS, leading to small and uniformly dispersed nanoparticles, even when high metal loading of up to 60 wt.% are deposited on supports. The ab-initio density functional theory, DFT, calculations, which are based on the d-band center theory, have been applied to correlate with the results of the ORR performances obtained by half-cell tests. Additionally, the cohesive energy, Ecoh, and dissolution potential, Um, for the Pd nanoparticles have been calculated to understand thermodynamic stability. To elucidate the d-band center shift, the Pd 3d5/2 core-level binding energies for Pd/GNS, Pd3Ag/GNS, Pd3Fe/GNS and Pd3Co/GNS have been investigated by X-ray photoelectron spectroscopy, XPS. The GNS-supported Pd, or Pd-based alloy-nanoparticle catalyst shows good ORR activity under acidic and alkaline conditions, suggesting it may offer potential replacement for Pt for use in cathode electrodes of anion-exchange membrane fuel cell, AEMFC, and acid based polymer electrolyte fuel cell, PEMFC.

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

PubMed

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

2018-03-30

Urinary platinum (Pt) excretion is a reliable biomarker for occupational Pt exposure and has been previously reported for precious metals refinery workers in Europe but not for South Africa, the world's largest producer of Pt. This study aimed to quantify the urinary Pt excretion of South African precious metals refinery workers. Spot urine samples were collected from 40 workers (directly and indirectly exposed to Pt) at two South African precious metals refineries on three consecutive mornings prior to their shifts. Urine samples were analysed for Pt using inductively coupled plasma-mass spectrometry and were corrected for creatinine content. The urinary Pt excretion of workers did not differ significantly between sampling days. Urinary Pt excretions ranged from <0.1 to 3.0 µg Pt/g creatinine with a geometric mean of 0.21 µg Pt/g creatinine (95% CI 0.17 to 0.26 µg Pt/g creatinine). The work area (P=0.0006; η 2 =0.567) and the number of years workers were employed at the refineries (P=0.003; η 2 =0.261) influenced their urinary Pt excretion according to effect size analyses. Directly exposed workers had significantly higher urinary Pt excretion compared with indirectly exposed workers (P=0.007). The urinary Pt excretion of South African precious metals refinery workers reported in this study is comparable with that of seven other studies conducted in precious metals refineries and automotive catalyst plants in Europe. The Pt body burden of workers is predominantly determined by their work area, years of employment in the refineries and whether they are directly or indirectly exposed to Pt. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Thin Metallic Films from Solvated Metal Atoms.

DTIC Science & Technology

1987-07-14

platinium , and especially indium are discussed. N, ; ,, -- !, : N) By Dist , , . N S f1 -- ~~r, 821-19 C[ Thin metallic films from solvated metal atoms...metallic films. Cold, palladium, platinium , and especially indium are discussed. 1- INTRQDUCTION In the field of chemistry an active and broad area of

A Pd/C-CeO2 Anode Catalyst for High-Performance Platinum-Free Anion Exchange Membrane Fuel Cells.

PubMed

Miller, Hamish A; Lavacchi, Alessandro; Vizza, Francesco; Marelli, Marcello; Di Benedetto, Francesco; D'Acapito, Francesco; Paska, Yair; Page, Miles; Dekel, Dario R

2016-05-10

One of the biggest obstacles to the dissemination of fuel cells is their cost, a large part of which is due to platinum (Pt) electrocatalysts. Complete removal of Pt is a difficult if not impossible task for proton exchange membrane fuel cells (PEM-FCs). The anion exchange membrane fuel cell (AEM-FC) has long been proposed as a solution as non-Pt metals may be employed. Despite this, few examples of Pt-free AEM-FCs have been demonstrated with modest power output. The main obstacle preventing the realization of a high power density Pt-free AEM-FC is sluggish hydrogen oxidation (HOR) kinetics of the anode catalyst. Here we describe a Pt-free AEM-FC that employs a mixed carbon-CeO2 supported palladium (Pd) anode catalyst that exhibits enhanced kinetics for the HOR. AEM-FC tests run on dry H2 and pure air show peak power densities of more than 500 mW cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

Müller, M; Heumann, K G

2000-09-01

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

Calculation of the superconducting transition temperature of a graphene layer doped with titanium and palladium

NASA Astrophysics Data System (ADS)

Vazquez, Gerardo; Magana, Fernando; Salas-Torres, Osiris

We explore the structural interactions between graphene and transition metals such as palladium (Pd) and titanium (Ti) and the possibility of inducing superconductivity in a graphene sheet in two cases, one by doping its surface with palladium atoms sit on the center of the hexagons of the graphene layer and other by covering the graphene layer with two layers of titanium metal atoms. The results here were obtained from first-principles density functional theory in the local density approximation. The Quantum-Espresso package was used with norm conserving pseudopotentials. All of the structures considered were relaxed to their minimum energy configuration. Phonon frequencies were calculated using the linear-response technique on several phonon wave-vector mesh. The electron-phonon coupling parameter was calculated with several electron momentum k-mesh. The superconducting critical temperature was estimated using the Allen-Dynes formula with μ* = 0.1 - 0.15. We note that palladium and titanium are good candidate materials to show a metal-to-superconductor transition. We thank Dirección General de Asuntos del Personal Académico de la Universidad Nacional Autónoma de México, partial financial support by Grant IN-106514 and we also thank Miztli Super-Computing center the technical assistance.

Miniaturized Metal (Metal Alloy)/PdO(x)/SiC Hydrogen and Hydrocarbon Gas Sensors

NASA Technical Reports Server (NTRS)

Hunter, Gary W. (Inventor); Xu, Jennifer C. (Inventor); Lukco, Dorothy (Inventor)

2008-01-01

A miniaturized Schottky diode hydrogen and hydrocarbon sensor and the method of making same is disclosed and claimed. The sensor comprises a catalytic metal layer, such as palladium, a silicon carbide substrate layer and a thin barrier layer in between the catalytic and substrate layers made of palladium oxide (PdO(x)). This highly stable device provides sensitive gas detection at temperatures ranging from at least 450 to 600 C. The barrier layer prevents reactions between the catalytic metal layer and the substrate layer. Conventional semiconductor fabrication techniques are used to fabricate the small-sided sensors. The use of a thicker palladium oxide barrier layer for other semiconductor structures such as a capacitor and transistor structures is also disclosed.

Ligand-free palladium-mediated site-specific protein labeling inside gram-negative bacterial pathogens.

PubMed

Li, Jie; Lin, Shixian; Wang, Jie; Jia, Shang; Yang, Maiyun; Hao, Ziyang; Zhang, Xiaoyu; Chen, Peng R

2013-05-15

Palladium, a key transition metal in advancing modern organic synthesis, mediates diverse chemical conversions including many carbon-carbon bond formation reactions between organic compounds. However, expanding palladium chemistry for conjugation of biomolecules such as proteins, particularly within their native cellular context, is still in its infancy. Here we report the site-specific protein labeling inside pathogenic Gram-negative bacterial cells via a ligand-free palladium-mediated cross-coupling reaction. Two rationally designed pyrrolysine analogues bearing an aliphatic alkyne or an iodophenyl handle were first encoded in different enteric bacteria, which offered two facial handles for palladium-mediated Sonogashira coupling reaction on proteins within these pathogens. A GFP-based bioorthogonal reaction screening system was then developed, allowing evaluation of both the efficiency and the biocompatibilty of various palladium reagents in promoting protein-small molecule conjugation. The identified simple compound-Pd(NO3)2 exhibited high efficiency and biocompatibility for site-specific labeling of proteins in vitro and inside living E. coli cells. This Pd-mediated protein coupling method was further utilized to label and visualize a Type-III Secretion (T3S) toxin-OspF in Shigella cells. Our strategy may be generally applicable for imaging and tracking various virulence proteins within Gram-negative bacterial pathogens.

Metallic and Ceramic Thin Film Thermocouples for Gas Turbine Engines

PubMed Central

Tougas, Ian M.; Amani, Matin; Gregory, Otto J.

2013-01-01

Temperatures of hot section components in today's gas turbine engines reach as high as 1,500 °C, making in situ monitoring of the severe temperature gradients within the engine rather difficult. Therefore, there is a need to develop instrumentation (i.e., thermocouples and strain gauges) for these turbine engines that can survive these harsh environments. Refractory metal and ceramic thin film thermocouples are well suited for this task since they have excellent chemical and electrical stability at high temperatures in oxidizing atmospheres, they are compatible with thermal barrier coatings commonly employed in today's engines, they have greater sensitivity than conventional wire thermocouples, and they are non-invasive to combustion aerodynamics in the engine. Thin film thermocouples based on platinum:palladium and indium oxynitride:indium tin oxynitride as well as their oxide counterparts have been developed for this purpose and have proven to be more stable than conventional type-S and type-K thin film thermocouples. The metallic and ceramic thin film thermocouples described within this paper exhibited remarkable stability and drift rates similar to bulk (wire) thermocouples. PMID:24217356

Metallic and ceramic thin film thermocouples for gas turbine engines.

PubMed

Tougas, Ian M; Amani, Matin; Gregory, Otto J

2013-11-08

Temperatures of hot section components in today's gas turbine engines reach as high as 1,500 °C, making in situ monitoring of the severe temperature gradients within the engine rather difficult. Therefore, there is a need to develop instrumentation (i.e., thermocouples and strain gauges) for these turbine engines that can survive these harsh environments. Refractory metal and ceramic thin film thermocouples are well suited for this task since they have excellent chemical and electrical stability at high temperatures in oxidizing atmospheres, they are compatible with thermal barrier coatings commonly employed in today's engines, they have greater sensitivity than conventional wire thermocouples, and they are non-invasive to combustion aerodynamics in the engine. Thin film thermocouples based on platinum:palladium and indium oxynitride:indium tin oxynitride as well as their oxide counterparts have been developed for this purpose and have proven to be more stable than conventional type-S and type-K thin film thermocouples. The metallic and ceramic thin film thermocouples described within this paper exhibited remarkable stability and drift rates similar to bulk (wire) thermocouples.

Bi-metallic nanoparticles as cathode electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Jun; Amine, Khalil; Wang, Xiaoping

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

Material and system for catalytic reduction of nitrogen oxide in an exhaust stream of a combustion process

DOEpatents

Gardner, Timothy J.; Lott, Stephen E.; Lockwood, Steven J.; McLaughlin, Linda I.

1998-01-01

A catalytic material of activated hydrous metal oxide doped with platinum, palladium, or a combination of these, and optionally containing an alkali or alkaline earth metal, that is effective for NO.sub.X reduction in an oxidizing exhaust stream from a combustion process is disclosed. A device for reduction of nitrogen oxides in an exhaust stream, particularly an automotive exhaust stream, the device having a substrate coated with the activated noble-metal doped hydrous metal oxide of the invention is also provided.

Functionalization of Platinum Complexes for Biomedical Applications.

PubMed

Wang, Xiaoyong; Wang, Xiaohui; Guo, Zijian

2015-09-15

Platinum-based anticancer drugs are the mainstay of chemotherapy regimens in clinic. Nevertheless, the efficacy of platinum drugs is badly affected by serious systemic toxicities and drug resistance, and the pharmacokinetics of most platinum drugs is largely unknown. In recent years, a keen interest in functionalizing platinum complexes with bioactive molecules, targeting groups, photosensitizers, fluorophores, or nanomaterials has been sparked among chemical and biomedical researchers. The motivation for functionalization comes from some of the following demands: to improve the tumor selectivity or minimize the systemic toxicity of the drugs, to enhance the cellular accumulation of the drugs, to overcome the tumor resistance to the drugs, to visualize the drug molecules in vitro or in vivo, to achieve a synergistic anticancer effect between different therapeutic modalities, or to add extra functionality to the drugs. In this Account, we present different strategies being used for functionalizing platinum complexes, including conjugation with bisphosphonates, peptides, receptor-specific ligands, polymers, nanoparticles, magnetic resonance imaging contrast agents, metal chelators, or photosensitizers. Among them, bisphosphonates, peptides, and receptor-specific ligands are used for actively targeted drug delivery, polymers and nanoparticles are for passively targeted drug delivery, magnetic resonance imaging contrast agents are for theranostic purposes, metal chelators are for the treatment or prevention of Alzheimer's disease (AD), and photosensitizers are for photodynamic therapy of cancers. The rationales behind these designs are explained and justified at the molecular or cellular level, associating with the requirements for diagnosis, therapy, and visualization of biological processes. To illustrate the wide range of opportunities and challenges that are emerging in this realm, representative examples of targeted drug delivery systems, anticancer conjugates

Platinum and palladium incorporation into phosphate/viologen-phosphonates of zirconium and hafnium: synthesis and characterization

NASA Astrophysics Data System (ADS)

Dokoutchaev, Alexandre; Krishnan, Venkatesan V.; Thompson, Mark E.; Balasubramanian, Mahalingam

1998-10-01

We have continued previous efforts to synthesize and characterize a microporous metal phosphate/viologen-phosphonate compound, [(ZrF) 2(PO 4)(O 3PCH 2CH 2-4,4'-bipyridinium-CH 2CH 2PO 3)] ṡF·2H 2O, ZrPO PV. A derivative of this material has been shown to be an efficient catalyst for the production of hydrogen peroxide from hydrogen and oxygen. This paper has two objectives—one is to optimize the synthetic routes leading to the preparation of MPO PV (M=zirconium or hafnium) and the second is to characterize MPO PV and the derivatives formed by Pt or Pd incorporation by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), inductively coupled plasma-mass spectrometry (ICP-MS) and X-ray absorption fine structure analysis (XAFS). Powder XRD data have shown much higher crystallinity in MPO PV samples prepared by hydrothermal methods than those prepared by reflux methods. In the hydrothermal synthesis, the amount of mineralizer (HF) present controlled the crystallite size (as determined from TEM micrographs). The larger the quantity of HF in the bomb, the larger the size of the crystals but the lower the yield of the MPO PV material. Crystal sizes of about 2.5 μm in length and 0.15 μm in diameter have been made with very large quantities of HF as mineralizer (10 times the required stoichiometric amount). Ion exchange of the material by PdCl 42- has resulted in the incorporation of the PdCl 42- ions in place of X - in the material. This has been confirmed by XAFS studies that demonstrate the oxidation state of Pd is 2+ and show four Cl atoms bound to Pd. Upon reduction it has been confirmed (by XAFS) that the palladium exists as metal with oxidation state of zero. Ion exchange by PdCl 42- and PtCl 42- and subsequent reduction of the material suspension by hydrogen result in the formation of separate Pt and Pd colloids in the close vicinity of the crystallites. TEM micrographs show clearly that the Pt metal

Homogeneous Palladium-Catalyzed Transfer Hydrogenolysis of Benzylic Alcohols Using Formic Acid as Reductant.

PubMed

Ciszek, Benjamin; Fleischer, Ivana

2018-04-12

Herein we report the first homogeneous palladium-based transfer hydrogenolysis of benzylic alcohols using an in situ formed palladium-phosphine complex and formic acid as reducing agent. The reaction requires a catalyst loading as low as only 1 mol% of palladium and just a slight excess of reductant to obtain the deoxygenated alkylarenes in good to excellent yields. Besides demonstrating the broad applicability for primary, secondary and tertiary benzylic alcohols, a reaction intermediate could be identified. Additionally, it could be shown that partial oxidation of the applied phosphine ligand was beneficial for the course of the reaction, presumably by stabilizing the active catalyst. Reaction profiles and catalyst poisoning experiments were used to characterize the catalyst, the results indicate a homogeneous metal complex as active species. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Linking structure to function: The search for active sites in non-platinum group metal oxygen reduction reaction catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holby, Edward F.; Zelenay, Piotr

Atomic-scale structures of oxygen reduction reaction (ORR) active sites in non-platinum group metal (non-PGM) catalysts, made from pyrolysis of carbon, nitrogen, and transition-metal (TM) precursors have been the subject of continuing discussion in the fuel cell electrocatalysis research community. We found that quantum chemical modeling is a path forward for understanding of these materials and how they catalyze the ORR. Here, we demonstrate through literature examples of how such modeling can be used to better understand non-PGM ORR active site relative stability and activity and how such efforts can also aid in the interpretation of experimental signatures produced by thesemore » materials.« less

Linking structure to function: The search for active sites in non-platinum group metal oxygen reduction reaction catalysts

DOE PAGES

Holby, Edward F.; Zelenay, Piotr

2016-05-17

Atomic-scale structures of oxygen reduction reaction (ORR) active sites in non-platinum group metal (non-PGM) catalysts, made from pyrolysis of carbon, nitrogen, and transition-metal (TM) precursors have been the subject of continuing discussion in the fuel cell electrocatalysis research community. We found that quantum chemical modeling is a path forward for understanding of these materials and how they catalyze the ORR. Here, we demonstrate through literature examples of how such modeling can be used to better understand non-PGM ORR active site relative stability and activity and how such efforts can also aid in the interpretation of experimental signatures produced by thesemore » materials.« less

Palladium-catalyzed cocyclotrimerization of arynes with a pyramidalized alkene.

PubMed

Alonso, José M; Quiroga, Sabela; Codony, Sandra; Turcu, Andreea L; Barniol-Xicota, Marta; Pérez, Dolores; Guitián, Enrique; Vázquez, Santiago; Peña, Diego

2018-05-23

The metal-catalyzed [2+2+2] cocycloaddition of arynes with pyramidalized alkenes is presented. The generation of a highly reactive pyramidalized alkene in the presence of a large excess of in situ-produced arynes led to the corresponding cocyclotrimerization (1 : 2)-adducts in good yields, establishing the first example of a palladium-based reaction of a pyramidalized alkene.

Resistivity and resistivity fluctuations of thin-film platinum-aluminum oxide granular metal-insulator composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mantese, J.V.

1986-01-01

Thin film metal-insulator composites were used to study how the resistivity and fluctuations in the resistivity were altered by changes in conduction mechanism so as to understand the source of the fluctuations and to better understand the conduction processes themselves. Metal-insulator composites were prepared by co-evaporation of platinum and aluminum oxide in a high vacuum system to create a series of films which had a range of metal volume fill fractions, p, from 23 to 100%. The samples were patterned using standard photolithographic techniques to form sample geometries of typical dimensions, length approx.40 ..mu..m, width approx.2 ..mu..m, and thickness approx.1500more » A. The resistivity rho, and power spectral density of the resistivity fluctuations, S/sub rho/(f), were measured as a function of p and temperature, T. Rho(p,T) was found to be a rapidly increasing function of decreasing p, rising monotonically by more than 7 orders of magnitude as p was decreased from 100% to 23%. For p greater than or equal to 59% the resistivity decreased linearly with decreasing temperature until limited by impurity scattering. The resistivities for the low metal fill fraction materials (P greater than or equal to 50%) increased as the temperature was reduced as expected of thermally assisted tunneling conduction in metal-insulator composites. The transition from metallic conduction to thermally assisted tunneling occurred at a critical value, p/sub c/, between 59% and 50% Pt.« less

STRONTIUM AS AN EFFICIENT PROMOTER FOR SUPPORTED PALLADIUM HYDROGENATION CATALYSTS

EPA Science Inventory

The effect of strontium promotion is studied for a series of supported palladium catalysts such as Pd/zeolite-β, Pd/Al₂O₃, Pd/SiO₂, Pd/hydrotalcite and Pd/MgO. Strontium is found to be an effective promoter for enhancing the metal area, perce...

Electroless plating of ultrathin palladium films: self-initiated deposition and application in microreactor fabrication

NASA Astrophysics Data System (ADS)

Muench, Falk; Oezaslan, Mehtap; Svoboda, Ingrid; Ensinger, Wolfgang

2015-10-01

We present new electroless palladium plating reactions, which can be applied to complex-shaped substrates and lead to homogeneous, dense and conformal palladium films consisting of small nanoparticles. Notably, autocatalytic and surface-selective metal deposition could be achieved on a wide range of materials without sensitization and activation pretreatments. This provides a facile and competitive route to directly deposit well-defined palladium nanofilms on e.g. carbon, paper, polymers or glass substrates. The reactions proceed at mild conditions and are based on easily accessible chemicals (reducing agent: hydrazine; metal source: PdCl2; ligands: ethylenediaminetetraacetic acid (EDTA), acetylacetone). Additionally, the water-soluble capping agent 4-dimethylaminopyridine (DMAP) is employed to increase the bath stability, to ensure the formation of small particles and to improve the film conformity. The great potential of the outlined reactions for micro- and nanofabrication is demonstrated by coating an ion-track etched polycarbonate membrane with a uniform Pd film of approximately 20 nm thickness. The as-prepared membrane is then employed as a highly miniaturized flow reactor, using the reduction of 4-nitrophenol with NaBH4 as a model reaction.

Pyrometallurgical Recovery of Platinum Group Metals from Spent Catalysts

NASA Astrophysics Data System (ADS)

Peng, Zhiwei; Li, Zhizhong; Lin, Xiaolong; Tang, Huimin; Ye, Lei; Ma, Yutian; Rao, Mingjun; Zhang, Yuanbo; Li, Guanghui; Jiang, Tao

2017-09-01

As an important secondary resource with abundant platinum group metals (PGMs), spent catalysts demand recycling for both economic and environmental benefits. This article reviews the main pyrometallurgical processes for PGM recovery from spent catalysts. Existing processes, including smelting, vaporization, and sintering processes, are discussed based in part on a review of the physiochemical characteristics of PGMs in spent catalysts. The smelting technology, which produces a PGM-containing alloy, is significantly influenced by the addition of various collectors, such as lead, copper, iron, matte, or printed circuit board (PCB), considering their chemical affinities for PGMs. The vaporization process can recover PGMs in vapor form at low temperatures (250-700°C), but it suffers high corrosion and potential environmental and health risks as a result of involvement of the hazardous gases, mainly Cl2 and CO. The sintering process serves as a reforming means for recycling of the spent catalysts by in situ reduction of their oxidized PGMs components. Among these processes, the smelting process seems more promising although its overall performance can be further improved by seeking a suitable target-oriented collector and flux, together with proper pretreatment and process intensification using an external field.

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.

Platinum Recovery from Synthetic Extreme Environments by Halophilic Bacteria.

PubMed

Maes, Synthia; Props, Ruben; Fitts, Jeffrey P; Smet, Rebecca De; Vilchez-Vargas, Ramiro; Vital, Marius; Pieper, Dietmar H; Vanhaecke, Frank; Boon, Nico; Hennebel, Tom

2016-03-01

Metal recycling based on urban mining needs to be established to tackle the increasing supply risk of critical metals such as platinum. Presently, efficient strategies are missing for the recovery of platinum from diluted industrial process streams, often characterized by extremely low pHs and high salt concentrations. In this research, halophilic mixed cultures were employed for the biological recovery of platinum (Pt). Halophilic bacteria were enriched from Artemia cysts, living in salt lakes, in different salt matrices (sea salt mixture and NH4Cl; 20-210 g L(-1) salts) and at low to neutral pH (pH 3-7). The main taxonomic families present in the halophilic cultures were Halomonadaceae, Bacillaceae, and Idiomarinaceae. The halophilic cultures were able to recover >98% Pt(II) and >97% Pt(IV) at pH 2 within 3-21 h (4-453 mg Ptrecovered h(-1) g(-1) biomass). X-ray absorption spectroscopy confirmed the reduction to Pt(0) and transmission electron microscopy revealed both intra- and extracellular Pt precipitates, with median diameters of 9-30 nm and 11-13 nm, for Pt(II) and Pt(IV), respectively. Flow cytometric membrane integrity staining demonstrated the preservation of cell viability during platinum recovery. This study demonstrates the Pt recovery potential of halophilic mixed cultures in acidic saline conditions.

Thin Metallic Films From Solvated Metal Atoms

NASA Astrophysics Data System (ADS)

Trivino, Galo C.; Klabunde, Kenneth J.; Dale, Brock

1988-02-01

Metals were evaporated under vacuum and the metal atoms solvated by excess organic solvents at low temperature. Upon warming stable colloidal metal particles were formed by controlled metal atom clustering. The particles were stabilized toward flocculation by solvation and electrostatic effects. Upon solvent removal the colloidal particles grew to form thin films that were metallic in appearance, but showed higher resistivities than pure metallic films. Gold, palladium, platinium, and especially indium are discussed.

Publications - RDF 2000-4 | Alaska Division of Geological & Geophysical

Science.gov Websites

Oxides; Palladium; Platinum; Rare Earth Elements; STATEMAP Project; Trace Metals Top of Page Department Surveys Skip to content State of Alaska myAlaska My Government Resident Business in Alaska Visiting Alaska State Employees DGGS State of Alaska search Alaska Division of Geological & Geophysical

Pt(II) and Pd(II) complexes with ibuprofen hydrazide: Characterization, theoretical calculations, antibacterial and antitumor assays and studies of interaction with CT-DNA

NASA Astrophysics Data System (ADS)

Manzano, Carlos M.; Bergamini, Fernando R. G.; Lustri, Wilton R.; Ruiz, Ana Lúcia T. G.; de Oliveira, Ellen C. S.; Ribeiro, Marcos A.; Formiga, André L. B.; Corbi, Pedro P.

2018-02-01

Palladium(II) and platinum(II) complexes with a hydrazide derivative of ibuprofen (named HIB) were synthesized and characterized by chemical and spectroscopic methods. Elemental and thermogravimetric analyses, as well as ESI-QTOF-MS studies for both complexes, confirmed a 1:2:2 metal/HIB/Cl- molar ratio. The crystal structure of the palladium(II) complex was solved by single crystal X-ray diffractometric analysis, which permitted identifying the coordination formula [PdCl2(HIB)2]. Crystallographic studies also indicate coordination of HIB to the metal by the NH2 group. Nuclear magnetic resonance and infrared spectroscopies reinforced the coordination observed in the crystal structure and suggested that the platinum(II) complex presents similar coordination modes and structure when compared with the Pd(II) complex. The complexes had their structures optimized with the aid of DFT methods. In vitro antiproliferative assays showed that the [PdCl2(HIB)2] complex is active over ovarian cancer cell line OVCAR-03, while biophysical studies indicated its capacity to interact with CT-DNA. The complexes were inactive over Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa bacterial strains.

Palladium-Catalyzed Allylic C-H Bond Functionalization of Olefins

NASA Astrophysics Data System (ADS)

Liu, Guosheng; Wu, Yichen

Transition metal-mediated carbon-hydrogen bond cleavage and functionalization is a mechanistically interesting and synthetically attractive process. One of the important cases is the removal of a allylic hydrogen from an olefin by a PdII salt to yield a π-allylpalladium complex, followed by nucleophilic attack to efficient produce allylic derivatives. In contrast to the well-known allylic acetoxylation of cyclohexene, the reaction of open-chain olefins is fairly poor until recent several years. Some palladium catalytic systems have been reported to achieve allylic C-H functionalization, including acetoxylation, amination and alkylation of terminal alkenes. In the most of cases, ligand is crucial to the success of the transformation. This review surveys the recent development of palladium-catalyzed allylic C-H functionalziation of alkenes. These results promise a significant increase in the scope of olefin transformation.

Synthesis, crystal structure, fluorescence and electrochemical studies of a new tridentate Schiff base ligand and its nickel(II) and palladium(II) complexes

NASA Astrophysics Data System (ADS)

Shafaatian, Bita; Soleymanpour, Ahmad; Kholghi Oskouei, Nasim; Notash, Behrouz; Rezvani, Seyyed Ahmad

2014-07-01

A new unsymmetrical tridentate Schiff base ligand was derived from the 1:1 M condensation of ortho-vanillin with 2-mercaptoethylamine. Nickel and palladium complexes were obtained by the reaction of the tridentate Schiff base ligand with nickel(II) acetate tetrahydrate and palladium(II) acetate in 2:1 M ratio. In nickel and palladium complexes the ligand was coordinated to metals via the imine N and enolic O atoms. The S groups of Schiff bases were not coordinated to the metals and S-S coupling was occured. The complexes have been found to possess 1:2 Metal:Ligand stoichiometry and the molar conductance data revealed that the metal complexes were non-electrolytes. The complexes exhibited octahedral coordination geometry. The emission spectra of the ligand and its complexes were studied in methanol. Electrochemical properties of the ligand and its metal complexes were investigated in the CH3CN solvent at the 100 mV s-1 scan rate. The ligand and metal complexes showed both reversible and quasi-reversible processes at this scan rate. The Schiff base and its complexes have been characterized by IR, 1H NMR, UV/Vis, elemental analyses and conductometry. The crystal structure of nickel complex has been determined by single crystal X-ray diffraction.

Miniaturized metal (metal alloy)/ PdO.sub.x/SiC hydrogen and hydrocarbon gas sensors

NASA Technical Reports Server (NTRS)

Hunter, Gary W. (Inventor); Xu, Jennifer C. (Inventor); Lukco, Dorothy (Inventor)

2011-01-01

A miniaturized Schottky diode hydrogen and hydrocarbon sensor and the method of making same is disclosed and claimed. The sensor comprises a catalytic metal layer, such as palladium, a silicon carbide substrate layer and a thin barrier layer in between the catalytic and substrate layers made of palladium oxide (PdO.sub.x ). This highly stable device provides sensitive gas detection at temperatures ranging from at least 450 to 600.degree. C. The barrier layer prevents reactions between the catalytic metal layer and the substrate layer. Conventional semiconductor fabrication techniques are used to fabricate the small-sized sensors. The use of a thicker palladium oxide barrier layer for other semiconductor structures such as a capacitor and transistor structures is also disclosed.

Miniaturized metal (metal alloy)/ PdO.sub.x/SiC hydrogen and hydrocarbon gas sensors

NASA Technical Reports Server (NTRS)

Xu, Jennifer C. (Inventor); Hunter, Gary W. (Inventor); Lukco, Dorothy (Inventor)

2008-01-01

A miniaturized Schottky diode hydrogen and hydrocarbon sensor and the method of making same is disclosed and claimed. The sensor comprises a catalytic metal layer, such as palladium, a silicon carbide substrate layer and a thin barrier layer in between the catalytic and substrate layers made of palladium oxide (PdO.sub.x). This highly stable device provides sensitive gas detection at temperatures ranging from at least 450 to 600.degree. C. The barrier layer prevents reactions between the catalytic metal layer and the substrate layer. Conventional semiconductor fabrication techniques are used to fabricate the small-sized sensors. The use of a thicker palladium oxide barrier layer for other semiconductor structures such as a capacitor and transistor structures is also disclosed.

Refractory metal joining for first wall applications

NASA Astrophysics Data System (ADS)

Cadden, C. H.; Odegard, B. C.

2000-12-01

The potential use of high temperature coolant (e.g. 900°C He) in first wall structures would preclude the applicability of copper alloy heat sink materials and refractory metals would be potential replacements. Brazing trials were conducted in order to examine techniques to join tungsten armor to high tungsten (90-95 wt%) or molybdenum TZM heat sink materials. Palladium-, nickel- and zirconium-based filler metals were investigated using brazing temperatures ranging from 1000°C to 1275°C. Palladium-nickel and palladium-cobalt braze alloys were successful in producing generally sound metallurgical joints in tungsten alloy/tungsten couples, although there was an observed tendency for the pure tungsten armor material to exhibit grain boundary cracking after bonding. The zirconium- and nickel-based filler metals produced defect-containing joints, specifically cracking and porosity, respectively. The palladium-nickel braze alloy produced sound joints in the Mo TZM/tungsten couple. Substitution of a lanthanum oxide-containing, fine-grained tungsten material (for the pure tungsten) eliminated the observed tungsten grain boundary cracking.

Hole doping, hybridization gaps, and electronic correlation in graphene on a platinum substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, Jinwoong; Hwang, Hwihyeon; Kim, Min-Jeong

The interaction between graphene and substrates provides a viable route to enhance the functionality of both materials. Depending on the nature of electronic interaction at the interface, the electron band structure of graphene is strongly influenced, allowing us to make use of the intrinsic properties of graphene or to design additional functionalities in graphene. In this paper, we present an angle-resolved photoemission study on the interaction between graphene and a platinum substrate. The formation of an interface between graphene and platinum leads to a strong deviation in the electronic structure of graphene not only from its freestanding form but alsomore » from the behavior observed on typical metals. Finally, the combined study on the experimental and theoretical electron band structure unveils the unique electronic properties of graphene on a platinum substrate, which singles out graphene/platinum as a model system investigating graphene on a metallic substrate with strong interaction.« less

Hole doping, hybridization gaps, and electronic correlation in graphene on a platinum substrate

DOE PAGES

Hwang, Jinwoong; Hwang, Hwihyeon; Kim, Min-Jeong; ...

2017-08-02

The interaction between graphene and substrates provides a viable route to enhance the functionality of both materials. Depending on the nature of electronic interaction at the interface, the electron band structure of graphene is strongly influenced, allowing us to make use of the intrinsic properties of graphene or to design additional functionalities in graphene. In this paper, we present an angle-resolved photoemission study on the interaction between graphene and a platinum substrate. The formation of an interface between graphene and platinum leads to a strong deviation in the electronic structure of graphene not only from its freestanding form but alsomore » from the behavior observed on typical metals. Finally, the combined study on the experimental and theoretical electron band structure unveils the unique electronic properties of graphene on a platinum substrate, which singles out graphene/platinum as a model system investigating graphene on a metallic substrate with strong interaction.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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.

The role of arsenic in the hydrolysis and DNA metalation processes in an arsenous acid-platinum(ii) anticancer complex.

PubMed

Marino, T; Parise, A; Russo, N

2017-01-04

Platinum(ii)-based molecules are the most commonly used anticancer drugs in the chemotherapeutic treatment of tumours but possess serious side effects and some cancer types exhibit resistance with respect to these compounds (e.g. cisplatin). For these reasons, the research of new compounds that can bypass this limitation is in continuous development. Recently, mixed Pt(ii)-As(iii) systems have been synthesized and tested as potential anticancer agents. The mechanism of action of these kinds of drugs is unclear. Since in other platinum(ii) containing drugs, hydrolysis plays an important role in the activation of the compound before it reaches DNA, we have explored the aquation process using density functional theory (DFT), focusing our attention on the arsenoplatin complex, [Pt(μ-NHC(CH 3 )O) 2 ClAs(OH) 2 ]. As DNA is believed to be the cellular target for Pt anticancer drugs, the metalation mechanism of DNA purine bases has been also investigated. Also for this new drug it appears that guanine is the preferred site with respect to adenine as with other platinum-containing compounds. A comparison with cisplatin is performed in order to highlight the contribution of arsenic in the anticancer activity of this new proposed anticancer agent.

Mineral resource of the month: tellurium

USGS Publications Warehouse

,

2013-01-01

The article offers information on tellerium, a rare and expensive metal. Tellerium is considered the 71st most abundant element in Earth's crust, along with platinum and palladium. The element belongs to the chalcogen chemical family, and is recovered as a byproduct of nonferrous metal mining. The global demand for tellerium has significantly increased due to the growth in solar cell production in the U.S. and Europe, and thermoplastics in China.

High-resolution electron microscopy and electron energy-loss spectroscopy of giant palladium clusters

NASA Astrophysics Data System (ADS)

Oleshko, V.; Volkov, V.; Gijbels, R.; Jacob, W.; Vargaftik, M.; Moiseev, I.; van Tendeloo, G.

1995-12-01

Combined structural and chemical characterization of cationic polynuclear palladium coordination compounds Pd561L60(OAc)180, where L=1,10-phenantroline or 2,2'-bipyridine has been carried out by high-resolution electron microscopy (HREM) and analytical electron microscopy methods including electron energy-loss spectroscopy (EELS), zero-loss electron spectroscopic imaging, and energy-dispersive X-ray spectroscopy (EDX). The cell structure of the cluster matter with almost completely uniform metal core size distributions centered around 2.3 ±0.5 nm was observed. Zero-loss energy filtering allowed to improve the image contrast and resolution. HREM images showed that most of the palladium clusters had a cubo-octahedral shape. Some of them had a distorted icosahedron structure exhibiting multiple twinning. The selected-area electron diffraction patterns confirmed the face centered cubic structure with lattice parameter close to that of metallic palladium. The energy-loss spectra of the populations of clusters contained several bands, which could be assigned to the delayed Pd M4, 5-edge at 362 eV, the Pd M3-edge at 533 eV and the Pd M2-edge at 561 eV, the NK-edge at about 400 eV, the O K-edge at 532 eV overlapping with the Pd M3-edge and the carbon C K-edge at 284 eV. Background subtraction was applied to reveal the exact positions and fine structure of low intensity elemental peaks. EELS evaluations have been confirmed by EDX. The recorded series of the Pd M-edges and the N K-edge in the spectra of the giant palladium clusters obviously were related to Pd-Pd- and Pd-ligand bonding.

Platinum(II) acetate complexes in hydrogenation of unsaturated compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berenblyum, A.S.; Goranskaya, T.P.; Mund, S.L.

1979-12-20

In order to further elucidate the effect of the ligand environment in the complexes of group VIII metals on the activity of H/sub 2/, the catalytic properties of Pt(II) compounds with oxygen-containing acido ligands was studied. The platinum(II) acetate complexes with aniline and triphenylphosphine were synthesized. IR spectral studies indicated that platinum(II) acetate formed complexes with either of the other compounds singly or together. Dimethylformamide(DMF) solutions of platinum acetate and its complexes with aniline and/or triphenylphosphine all absorb H/sub 2/ in the temperature range of 20 to 90/sup 0/C and at a H/sub 2/ pressure of 1 atm. After themore » absorption of H/sub 2/, the DMF solutions of (aniline)(triphenylphosphine)platinum(II)diacetate complex were found to catalyze the hydrogenaton of O/sub 2/ and 1,3-pentadiene.« less

The Effect of Palladium Additions on the Solidus/Liquidus Temperatures and Wetting Properties of Ag-CuO Based Air Brazes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darsell, Jens T.; Weil, K. Scott

2007-05-16

As a means of increasing the use temperature of ceramic-ceramic and ceramic-metal air brazes, palladium was investigated as possible ternary addition to the currently employed silver - copper oxide system. The silver component was directly substituted with palladium to form the following series of alloys: (100-y)[(100-z)Pd - (z)Ag] - (y)CuOx where y = 0 - 34 mol% CuOx, z = 50 - 100 mol% silver, and x = 0, 0.5, and 1, denoting copper metal, Cu2O, or CuO. From differential scanning calorimetry, it was determined that the addition of palladium causes an increase in the solidus and liquidus temperatures ofmore » the resulting Pd-Ag-CuO brazes. In general, the liquidus was found to increase by approximately 220°C for the (100-y)(25Pd - 75Ag) - (z)CuOx filler metal compositions relative to comparable Ag-CuOx alloys. Likewise, the solidus was found to increase for these alloys, respectively by 185°C and 60°C, respectively for CuOx contents of y = 0 - 1mol% and 4 - 10 mol%. For the (100-y)(50Pd - 50Ag) - (y)CuOx alloys, the solidus increased between 280 - 390°C over a copper oxide compositional range of x = 0 to 8 mol%. It was determined from sessile drop experiments conducted on alumina substrates that in all cases the palladium causes an increase in the wetting angle relative to the corresponding binary braze. Alloy compositions of (100-y)(25Pd - 75Ag) - (y)CuOx displayed increased wetting angles of 5-20° relative to comparable binary compositions. (100-y)(50Pd - 50Ag) - (y)CuOx alloys exhibited an increase in contact angle of 10-60° and compositions containing less than 10 mol% CuOx were not able to wet the substrate. Scanning electron microscopy indicated that the microstructure of the braze consists of discrete CuOx precipitates in an alloyed silver-palladium matrix. In both the binary and ternary filler metal formulations, a reaction layer consisting of CuAlO2 was observed along the interface with the alumina substrate. This reaction product appears to be

Platinum clusters with precise numbers of atoms for preparative-scale catalysis.

PubMed

Imaoka, Takane; Akanuma, Yuki; Haruta, Naoki; Tsuchiya, Shogo; Ishihara, Kentaro; Okayasu, Takeshi; Chun, Wang-Jae; Takahashi, Masaki; Yamamoto, Kimihisa

2017-09-25

Subnanometer noble metal clusters have enormous potential, mainly for catalytic applications. Because a difference of only one atom may cause significant changes in their reactivity, a preparation method with atomic-level precision is essential. Although such a precision with enough scalability has been achieved by gas-phase synthesis, large-scale preparation is still at the frontier, hampering practical applications. We now show the atom-precise and fully scalable synthesis of platinum clusters on a milligram scale from tiara-like platinum complexes with various ring numbers (n = 5-13). Low-temperature calcination of the complexes on a carbon support under hydrogen stream affords monodispersed platinum clusters, whose atomicity is equivalent to that of the precursor complex. One of the clusters (Pt 10 ) exhibits high catalytic activity in the hydrogenation of styrene compared to that of the other clusters. This method opens an avenue for the application of these clusters to preparative-scale catalysis.The catalytic activity of a noble metal nanocluster is tied to its atomicity. Here, the authors report an atom-precise, fully scalable synthesis of platinum clusters from molecular ring precursors, and show that a variation of only one atom can dramatically change a cluster's reactivity.

Study of palladium plating components

NASA Technical Reports Server (NTRS)

1977-01-01

Palladium deposits were prepared by electrolysis for evaluation as catalytic materials. Electrolysis was carried out in acidic solutions consisting of either 1.0 M in NaCl and 0.01 M PdCl2 or 1.0 M NaCl and 0.04 M PdCl2. It was during the preparation of the palladium deposits that unexpected observations were made that led to the request for analytical services. The analyses did not, nor were they intended to, answer all of the questions. They did, however, shed light on the nature and magnitude of some of the contaminants in the solutions and in the palladium electrodes, as well as characterize the forms of the palladium deposits. Results of analyses are grouped into solution, deposit, and electrode categories for comparison purposes.

Precise Control Over Morphology and Density of Metal and Transition Metal Nanostructures for Sensing and Energy Related Applications

NASA Astrophysics Data System (ADS)

Tran, Minh

Metallic nanostructures are of great interest due to their applicability in various modern technologies, such as catalysis, sensing, and optoelectronics. In this work, we employed three solution-based methods, including colloidal suspension synthesis, modified galvanic displacement, and electrodeposition, to synthesize nanostructured metals and transition metals, including gold (Au), copper (Cu), platinum (Pt), palladium (Pd), nickel (Ni), and cobalt (Co). Our focus was to establish process-structure-property relationship and explore their applicability in the field of sensing and clean energy generation. More precisely we established relationships between experimental parameters, such as temperature, applied potential, electrolyte pH, reactant concentration, additive, and the number of deposition cycles, and the characteristics of the nanostructures, such as morphology, density, size, and size distribution. Our results indicated that the nanostructures were tunable by adjusting the process parameters. This provided insight into the growth mechanisms of the metallic nanostructures. Since properties of the nanostructures are tunable by controlling the structure, our results provided researchers with additional tools to obtain nanomaterials with desired properties for specific applications. The materials synthesized by our methods were utilized to as substrates for surface enhanced Raman spectroscopy (SERS) and as photocathodes for photoelectrochemical production of hydrogen. The results showed that the performances of our materials were either promising or compatible with those reported in the literature, thus bringing new opportunities to the development of low-cost, high-performance, and flexible nanomaterials for the current and future technologies.

Hydroisomerization of n-Hexane Using Acidified Metal-Organic Framework and Platinum Nanoparticles.

PubMed

Sabyrov, Kairat; Jiang, Juncong; Yaghi, Omar M; Somorjai, Gabor A

2017-09-13

Exceptionally high surface area and ordered nanopores of a metal-organic framework (MOF) are exploited to encapsulate and homogeneously disperse a considerable amount of phosphotungstic acid (PTA). When combined with platinum nanoparticles positioned on the external surface of the MOF, the construct shows a high catalytic activity for hydroisomerization of n-hexane, a reaction requiring hydrogenation/dehydrogenation and moderate to strong Brønsted acid sites. Characterization of the catalytic activity and acidic sites as a function of PTA loading demonstrates that both the concentration and strength of acidic sites are highest for the catalyst with the largest amount of PTA. The MOF construct containing 60% PTA by weight produces isoalkanes with 100% selectivity and 9-fold increased mass activity as compared to a more traditional aluminosilicate catalyst, further demonstrating the capacity of the MOF to contain a high concentration of active sites necessary for the isomerization reaction.

The Mechanochemical Reaction of Palladium(II) Chloride with a Bidentate Phosphine

ERIC Educational Resources Information Center

Berry, David E.; Carrie, Philippa; Fawkes, Kelli L.; Rebner, Bruce; Xing, Yao

2010-01-01

This experiment describes the reaction of palladium(II) chloride with 1,5-bis(diphenylphosphino)pentane by grinding the two powders together in the solid state. The product is the precursor for the metalation reaction at one of the methylene carbon atoms of the ligand's backbone. The final product is known to be a catalyst for Suzuki-Miyaura…

Platinum-Based Nanocages with Subnanometer-Thick Walls and Well-Defined Facets

DOE PAGES

Zhang, Lei; Wang, Xue; Chi, Miaofang; ...

2015-07-24

A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few atomic layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. Density functional theory calculations suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra asmore » templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, respectively, which exhibited distinctive catalytic activities toward oxygen reduction.« less

Pd-loaded carbon felt as the cathode for selective dechlorination of 2,4-dichlorophenoxyacetic acid in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsyganok, A.I.; Yamanaka, Ichiro; Otsuka, Kiyoshi

1998-11-01

Electrocatalytic reductive dehalogenation of 2,4-dichlorophenoxyacetic acid (2,4-D) to phenoxyacetic acid in aqueous solution containing MeOH, trifluoroacetic acid, and tetraalkylammonium salt was studied. A Teflon-made two-compartment flow-through cell with a permeable carbon felt cathode and a platinum foil anode was employed. Several noble metals were tested as electrocatalysts. Palladium-loaded carbon felt was found to be the most suitable significantly enhanced its electrocatalytic activity toward 2,4-D dechlorination. The reaction was hypothesized to proceed at carbon-palladium interface areas through 4-chlorine cleavage to form 2-chlorophenoxyacetic acid as the main reaction intermediate.

Catalytic oxidation of dimethyl ether

DOEpatents

Zelenay, Piotr; Wu, Gang; Johnston, Christina M.; Li, Qing

2016-05-10

A composition for oxidizing dimethyl ether includes an alloy supported on carbon, the alloy being of platinum, ruthenium, and palladium. A process for oxidizing dimethyl ether involves exposing dimethyl ether to a carbon-supported alloy of platinum, ruthenium, and palladium under conditions sufficient to electrochemically oxidize the dimethyl ether.

Rapid epitaxy-free graphene synthesis on silicidated polycrystalline platinum

PubMed Central

Babenko, Vitaliy; Murdock, Adrian T.; Koós, Antal A.; Britton, Jude; Crossley, Alison; Holdway, Philip; Moffat, Jonathan; Huang, Jian; Alexander-Webber, Jack A.; Nicholas, Robin J.; Grobert, Nicole

2015-01-01

Large-area synthesis of high-quality graphene by chemical vapour deposition on metallic substrates requires polishing or substrate grain enlargement followed by a lengthy growth period. Here we demonstrate a novel substrate processing method for facile synthesis of mm-sized, single-crystal graphene by coating polycrystalline platinum foils with a silicon-containing film. The film reacts with platinum on heating, resulting in the formation of a liquid platinum silicide layer that screens the platinum lattice and fills topographic defects. This reduces the dependence on the surface properties of the catalytic substrate, improving the crystallinity, uniformity and size of graphene domains. At elevated temperatures growth rates of more than an order of magnitude higher (120 μm min−1) than typically reported are achieved, allowing savings in costs for consumable materials, energy and time. This generic technique paves the way for using a whole new range of eutectic substrates for the large-area synthesis of 2D materials. PMID:26175062

Method for forming gold-containing catalyst with porous structure

DOEpatents

Biener, Juergen; Hamza, Alex V; Baeumer, Marcus; Schulz, Christian; Jurgens, Birte; Biener, Monika M.

2014-07-22

A method for forming a gold-containing catalyst with porous structure according to one embodiment of the present invention includes producing a starting alloy by melting together of gold and at least one less noble metal that is selected from the group consisting of silver, copper, rhodium, palladium, and platinum; and a dealloying step comprising at least partial removal of the less noble metal by dissolving the at least one less noble metal out of the starting alloy. Additional methods and products thereof are also presented.

Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

NASA Astrophysics Data System (ADS)

Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

2016-07-01

For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Qinhua

2004-12-19

The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I 2, ICl, PhSeCl, PhSCl and p-O 2NC 6H 4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellentmore » yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that these

Viscoplasticity of simulated high-level radioactive waste glass containing platinum group metal particles

NASA Astrophysics Data System (ADS)

Uruga, Kazuyoshi; Usami, Tsuyoshi; Tsukada, Takeshi; Komamine, Satoshi; Ochi, Eiji

2014-09-01

The shear rate dependency of the viscosity of three simulated high-level radioactive waste glasses containing 0, 1.2 and 4.5 wt% platinum group metals (PGMs) was examined at a temperature range of 1173-1473 K by a rotating viscometer. Shear stress when the shear rate equals zero, i.e. yield stress, was also measured by capillary method. The viscosity of the glass containing no PGM was shear rate-independent Newtonian fluid. On the other hand, the apparent viscosity of the glasses containing PGMs increased with decreasing shear rate, and nonzero amount of yield stresses were detected from both glasses. The viscosity and yield stress of the glass containing 4.5 wt% PGMs was roughly one to two orders of magnitude greater than the glass containing 1.2 wt% PGMs. These viscoplastic properties were numerically expressed by Casson equation.

Palladium-cobalt particles as oxygen-reduction electrocatalysts

DOEpatents

Adzic, Radoslav [East Setauket, NY; Huang, Tao [Manorville, NY

2009-12-15

The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

Enhanced Dissolution of Platinum Group Metals Using Electroless Iron Deposition Pretreatment

NASA Astrophysics Data System (ADS)

Taninouchi, Yu-ki; Okabe, Toru H.

2017-12-01

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

Platinum and lead markers as indicators of transportation impact.

DOT National Transportation Integrated Search

2009-08-20

The intent of this study was to provide information necessary to characterize the present concentrations of an emerging transportation related contaminant, the platinum group metals (PGM), and to provide background information necessary to explore th...

Nanoscale patterning of two metals on silicon surfaces using an ABC triblock copolymer template.

PubMed

Aizawa, Masato; Buriak, Jillian M

2006-05-03

Patterning technologically important semiconductor interfaces with nanoscale metal films is important for applications such as metallic interconnects and sensing applications. Self-assembling block copolymer templates are utilized to pattern an aqueous metal reduction reaction, galvanic displacement, on silicon surfaces. Utilization of a triblock copolymer monolayer film, polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO), with two blocks capable of selective transport of different metal complexes to the surface (PEO and P2VP), allows for chemical discrimination and nanoscale patterning. Different regions of the self-assembled structure discriminate between metal complexes at the silicon surface, at which time they undergo the spontaneous reaction at the interface. Gold deposition from gold(III) compounds such as HAuCl4(aq) in the presence of hydrofluoric acid mirrors the parent block copolymer core structure, whereas silver deposition from Ag(I) salts such as AgNO3(aq) does the opposite, localizing exclusively under the corona. By carrying out gold deposition first and silver second, sub-100-nm gold features surrounded by silver films can be produced. The chemical selectivity was extended to other metals, including copper, palladium, and platinum. The interfaces were characterized by a variety of methods, including scanning electron microscopy, scanning Auger microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy.

Bioinspired hierarchical nanotubular titania immobilized with platinum nanoparticles for photocatalytic hydrogen production.

PubMed

Liu, Xiaoyan; Li, Jiao; Zhang, Yiming; Huang, Jianguo

2015-05-11

A bioinspired nanocomposite composed of platinum nanoparticles and nanotubular titania was fabricated in which the titania matter was templated by natural cellulose substance. The composite possesses three- dimensional hierarchical structures, and ultrafine metallic platinum particles with sizes of ca. 2 nm were immobilized uniformly on the surfaces of the titania nanotubes. Such a nanocomposite with 1.06 wt % of platinum content shows the optimal photocatalytic hydrogen production activity from water splitting of 16.44 mmol h(-1)  g(-1) , and excessive loading of platinum results in poorer photocatalytic performance. The structural integrity of the nanocomposite upon cyclic water-splitting processes results in its sufficient photocatalytic stability. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

What do we know about metal recycling rates?

USGS Publications Warehouse

Graedel, T.E.; Allwood, J.; Birat, J.-P.; Buchert, M.; Hageluken, C.; Reck, B.K.; Sibley, S.F.; Sonnemann, G.

2011-01-01

The recycling of metals is widely viewed as a fruitful sustainability strategy, but little information is available on the degree to which recycling is actually taking place. This article provides an overview on the current knowledge of recycling rates for 60 metals. We propose various recycling metrics, discuss relevant aspects of recycling processes, and present current estimates on global end-of-life recycling rates (EOL-RR; i.e., the percentage of a metal in discards that is actually recycled), recycled content (RC), and old scrap ratios (OSRs; i.e., the share of old scrap in the total scrap flow). Because of increases in metal use over time and long metal in-use lifetimes, many RC values are low and will remain so for the foreseeable future. Because of relatively low efficiencies in the collection and processing of most discarded products, inherent limitations in recycling processes, and the fact that primary material is often relatively abundant and low-cost (which thereby keeps down the price of scrap), many EOL-RRs are very low: Only for 18 metals (silver, aluminum, gold, cobalt, chromium, copper, iron, manganese, niobium, nickel, lead, palladium, platinum, rhenium, rhodium, tin, titanium, and zinc) is the EOL-RR above 50% at present. Only for niobium, lead, and ruthenium is the RC above 50%, although 16 metals are in the 25% to 50% range. Thirteen metals have an OSR greater than 50%. These estimates may be used in considerations of whether recycling efficiencies can be improved; which metric could best encourage improved effectiveness in recycling; and an improved understanding of the dependence of recycling on economics, technology, and other factors. ?? 2011 by Yale University.

Norilsk, Siberia

NASA Technical Reports Server (NTRS)

2008-01-01

Norilsk is a major city in Krasnoyarsk Krai, Russia, and the northernmost city in Siberia. The city was founded in the 1930s as a settlement for the Norilsk mining-metallurgic complex, sitting near the largest nickel-copper-palladium deposits on Earth. Mining and smelting of nickel, copper, cobalt, platinum, palladium are the major industries. The nickel ore is smelted on site at Norilsk. The smelting is directly responsible for severe pollution, generally acid rain and smog. By some estimates, 1 percent of the entire global emissions of sulfur dioxide comes from this one city. Heavy metal pollution near Norilsk is so severe that it is now economically feasible to mine the soil, which has been polluted so severely that it has economic grades of platinum and palladium.

The image was acquired July 21, 2000, covers an area of 36.9 x 37.6 km, and is located at 69.3 degrees north latitude, 88.2 degrees east longitude.

The U.S. science team is located at NASA's Jet Propulsion Laboratory, Pasadena, Calif. The Terra mission is part of NASA's Science Mission Directorate.

Development of Platinum(iv) Complexes as Anticancer Prodrugs: the Story so Far

NASA Astrophysics Data System (ADS)

Wong, Daniel Yuan Qiang; Ang, Wee Han

2012-06-01

The serendipitous discovery of the antitumor properties of cisplatin by Barnett Rosenberg some forty years ago brought about a paradigm shift in the field of medicinal chemistry and challenged conventional thinking regarding the role of potentially toxic heavy metals in drugs. Platinum(II)-based anticancer drugs have since become some of the most effective and widely-used drugs in a clinician's arsenal and have saved countless lives. However, they are limited by high toxicity, severe side-effects and the incidence of drug resistance. In recent years, attention has shifted to stable platinum(IV) complexes as anticancer prodrugs. By exploiting the unique chemical and structural attributes of their scaffolds, these platinum(IV) prodrugs offer new strategies of targeting and killing cancer cells. This review summarizes the development of anticancer platinum(IV) prodrugs to date and some of the exciting strategies that utilise the platinum(IV) construct as targeted chemotherapeutic agents against cancer.

Nanoscale platinum printing on insulating substrates.

PubMed

O'Connell, C D; Higgins, M J; Sullivan, R P; Jamali, S S; Moulton, S E; Wallace, G G

2013-12-20

The deposition of noble metals on soft and/or flexible substrates is vital for several emerging applications including flexible electronics and the fabrication of soft bionic implants. In this paper, we describe a new strategy for the deposition of platinum electrodes on a range of materials, including insulators and flexible polymers. The strategy is enabled by two principle advances: (1) the introduction of a novel, low temperature strategy for reducing chloroplatinic acid to platinum using nitrogen plasma; (2) the development of a chloroplatinic acid based liquid ink formulation, utilizing ethylene glycol as both ink carrier and reducing agent, for versatile printing at nanoscale resolution using dip-pen nanolithography (DPN). The ink formulation has been printed and reduced upon Si, glass, ITO, Ge, PDMS, and Parylene C. The plasma treatment effects reduction of the precursor patterns in situ without subjecting the substrate to destructively high temperatures. Feature size is controlled via dwell time and degree of ink loading, and platinum features with 60 nm dimensions could be routinely achieved on Si. Reduction of the ink to platinum was confirmed by energy dispersive x-ray spectroscopy (EDS) elemental analysis and x-ray diffraction (XRD) measurements. Feature morphology was characterized by optical microscopy, SEM and AFM. The high electrochemical activity of individually printed Pt features was characterized using scanning electrochemical microscopy (SECM).

Platinum Partitioning at Low Oxygen Fugacity: Implications for Core Formation Processes

NASA Technical Reports Server (NTRS)

Medard, E.; Martin, A. M.; Righter, K.; Lanziroti, A.; Newville, M.

2016-01-01

Highly siderophile elements (HSE = Au, Re, and the Pt-group elements) are tracers of silicate / metal interactions during planetary processes. Since most core-formation models involve some state of equilibrium between liquid silicate and liquid metal, understanding the partioning of highly siderophile elements (HSE) between silicate and metallic melts is a key issue for models of core / mantle equilibria and for core formation scenarios. However, partitioning models for HSE are still inaccurate due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variable like temperature, pressure, and oxygen fugacity. In this abstract, we describe a self-consistent set of experiments aimed at determining the valence of platinum, one of the HSE, in silicate melts. This is a key information required to parameterize the evolution of platinum partitioning with oxygen fugacity.

Palladium- and Copper-Catalyzed Arylation of Carbon-Hydrogen Bonds

PubMed Central

Daugulis, Olafs; Do, Hien-Quang; Shabashov, Dmitry

2010-01-01

The transition-metal-catalyzed functionalization of C-H bonds is a powerful method for generating carbon-carbon bonds. Although significant advances to this field have been reported during the last decade, many challenges remain. First, most of the methods are substrate-specific and thus cannot be generalized. Second, conversions of unactivated (i.e. not benzylic or alpha to heteroatom) sp3 C–H bonds to C–C bonds are rare, with most examples limited to t-butyl groups—a conversion that is inherently simple because there are no β-hydrogens that can be eliminated. Finally, the palladium, rhodium, and ruthenium catalysts routinely used for the conversion of C–H bonds to C–C bonds are expensive. Catalytically active metals that are cheaper and less exotic (e.g. copper, iron, and manganese) are rarely used. This Account describes our attempts to provide solutions to these three problems. We have developed a general method for directing-group-containing arene arylation by aryl iodides. Using palladium acetate as the catalyst, we arylated anilides, benzamides, benzoic acids, benzylamines, and 2-substituted pyridine derivatives under nearly identical conditions. We have also developed a method for the palladium-catalyzed auxiliary-assisted arylation of unactivated sp3 C–H bonds. This procedure allows for the β-arylation of carboxylic acid derivatives and the γ-arylation of amine derivatives. Furthermore, copper catalysis can be used to mediate the arylation of acidic arene C–H bonds (i.e. those with pKa values <35 in DMSO). Using a copper iodide catalyst in combination with a base and a phenanthroline ligand, we successfully arylated electron-rich and electron-deficient heterocycles and electron-poor arenes possessing at least two electron-withdrawing groups. The reaction exhibits unusual regioselectivity: arylation occurs at the most hindered position. This copper-catalyzed method supplements the well-known C–H activation/borylation methodology, in which

Palladium- and copper-catalyzed arylation of carbon-hydrogen bonds.

PubMed

Daugulis, Olafs; Do, Hien-Quang; Shabashov, Dmitry

2009-08-18

The transition-metal-catalyzed functionalization of C-H bonds is a powerful method for generating carbon-carbon bonds. Although significant advances to this field have been reported during the past decade, many challenges remain. First, most of the methods are substrate-specific and thus cannot be generalized. Second, conversions of unactivated (i.e., not benzylic or alpha to heteroatom) sp(3) C-H bonds to C-C bonds are rare, with most examples limited to t-butyl groups, a conversion that is inherently simple because there are no beta-hydrogens that can be eliminated. Finally, the palladium, rhodium, and ruthenium catalysts routinely used for the conversion of C-H bonds to C-C bonds are expensive. Catalytically active metals that are cheaper and less exotic (e.g., copper, iron, and manganese) are rarely used. This Account describes our attempts to provide solutions to these three problems. We have developed a general method for directing-group-containing arene arylation by aryl iodides. Using palladium acetate as the catalyst, we arylated anilides, benzamides, benzoic acids, benzylamines, and 2-substituted pyridine derivatives under nearly identical conditions. We have also developed a method for the palladium-catalyzed auxiliary-assisted arylation of unactivated sp(3) C-H bonds. This procedure allows for the beta-arylation of carboxylic acid derivatives and the gamma-arylation of amine derivatives. Furthermore, copper catalysis can be used to mediate the arylation of acidic arene C-H bonds (i.e., those with pK(a) values <35 in DMSO). Using a copper iodide catalyst in combination with a base and a phenanthroline ligand, we successfully arylated electron-rich and electron-deficient heterocycles and electron-poor arenes possessing at least two electron-withdrawing groups. The reaction exhibits unusual regioselectivity: arylation occurs at the most hindered position. This copper-catalyzed method supplements the well-known C-H activation/borylation methodology, in

Phenomenological in-situ TEM gas exposure studies of palladium particles on MgO at room temperature

NASA Technical Reports Server (NTRS)

Heinemann, K.; Poppa, H.; Osaka, T.

1983-01-01

It has been found that very small vapor-deposited catalytically active metal particles in the 1-2 nm size range on metal oxide substrates can undergo significant changes when they are exposed to gases such as oxygen or air, or even when allowed to 'anneal' at room temperature (RT) under vacuum conditions. The present investigation is concerned with continued in-situ gas exposures of as-deposited, 1 to 2 nm size palladium particles on MgO to air, oxygen, nitrogen, hydrogen, CO, and water vapor at RT. It is found that the low-pressure exposure to various gases at RT can significantly affect small palladium particles supported on MgO surfaces. Exposure to oxygen for 3 min at 0.0002 m bar produces a considerable amount of coalescence, flattening of the particles, and some distinct crystallographic particle shapes.

Carbon monoxide tolerant electrocatalyst with low platinum loading and a process for its preparation

DOEpatents

Adzic, Radoslav; Brankovic, Stanko; Wang, Jia

2003-12-30

An electrocatalyst is provided for use in a fuel cell that has low platinum loading and a high tolerance to carbon monoxide poisoning. The fuel cell anode includes an electrocatalyst that has a conductive support material, ruthenium nanoparticles reduced in H.sub.2 and a Group VIII noble metal in an amount of between about 0.1 and 25 wt % of the ruthenium nanoparticles, preferably between about 0.5 and 15 wt %. The preferred Group VIII noble metal is platinum. In one embodiment, the anode can also have a perfluorinated polymer membrane on its surface.

Finding Platinum-Coating Gaps On Titanium Anodes

NASA Technical Reports Server (NTRS)

Bodemeijer, Ronnald; Flowers, Cecil E.

1990-01-01

Simple procedure makes gaps visible to eye. New gap-detection method consists of plating thin layer of non-silver-colored metal like copper or gold on anode. Contrast in color between plated metal and bare anode material makes gaps stand out. If anode passes inspection, copper or gold plate removable by reversal of test-plating current. Remains to be determined whether test plating and removal damages anode. New method simpler and more economical than previous attempts to identify gaps in platinum.

Spectrometric determination of platinum with methoxypromazine maleate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thimmegowda, A.; Sankegowda, H.; Gowda, N.M.M.

1984-03-01

A simple, rapid, and sensitive spectrophotometric method has been developed for the determination of platinum in solution. The chromogenic reagent, methoxypromazine maleate, reacts with platinum(IV) almost instantaneously in phosphoric acid medium containing copper(II) catalyst to form a bluish pink 1:1 complex with an absorption maximum at 562 nm. The complexation is complete within 1 min. A 30-fold molar excess of the reagent over metal ion is necessary for completion of the reaction. Beer's law is obeyed over the concentration range of 0.4-9.8 ppm of platinum(IV) with an optimal range of 1.5-8.6 ppm. The molar absorptivity is 1.71 x 10/sub 4/more » L mol/sup -1/ cm/sup -1/ and the Sandell sensitivity is 11.4 ng cm/sup -2/. The apparent stability constant of the complex is log K = 5.58 +/- 0.1 at 27/sup 0/C. The effects of acid concentration, time, temperature, concentration of the reagent and copper, order of addition of reagents, and the interferences from various ions are investigated. The method has been used for the determination of platinum in synthetic solutions that approximate the composition of some alloys and minerals. 25 references, 1 figure, 2 tables.« less

Effect of platinum nanoparticle deposition parameters on hydrogen peroxide transduction for applications in wearable electrochemical glucose biosensors

NASA Astrophysics Data System (ADS)

Cargill, Allison A.; Neil, Kathrine M.; Hondred, John A.; McLamore, Eric S.; Claussen, Jonathan C.

2016-05-01

Enhanced interest in wearable biosensor technology over the past decade is directly related to the increasing prevalence of diabetes and the associated requirement of daily blood glucose monitoring. In this work we investigate the platinum-carbon transduction element used in traditional first-generation glucose biosensors which rely on the concentration of hydrogen peroxide produced by the glucose-glucose oxidase binding scheme. We electrodeposit platinum nanoparticles on a commercially-available screen printed carbon electrode by stepping an applied current between 0 and 7.12 mA/cm2 for a varying number of cycles. Next, we examine the trends in deposition and the effect that the number of deposition cycles has on the sensitivity of electrochemical glucose sensing. Results from this work indicate that applying platinum nanoparticles to screen printed carbon via electrodeposition from a metal salt solution improves overall biosensor sensitivity. This work also pinpoints the amount of platinum (i.e., number of deposition cycles) that maximizes biosensor sensitivity in an effort to minimize the use of the precious metals, viz., platinum, in electrode fabrication. In summary, this work quantifies the relationship between platinum electrodeposition and sensor performance, which is crucial in designing and producing cost-effective sensors.

Characterization of Platinum and Iridium Oxyhydrate Surface Layers from Platinum and Iridium Foils.

PubMed

Johnson, Benjamin; Ranjan, Chinmoy; Greiner, Mark; Arrigo, Rosa; Schuster, Manfred Erwin; Höpfner, Britta; Gorgoi, Mihaela; Lauermann, Iver; Willinger, Marc; Knop-Gericke, Axel; Schlögl, Robert

2016-07-07

Platinum and iridium polycrystalline foils were oxidized electrochemically through anodization to create thin platinum and iridium hydrous oxide layers, which were analyzed through laboratory photoelectron spectroscopy during heating and time series (temperature-programmed spectroscopy). The films contain oxygen in the form of bound oxides, water, and hydroxides and were investigated by depth profiling with high-energy photoelectron spectroscopy. The Pt films are unstable and begin to degrade immediately after removal from the electrolyte to form core-shell structures with a metallic inner core and a hydrous oxide outer shell almost devoid of Pt. However, evidence was found for metastable intermediate states of degradation; therefore, it may be possible to manufacture PtOx phases with increased stability. Heating the film to even 100 °C causes accelerated degradation, which shows that stoichiometric oxides such as PtO2 or PtO are not the active species in the electrolyte. The Ir films exhibit increased stability and higher surface Ir content, and gentle heating at low temperatures leads to a decrease in defect density. Although both layers are based on noble metals, their surface structures are markedly different. The complexity of such hydrous oxide systems is discussed in detail with the goal of identifying the film composition more precisely. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Properties of the carbon-palladium nanocomposites studied by Raman spectroscopy method

NASA Astrophysics Data System (ADS)

Belka, Radosław; Suchańska, Małgorzata

2013-10-01

In this paper, the results for thin carbon-palladium (C-Pd) nanocomposites obtained by PVD (Physical Vapour Deposition) and PVD/CVD (Chemical Vapour Deposition) method, carried out using Raman spectroscopy method are presented. Studies reveal the dominance of fullerene-like structure for PVD samples and graphite-like structures for CVD samples. The type of substrate and metal content have great impact on spectra shapes.

Advances in UV-Plasmonics: A Detailed Analysis of Metallic Materials as Candidates for New Applications in Nanothecnology

DTIC Science & Technology

2014-08-26

Indium, Rhodium, Ruthenium, Tungsten, Titanium, Chromium, Palladium, Copper, Platinum and Magnesium . These have been chosen because all of them...performance. vii. Considering that the observed behaviors occur precisely where UV surface-enhanced Raman spectra indicated strong local field...research objective was centered on the UV plasmonic properties of Rh NPs by means of surface-enhanced Raman spectroscopy, surface-enhanced

GREEN SYNTHESIS OF SILVER AND PALLADIUM NANOPARTICLES AT ROOM TEMPERATURE USING COFFEE AND TEA EXTRACT

EPA Science Inventory

An extremely simple green approach that generates bulk quantities of nanocrystals of noble metals such as silver (Ag) and palladium (Pd) using coffee and tea extract at room temperature is described. The single-pot method uses no surfactant, capping agent, and/or template. The ob...

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

PubMed

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

2016-03-01

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

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

PubMed Central

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

2016-01-01

Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER. PMID:27034988

Effect of silver on the shape of palladium nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Dikshita, E-mail: dgmonugupta@gmail.com; Barman, P. B.; Hazra, S. K.

We report a facile route to prepare palladium-silver nanoparticles at considerably low temperature. First the controlled synthesis of palladium nanoparticles was performed via reduction of sodium tetrachloropalladate (II) in ethylene glycol in the presence of PVP(polyvinylpyrrolidone) as capping agent. The reaction was carried out at three different temperatures-80°C, 100°C and 120°C for one hour. Short reaction time and low synthesis temperature adds advantage to this method over others. Formed palladium nanoparticles were nearly spherical with the average particle size of 7.5±0.5 nm, 9.5±0.5 nm and 10.5±0.5 nm at 80°C, 100°C and 120°C respectively. Secondly, the palladium-silver nanoparticles were prepared bymore » the simultaneous reduction of palladium and silver from their respective precursors in ethylene glycol at 100°C (optimized temperature). The shape and size distribution was studied by TEM (Transmission Electron Microscopy). The role of silver in transforming the shape of palladium nanoparticles from spherical to triangular has been discussed. Spherical symmetry of palladium nanoparticles is disturbed by the interaction of silver ions on the crystal facets of palladium nanoparticles. From UV-vis spectra, the absorption maxima of palladium nanoparticles at 205 nm and absorption maxima of palladium-silver nanoparticles at 272 nm revealed the partial evidence of their formation.« less

Formation and electronic properties of palladium hydrides and palladium-rhodium dihydride alloys under pressure.

PubMed

Yang, Xiao; Li, Huijian; Ahuja, Rajeev; Kang, Taewon; Luo, Wei

2017-06-14

We present the formation possibility for Pd-hydrides and Pd-Rh hydrides system by density functional theory (DFT) in high pressure upto 50 GPa. Calculation confirmed that PdH 2 in face-centered cubic (fcc) structure is not stable under compression that will decomposition to fcc-PdH and H 2 . But it can be formed under high pressure while the palladium is involved in the reaction. We also indicate a probably reason why PdH 2 can not be synthesised in experiment due to PdH is most favourite to be formed in Pd and H 2 environment from ambient to higher pressure. With Rh doped, the Pd-Rh dihydrides are stabilized in fcc structure for 25% and 75% doping and in tetragonal structure for 50% doping, and can be formed from Pd, Rh and H 2 at high pressure. The electronic structural study on fcc type Pd x Rh 1-x H 2 indicates the electronic and structural transition from metallic to semi-metallic as Pd increased from x = 0 to 1.

Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof

DOEpatents

Adzic, Radoslav; Zhang, Junliang

2010-04-27

The invention relates to gold-coated particles useful as fuel cell electrocatalysts. The particles are composed of an electrocatalytically active core at least partially encapsulated by an outer shell of gold or gold alloy. The invention more particularly relates to such particles having a noble metal-containing core, and more particularly, a platinum or platinum alloy core. In other embodiments, the invention relates to fuel cells containing these electrocatalysts and methods for generating electrical energy therefrom.

Synthesis of Water-Soluble Palladium Nanoparticles Stabilized by Sulfonated N-Heterocyclic Carbenes.

PubMed

Asensio, Juan M; Tricard, Simon; Coppel, Yannick; Andrés, Román; Chaudret, Bruno; de Jesús, Ernesto

2017-09-27

A strategy involving the decomposition of palladium(II) organometallic complexes with sulfonated N-heterocyclic carbene ligands leads to the formation of stable and water-soluble Pd nanoparticles. Three different methodologies (thermal decomposition, reduction under 13 CO atmosphere, and reduction with H 2 ) gave particles with different shapes and sizes, ranging from 1.5 to 7 nm. The structures of the organometallic intermediates and organic decomposition products were elucidated by NMR spectroscopy. To check the accessibility of the surface, the nanoparticles were tested as catalysts for the chemoselective hydrogenation of styrene in water. An effect of the particle size on the catalyst activity was observed. The aqueous phase was recycled up to ten times without any precipitation of metallic palladium. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic properties of a molecular system with Platinum

NASA Astrophysics Data System (ADS)

Ojeda, J. H.; Medina, F. G.; Becerra-Alonso, David

2017-10-01

The electronic properties are studied using a finite homogeneous molecule called Trans-platinum-linked oligo(tetraethenylethenes). This system is composed of individual molecules such as benzene rings, platinum, Phosphore and Sulfur. The mechanism for the study of the electron transport through this system is based on placing the molecule between metal contacts to control the current through the molecular system. We study this molecule based on the tight-binding approach for the calculation of the transport properties using the Landauer-Büttiker formalism and the Fischer-Lee relationship, based on a semi-analytic Green's function method within a real-space renormalization approach. Our results show a significant agreement with experimental measurements.

Nanostructured gold and platinum electrodes on silicon structures for biosensing

NASA Astrophysics Data System (ADS)

Ogurtsov, V. I.; Sheehan, M. M.

2005-01-01

Gold and platinum metal electrodes on Si/SiO2 having undergone anisotropic potassium hydroxide (KOH) etch treatment are considered. This treatment etches at different rates and directions in the material resulting in creation of numerous pyramid shaped holes in the silicon substrate. This surface is used to make metal electrodes with increased electrode efficiency. The electrodes can serve as the sensors or as the sensor substrates (for surface polymer modification) and because both gold and platinum are inert they have applications for food safety biosensing. Wine, an economically significant food product, was chosen as a matrix, and impedance spectroscopy (EIS) was selected as a method of investigation of electrode behaviour. Based on results of EIS, different complexity equivalent circuits were determined by applying fitting mean square root optimisation of sensor complex impedance measurements.

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

PubMed

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

2016-11-01

In this study the exposure of the general population in Germany to platinum and rhodium and its determinants was investigated in 259 participants (subdivided in three groups) by urine analyses and assessment of the dental status. Complementary, an interview including questions characterising possible exposure to traffic exhaust was conducted. The median excretion was 2.42ng platinum/g creatinine and 7.27ng rhodium/g creatinine. The detailed analysis of the collected data showed significant higher platinum excretion values with increasing number of surfaces covered with restorations containing precious metals (R=0.389; p<0.001), but also higher values for habitants of urban areas (median=3.43ng/g creatinine; 95th percentile=25.2ng/g) compared with those of rural areas (median=2.06ng/g creatinine; 95th percentile=20.0ng/g). Also, participants working in urban areas showed higher platinum excretion values (median=3.27ng/g; 95th percentile=19.6ng/g). Male participants living and working next to highly frequented roads showed higher rhodium excretion values (median=7.27ng/g; 95th percentile=13.5 ng/g). In summary, the study showed that exhaust emissions have an influence on platinum and rhodium excretion, but for platinum this influence is rather low compared to the influence of precious metals containing restorations. Copyright © 2016 Elsevier GmbH. All rights reserved.

Synthesis of Metal Nanoparticles in Metal-Phenolic Networks: Catalytic and Antimicrobial Applications of Coated Textiles.

PubMed

Yun, Gyeongwon; Pan, Shuaijun; Wang, Ting-Yi; Guo, Junling; Richardson, Joseph J; Caruso, Frank

2018-03-01

The synthesis of metal nanoparticle (NP)-coated textiles (nanotextiles) is achieved by a dipping process in water without toxic chemicals or complicated synthetic procedures. By taking advantage of the unique nature of tannic acid, metal-phenolic network-coated textiles serve as reducing and stabilizing sites for the generation of metal nanoparticles of controllable size. The textiles can be decorated with various metal nanoparticles, including palladium, silver, or gold, and exhibit properties derived from the presence of the metal nanoparticles, for example, catalytic activity in water (>96% over five cycles using palladium nanoparticles) and antibacterial activity against Gram-negative bacteria (inhibition of Escherichia coli using silver nanoparticles) that outperforms a commercial bandage. The reported strategy offers opportunities for the development of hybrid nanomaterials that may have application in fields outside of catalysis and antimicrobials, such as sensing and smart clothing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stereocontrolled Additions to a Rigid Bicyclo [3.3.0] Octane Ring System

DTIC Science & Technology

2008-05-05

bridgehead carbon. The metals studied were palladium, platinum, and the Raney nickel catalyst . The catalysts themselves are usually absorbed on an...Catalytic Hydrogenation Reaction The Raney nickel catalyst yielded extremely pure product in a single isomeric form when the reaction was run with...ethyl acetate was 68.7%, a noted increase over that obtained with the Raney nickel catalyst . 31 Disappearance of the double bond peak again

Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores

PubMed Central

El-Safty, Sherif A.; Shenashen, Mohamed A.; Sakai, Masaru; Elshehy, Emad; Halada, Kohmei

2015-01-01

Developing low-cost, efficient processes for recovering and recycling palladium, gold and cobalt metals from urban mine remains a significant challenge in industrialized countries. Here, the development of optical mesosensors/adsorbents (MSAs) for efficient recognition and selective recovery of Pd(II), Au(III), and Co(II) from urban mine was achieved. A simple, general method for preparing MSAs based on using high-order mesoporous monolithic scaffolds was described. Hierarchical cubic Ia3d wagon-wheel-shaped MSAs were fabricated by anchoring chelating agents (colorants) into three-dimensional pores and micrometric particle surfaces of the mesoporous monolithic scaffolds. Findings show, for the first time, evidence of controlled optical recognition of Pd(II), Au(III), and Co(II) ions and a highly selective system for recovery of Pd(II) ions (up to ~95%) in ores and industrial wastes. Furthermore, the controlled assessment processes described herein involve evaluation of intrinsic properties (e.g., visual signal change, long-term stability, adsorption efficiency, extraordinary sensitivity, selectivity, and reusability); thus, expensive, sophisticated instruments are not required. Results show evidence that MSAs will attract worldwide attention as a promising technological means of recovering and recycling palladium, gold and cobaltmetals. PMID:26709467

Platinum recovery from industrial process streams by halophilic bacteria: Influence of salt species and platinum speciation.

PubMed

Maes, Synthia; Claus, Mathias; Verbeken, Kim; Wallaert, Elien; De Smet, Rebecca; Vanhaecke, Frank; Boon, Nico; Hennebel, Tom

2016-11-15

The increased use and criticality of platinum asks for the development of effective low-cost strategies for metal recovery from process and waste streams. Although biotechnological processes can be applied for the valorization of diluted aqueous industrial streams, investigations considering real stream conditions (e.g., high salt levels, acidic pH, metal speciation) are lacking. This study investigated the recovery of platinum by a halophilic microbial community in the presence of increased salt concentrations (10-80 g L -1 ), different salt matrices (phosphate salts, sea salts and NH 4 Cl) and a refinery process stream. The halophiles were able to recover 79-99% of the Pt at 10-80 g L -1 salts and at pH 2.3. Transmission electron microscopy suggested a positive correlation between intracellular Pt cluster size and elevated salt concentrations. Furthermore, the halophiles recovered 46-95% of the Pt-amine complex Pt[NH 3 ] 4 2+ from a process stream after the addition of an alternative Pt source (K 2 PtCl 4 , 0.1-1.0 g L -1 Pt). Repeated Pt-tetraamine recovery (from an industrial process stream) was obtained after concomitant addition of fresh biomass and harvesting of Pt saturated biomass. This study demonstrates how aqueous Pt streams can be transformed into Pt rich biomass, which would be an interesting feed of a precious metals refinery. Copyright © 2016 Elsevier Ltd. All rights reserved.

Novel platinum–palladium bimetallic nanoparticles synthesized by Dioscorea bulbifera: anticancer and antioxidant activities

PubMed Central

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

DNA Binding and Antitumor Activity of α-Diimineplatinum(II) and Palladium(II) Dithiocarbamate Complexes

PubMed Central

Mansouri-Torshizi, Hassan; Saeidifar, Maryam; Khosravi, Fatemeh; Divsalar, Adeleh; Saboury, Ali Akbar; Hassani, Fatemeh

2011-01-01

The two water-soluble designed platinum(II) complex, [Pt(Oct-dtc)(bpy)]NO3 (Oct-dtc = Octyldithiocarbamate and bpy = 2,2′ -bipyridine) and palladium(II) complex, [Pd(Oct-dtc)(bpy)]NO3, have been synthesized and characterized by elemental analyses, molar conductivity measurements, IR, 1H NMR, and electronic spectra studies. Studies of antitumor activity of these complexes against human cell tumor lines (K562) have been carried out. They show Ic50 values lower than that of cisplatin. The complexes have been investigated for their interaction with calf thymus DNA (CT-DNA) by utilizing the electronic absorption spectroscopy, fluorescence spectra, and ethidium bromide displacement and gel filtration techniques. Both of these water-soluble complexes bound cooperatively and intercalatively to the CT-DNA at very low concentrations. Several binding and thermodynamic parameters are also described. PMID:22110410

Metal chelates as anti-cancer agents. II cytotoxic action of palladium and platinum complexes of 6-mercaptopurine and thioguanine.

PubMed Central

Das, M.; Livingstone, S. E.

1978-01-01

The metal complexes Pd(MP)2.2H2O, Pt(MP)2H2O (MPH=6-mercaptopurine), Pt(AMP2.3H2O and Pd3(AMP)4Cl2(AMPH).4H2O (AMPH=thioguanine) have been isolated. They were screened for anti-tumour activity in the L-1210 lymphoid leukaemia test system in mice. All 4 show marked anti-tumour activity, the complex Pt(AMP)2.3H2O giving a T/C of 185 at the optimum dosage. However, the anti-tumour activity of the metal complexes is somewhat less than that shown by the parent purines under the same conditions. PMID:698049

Spectrophotometric complexation of cephalosporins with palladium (II) chloride in aqueous and non-aqueous solvents

NASA Astrophysics Data System (ADS)

Bagheri Gh., A.; Yosefi rad, A.; Rezvani, M.; Roshanzamir, S.

2012-04-01

The complexation reaction of cephalosporins namely cefotaxime (CTX), cefuroxime (CRX), and cefazolin (CEFAZ) with palladium (II) ions have been studied in water and DMF in 25 °C by the spectrophotometric methods. The method is based on the formation of yellow to yellowish brown complex between palladium (II) chloride and the investigated cephalosporins in the presence of sodium lauryl sulfate (SLS) as surfactant. The complexation process was optimized in terms of pH, temperature and contact time. The stoichiometry of all the complexes was found to be 2:1 (metal ion/ligand) for CTX, CRX, and 1:2 for CEFAZ. The stoichiometry of palladium (II)-cephalosporins was estimated by mole ratio and continuous variation methods and emphasized by the KINFIT program. These drugs could be determined by measuring the absorbance of each complex at its specific λmax. The results obtained are in good agreement with those obtained using the official methods. The proposed method was successfully applied for the determination of these compounds in their dosage forms.

Hydrogen dissolution in palladium: A resistometric study under pressure

NASA Astrophysics Data System (ADS)

Magnouche, A.; Fromageau, R.

1984-09-01

The hydrogen solubility in palladium in equilibrium with H2 gas has been measured, between room temperature and 540 °C, using a resistometric method, for pressures ranging between 0.01 and 10 MPa. In these conditions, the experimentally determined values of the solubility and of the dissolution enthalpy exhibit very close agreement with those obtained by other methods (calorimetry, volumetry, etc.), or after electrolytic charging. This good agreement demonstrates the validity of the resistometric method for determination of the solubility of hydrogen in metals.

Haemocompatibility assessment of synthesised platinum nanoparticles and its implication in biology.

PubMed

Shiny, P J; Mukherjee, Amitava; Chandrasekaran, N

2014-06-01

The growing need for advanced treatment of evolving diseases has become a motivation for this study. Among the noble metals, platinum nanoparticles are of importance because of their catalytic property, antioxidant potential, minimal toxicity and diverse applications. Biological process of synthesis has retained its significance, because it is a simple one-step process yielding stable nanoparticles. Herein, we have synthesised platinum nanoparticles through a green process using the unexplored seaweed Padina gymnospora, a brown alga. The course of synthesis was monitored and the nanoparticles were characterised using UV-visible spectroscopy. The synthesised nanoparticles were studied using TEM, XRD and FTIR. The TEM and XRD studies reveal the size of the nanoparticle to be <35 nm. The catalytic nanoparticles were capable of oxidising NADH to NAD(+). The biocompatibility was tested by haemolytic assay for the furtherance of the application of platinum nanoparticles in medicine. This is the first report on the biogenic synthesis of platinum nanoparticles using seaweed.

Passive fit of frameworks in titanium and palladium-silver alloy submitted the laser welding.

PubMed

de Sousa, S A; de Arruda Nobilo, M A; Henriques, G E P; Mesquita, M F

2008-02-01

This study evaluated the precision of fit of implant frameworks cast in titanium (cp Ti) and palladium-silver alloy (Pd-Ag), made by the one-piece cast and laser welding techniques. From a metal matrix with five implants, 20 master casts were obtained, to which replicas of implants were incorporated. On these masters 10 frameworks were made for each type of material (cp Ti and Pd-Ag alloy). Half of these were made by the one-piece cast technique and the other half by the laser welding technique. The implant/prosthesis interface was analysed and measured in the vestibular and lingual regions of the central and distal implants with the help of a measuring microscope. The results indicated that in the central cylinders, the Tukey test (P<0.0005) showed a significant difference in the passive fit between the laser-welded frameworks (34.73 microm) and those one-piece cast frameworks (151.39 microm), and as regards materials, the palladium-silver alloy (66.30 microm) showed better results than the titanium (119.83 microm). In the distal cylinders there was no significant difference between the frameworks cast in titanium and palladium-silver by the one-piece technique. However, after laser welding, there was a significant difference for the frameworks cast in titanium (31.37 microm) and palladium-silver (106.59 microm).

Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

PubMed Central

Bai, Da-Chang; Yu, Fei-Le; Wang, Wan-Ying; Chen, Di; Li, Hao; Liu, Qing-Rong; Ding, Chang-Hua; Chen, Bo; Hou, Xue-Long

2016-01-01

The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of β-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a (syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. Mechanistic studies by both experiments and density functional theory (DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism—nucleophilic attack of enolate oxygen on Palladium followed by C–C bond-forming [3,3']-reductive elimination. PMID:27283477

Selective growth of palladium and titanium dioxide nanostructures inside carbon nanotube membranes.

PubMed

Hevia, Samuel; Homm, Pía; Cortes, Andrea; Núñez, Verónica; Contreras, Claudia; Vera, Jenniffer; Segura, Rodrigo

2012-06-25

Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors.

Selective growth of palladium and titanium dioxide nanostructures inside carbon nanotube membranes

PubMed Central

2012-01-01

Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors. PMID:22731888

Selective growth of palladium and titanium dioxide nanostructures inside carbon nanotube membranes

NASA Astrophysics Data System (ADS)

Hevia, Samuel; Homm, Pía; Cortes, Andrea; Núñez, Verónica; Contreras, Claudia; Vera, Jenniffer; Segura, Rodrigo

2012-06-01

Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors.

Therapeutic gold, silver, and platinum nanoparticles.

PubMed

Yamada, Miko; Foote, Matthew; Prow, Tarl W

2015-01-01

There are an abundance of nanoparticle technologies being developed for use as part of therapeutic strategies. This review focuses on a narrow class of metal nanoparticles that have therapeutic potential that is a consequence of elemental composition and size. The most widely known of these are gold nanoshells that have been developed over the last two decades for photothermal ablation in superficial cancers. The therapeutic effect is the outcome of the thickness and diameter of the gold shell that enables fine tuning of the plasmon resonance. When these metal nanoparticles are exposed to the relevant wavelength of light, their temperature rapidly increases. This in turn induces a localized photothermal ablation that kills the surrounding tumor tissue. Similarly, gold nanoparticles have been developed to enhance radiotherapy. The high-Z nature of gold dramatically increases the photoelectric cross-section. Thus, the photoelectric effects are significantly increased. The outcome of these interactions is enhanced tumor killing with lower doses of radiation, all while sparing tissue without gold nanoparticles. Silver nanoparticles have been used for their wound healing properties in addition to enhancing the tumor-killing effects of anticancer drugs. Finally, platinum nanoparticles are thought to serve as a reservoir for platinum ions that can induce DNA damage in cancer cells. The future is bright with the path to clinical trials is largely cleared for some of the less complex therapeutic metal nanoparticle systems. © 2014 The Authors. WIREs Nanomedicine and Nanobiotechnology published by Wiley Periodicals, Inc.

Selection of a platinum-binding sequence in a loop of a four-helix bundle protein.

PubMed

Yagi, Sota; Akanuma, Satoshi; Kaji, Asumi; Niiro, Hiroya; Akiyama, Hayato; Uchida, Tatsuya; Yamagishi, Akihiko

2018-02-01

Protein-metal hybrids are functional materials with various industrial applications. For example, a redox enzyme immobilized on a platinum electrode is a key component of some biofuel cells and biosensors. To create these hybrid materials, protein molecules are bound to metal surfaces. Here, we report the selection of a novel platinum-binding sequence in a loop of a four-helix bundle protein, the Lac repressor four-helix protein (LARFH), an artificial protein in which four identical α-helices are connected via three identical loops. We created a genetic library in which the Ser-Gly-Gln-Gly-Gly-Ser sequence within the first inter-helical loop of LARFH was semi-randomly mutated. The library was then subjected to selection for platinum-binding affinity by using the T7 phage display method. The majority of the selected variants contained the Tyr-Lys-Arg-Gly-Tyr-Lys (YKRGYK) sequence in their randomized segment. We characterized the platinum-binding properties of mutant LARFH by using quartz crystal microbalance analysis. Mutant LARFH seemed to interact with platinum through its loop containing the YKRGYK sequence, as judged by the estimated exclusive area occupied by a single molecule. Furthermore, a 10-residue peptide containing the YKRGYK sequence bound to platinum with reasonably high affinity and basic side chains in the peptide were crucial in mediating this interaction. In conclusion, we have identified an amino acid sequence, YKRGYK, in the loop of a helix-loop-helix motif that shows high platinum-binding affinity. This sequence could be grafted into loops of other polypeptides as an approach to immobilize proteins on platinum electrodes for use as biosensors among other applications. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Selective speciation improves efficacy and lowers toxicity of platinum anticancer and vanadium antidiabetic drugs.

PubMed

Doucette, Kaitlin A; Hassell, Kelly N; Crans, Debbie C

2016-12-01

Improving efficacy and lowering resistance to metal-based drugs can be addressed by consideration of the coordination complex speciation and key reactions important to vanadium antidiabetic drugs or platinum anticancer drugs under biological conditions. The methods of analyses vary depending on the specific metal ion chemistry. The vanadium compounds interconvert readily, whereas the reactions of the platinum compounds are much slower and thus much easier to study. However, the vanadium species are readily differentiated due to vanadium complexes differing in color. For both vanadium and platinum systems, understanding the processes as the compounds, Lipoplatin and Satraplatin, enter cells is needed to better combat the disease; there are many cellular metabolites, which may affect processing and thus the efficacy of the drugs. Examples of two formulations of platinum compounds illustrate how changing the chemistry of the platinum will result in less toxic and better tolerated drugs. The consequence of the much lower toxicity of the drug, can be readily realized because cisplatin administration requires hospital stay whereas Lipoplatin can be done in an outpatient manner. Similarly, the properties of Satraplatin allow for development of an oral drug. These forms of platinum demonstrate that the direct consequence of more selective speciation is lower side effects and cheaper administration of the anticancer agent. Therefore we urge that as the community goes forward in development of new drugs, control of speciation chemistry will be considered as one of the key strategies in the future development of anticancer drugs. Copyright © 2016 Elsevier Inc. All rights reserved.

On the corrosion behavior and biocompatibility of palladium-based dental alloys

NASA Astrophysics Data System (ADS)

Sun, Desheng

Palladium-based alloys have been used as dental restorative materials for about two decades with good clinical history. But there have been clinical case reports showing possible allergy effects from these alloys. The aim of this study was to characterize the corrosion behavior and mechanisms of several palladium-based dental alloys by potentiodynamic polarization methods, electrochemical impedance spectroscopy (EIS), and scanning Kelvin probe force microscopy/atomic force microscopy (SKPFM/AFM), and to evaluate their biocompatibility by a cell culture technique and an animal model. Using SKPFM/AFM and scanning electron microscopy, the Ru-enriched phase from the use of ruthenium as a grain-refining element was identified as being slightly more noble than the palladium solid solution matrix in a high-palladium alloy. Other secondary precipitates that exist in the microstructures of these high-palladium alloys have minimal differences in Volta potential compared to the matrix. For high-palladium alloys, corrosion is generally uniform due to the predominant palladium content in the different phases. Potentiodynamic polarization and EIS have shown that representative palladium-silver alloys have low corrosion tendency and high corrosion resistance, which are equivalent to a well-known high-noble gold-palladium alloy in simulated body fluid and oral environments. The palladium-silver alloys tested are resistant to chloride ion corrosion. Passivation and dealloying have been identified for all of the tested palladium-silver alloys. The great similarity in corrosion behavior among the palladium-silver alloys is attributed to their similar chemical compositions. The variation in microstructures of palladium-silver alloys tested does not cause significant difference in corrosion behavior. The corrosion resistance of these palladium-silver alloys at elevated potentials relevant to oral environment is still satisfactory. The release of elements from representative dental

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides.

PubMed

Kulesza, Pawel J; Pieta, Izabela S; Rutkowska, Iwona A; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A

2013-11-01

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO 3 , MoO 3 , TiO 2 , ZrO 2 , V 2 O 5 , and CeO 2 ) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems.

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides

PubMed Central

Kulesza, Pawel J.; Pieta, Izabela S.; Rutkowska, Iwona A.; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A.

2013-01-01

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO3, MoO3, TiO2, ZrO2, V2O5, and CeO2) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems. PMID:24443590

Ultrafine nanoporous palladium-aluminum film fabricated by citric acid-assisted hot-water-treatment of aluminum-palladium alloy film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harumoto, Takashi; Tamura, Yohei; Ishiguro, Takashi, E-mail: ishiguro@rs.noda.tus.ac.jp

Hot-water-treatment has been adapted to fabricate ultrafine nanoporous palladium-aluminum film from aluminum-palladium alloy film. Using citric acid as a chelating agent, a precipitation of boehmite (aluminum oxide hydroxide, AlOOH) on the nanoporous palladium-aluminum film was suppressed. According to cross-sectional scanning transmission electron microscopy observations, the ligament/pore sizes of the prepared nanoporous film were considerably small (on the order of 10 nm). Since this fabrication method only requires aluminum alloy film and hot-water with chelating agent, the ultrafine nanoporous film can be prepared simply and environmentally friendly.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ayers, Katherine; Capuano, Christopher; Atanassov, Plamen

The quantitative goal of this project was to produce a high-performance anion exchange membrane water electrolyzer (AEM-WE) completely free of platinum group metals (PGMs), which could operate for at least 500 hours with less than 50 microV/hour degradation, at 500 mA/cm 2. To achieve this goal, work focused on the optimization of electrocatalyst conductivity, with dispersion and utilization in the membrane electrode assembly (MEA) improved through refinement of deposition techniques. Critical factors were also explored with significant work undertaken by Northeastern University to further understand catalyst-membrane-ionomer interfaces and how they differ from liquid electrolyte. Water management and optimal cell operationalmore » parameters were established through the design, fabrication, and test of a new test station at Proton specific for AEM evaluation. Additionally, AEM material stability and robustness at high potentials and gas evolution conditions were advanced at Penn State.« less

Experimental observations on noble metal nanonuggets and Fe-Ti oxides, and the transport of platinum group elements in silicate melts

NASA Astrophysics Data System (ADS)

Anenburg, Michael; Mavrogenes, John A.

2016-11-01

Platinum group element (PGE) nanonuggets are a nuisance in experimental studies designed to measure solubility or partitioning of noble metals in silicate melts. Instead of treating nanonuggets as experimental artifacts, we studied their behaviour motivated by recent discoveries of PGE nanonuggets in a variety of natural settings. We used an experimental setup consisting of AgPd, Pt or AuPd capsules and Fe(-Ti) oxide-saturated hydrous peralkaline silicate melts to maximise nanonugget production. TABS (Te, As, Bi, Sb, Sn) commonly occur in PGM (platinum group minerals), prompting addition of Bi to our experiments to investigate its properties as well. Three-dimensional optical examination by 100× objective and immersion oil reveals variable colour which correlates with nanonugget size and shape due to plasmon resonance effects. We observe two textural types: (1) intermediate-sized nanonuggets dispersed in the glass and adhering to oxides, and (2) abundant fine nanonuggets dispersed in the glass with coarse euhedral crystals in contact with oxides. Slow cooling removes dispersed nanonuggets and greatly coarsens existing oxide-associated metal crystals. Nanonugget-free halos are commonly observed around oxide grains. All metal phases are composed of major (Ag, Pd) and trace (Pt, Ir, Au) capsule material. Our results show reduction processes, imposed by growing oxides, causing local metal saturation in the oxide rich zones with preferential nucleation on smaller oxide grains. The redox gradient then blocks additional metals from diffusing into oxide rich zones, forming halos. As the entire experimental charge is reduced throughout the run, nanonuggets form in the distal glass. Bismuth contents of metal phases do not depend on Bi2O3 amounts dissolved in the melt. Further PGM crystallisation consumes nanonuggets as feedstock. We conclude that the appearance of metallic PGE phases happens in two stages: first as nanonuggets and then as larger PGM. Once formed

Self-Assembled Novel BODIPY-Based Palladium Supramolecules and Their Cellular Localization.

PubMed

Gupta, Gajendra; Das, Abhishek; Park, Kyoung Chul; Tron, Artur; Kim, Hyunuk; Mun, Junyoung; Mandal, Nripendranath; Chi, Ki-Whan; Lee, Chang Yeon

2017-04-17

Four new palladium metal supramolecules with triangular/square architectures derived from boron dipyrromethane (BODIPY) ligands were synthesized by self-assembly and fully characterized by 1 H and 31 P NMR, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction. These supramolecules were more cytotoxic to brain cancer (glioblastoma) cells than to normal lung fibroblasts. Their cytotoxicity to the glioblastoma cells was higher than that of a benchmark metal-based chemotherapy drug, cisplatin. The characteristic green fluorescence of the BODIPY ligands in these supramolecules permitted their intracellular visualization using confocal microscopy, and the compounds were localized in the cytoplasm and on the plasma membrane.

The coordination chemistry of dipyridylbenzene: N-deficient terpyridine or panacea for brightly luminescent metal complexes?

PubMed

Williams, J A Gareth

2009-06-01

1,3-Di(2-pyridyl)benzene (dpybH) structurally resembles the widely-used ligand terpyridine (tpy), with which it is isoelectronic. In this critical review, following a brief overview of synthetic strategies for dpybH and derivatives, we survey the different types of complex that are possible with these ligands. Whilst metals such as ruthenium(ii), osmium(ii) and platinum(ii) give a terdentate N--C--N binding mode in which cyclometallation occurs at C(2), the ions iridium(iii), rhodium(iii) and palladium(ii) favour C(4) metallation. The latter process can be blocked by appropriate ligand modification, to allow the N--C--N mode to be accessed with these metal ions too. The luminescence properties of the complexes are discussed. A huge range of emission efficiencies are encountered amongst Ir(iii) complexes containing dpyb derivatives, according to the other ligands present. Trends can be rationalised with the aid of simple frontier-orbital considerations. The Pt(ii) complexes of dipyridylbenzenes are also intensely luminescent. Their application to contemporary organic light-emitting device (OLED) technology is discussed, including white light emitters exploiting excimer emission. Their potential as cell imaging agents amenable to time-resolved detection procedures on the microsecond timescale has also been demonstrated (118 references).

Metal oxide films on metal

DOEpatents

Wu, Xin D.; Tiwari, Prabhat

1995-01-01

A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

Thermally stable single-atom platinum-on-ceria catalysts via atom trapping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, John; Xiong, Haifeng; DelaRiva, Andrew

2016-07-08

Catalysts based on single atoms of scarce precious metals can lead to more efficient use through enhanced reactivity and selectivity. However, single atoms on catalyst supports can be mobile and aggregate into nanoparticles when heated at elevated temperatures. High temperatures are detrimental to catalyst performance unless these mobile atoms can be trapped. We used ceria powders having similar surface areas but different exposed surface facets. When mixed with a platinum/ aluminum oxide catalyst and aged in air at 800°C, the platinum transferred to the ceria and was trapped. Polyhedral ceria and nanorods were more effective than ceria cubes at anchoringmore » the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst.« less

Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai, Da -Chang; Yu, Fei -Le; Wang, Wan -Ying

The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of beta-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a ( syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. As a result, mechanisticmore » studies by both experiments and density functional theory ( DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism-nucleophilic attack of enolate oxygen on Palladium followed by C-C bond-forming [3,3']-reductive elimination.« less

Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

DOE PAGES

Bai, Da -Chang; Yu, Fei -Le; Wang, Wan -Ying; ...

2016-06-10

The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of beta-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a ( syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. As a result, mechanisticmore » studies by both experiments and density functional theory ( DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism-nucleophilic attack of enolate oxygen on Palladium followed by C-C bond-forming [3,3']-reductive elimination.« less

Bio-inspired routes for synthesizing efficient nanoscale platinum electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cha, Jennifer N.; Wang, Joseph

2014-08-31

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

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

USGS Publications Warehouse

Desborough, George A.; Criddle, Alan J.

1984-01-01

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

Nickel(II) and palladium(II) triphenylphosphine complexes incorporating tridentate Schiff base ligands: Synthesis, characterization and biocidal activities

NASA Astrophysics Data System (ADS)

Shabbir, Muhammad; Akhter, Zareen; Ashraf, Ahmad Raza; Ismail, Hammad; Habib, Anum; Mirza, Bushra

2017-12-01

Nickel(II) and palladium(II) triphenylphosphine complexes incorporating tridentate Schiff bases have been prepared and characterized by elemental analysis as well as by spectroscopic techniques (FTIR & NMR). The synthesized compounds were assessed to check their potential biocidal activity by using different biological assays (brine shrimp cytotoxicity, antimicrobial, antioxidant, antitumor and drug-DNA interaction). Results of brine shrimp cytotoxicity assay showed that ligand molecules are more bioactive than metal complexes with LD50 as low as 12.4 μg/mL. The prominent antitumor activity was shown by nickel complexes while the palladium complexes exhibited moderate activity. The synthesized compounds have shown high propensity for DNA binding either through intercalation or groove binding which represents the mechanism of antitumor effect of these compounds. Additionally, ligand molecules and nickel metal complexes showed significant antioxidant activity with IC50 values as low as 3.1 μg/mL and 18.9 μg/mL respectively while palladium complexes exhibited moderate activity. Moreover, in antimicrobial assays H2L1, Ni(L1)PPh3 and H2L3 showed dual inhibition against bacterial and fungal strains while for the rest of the compounds varying degree of activity was recorded against different strains. Overall comparison of results suggests that the synthesized compounds can be promising candidate for drug formulation and development.

Metal Decorated Multi-Walled Carbon Nanotube/Polyimide Composites with High Dielectric Constants and Low Loss Factors

NASA Technical Reports Server (NTRS)

Ghose, Sayata; Watson, Kent A.; Dudley, Kenneth L.; Elliott, Holly A.; Smith, Joseph G.; Connell, John W.

2009-01-01

The measurement of observable electromagnetic phenomena in materials and their derived intrinsic electric material properties are of prime importance in the discovery and development of material systems for electronic and aerospace applications. Nanocomposite materials comprised of metal decorated multi-walled carbon nanotubes (MWCNTs) were prepared by a facile method and characterized. Metal particles such as silver, platinum and palladium with diameters ranging from less than 5 to over 50 nanometers were distributed randomly on the MWCNTs. The metal-containing MWCNTs were then melt mixed into a polymer matrix and the mixture extruded as ribbons. These extruded ribbons exhibited a moderate to high degree of MWCNT alignment as determined by HRSEM. These ribbons were then fabricated into test specimens while maintaining MWCNT alignment and subsequently characterized for electromagnetic properties at 8-12 GHz. The present study is focused on silver decorated MWCNTs dispersed in an Ultem polyimide matrix. The results of the electromagnetic characterization showed that certain sample configurations exhibited a decoupling of the permittivity and loss factor (?? and ??) indicating that these properties could be tailored within certain limits. The decoupling and independent control of these fundamental electrical material parameters offer a new class of materials with potential applications in electronics, microwave engineering and optics.

Redbed-type gold mineralisation, Kupferschiefer, south-west Poland

NASA Astrophysics Data System (ADS)

Piestrzyński, Adam; Pieczonka, Jadwiga; Głuszek, Adam

2002-06-01

A new type of gold mineralisation containing minor amounts of platinum and palladium has been found proximal to the secondary redox interface located below the Cu-Ag Kupferschiefer orebody of the Polkowice-Sieroszowice mine in the south-western part of the Lubin-Sieroszowice district, Poland. This deposit can be classified as redbed-type gold. Our study shows that gold, platinum and palladium occur in secondary red-coloured sections of the basal Zechstein sedimentary rocks and in the uppermost Weissliegendes sandstone. Noble metal mineralisation occurs within an average interval of 0.22 m, which lies directly below the copper ores. The average grade of the horizon is 2.25 ppm Au, 0.138 ppm Pt and 0.082 ppm Pd with a metal content of several tens of tonnes of gold. A transition zone has been recognised between the gold-bearing horizon and the copper deposit. This transition zone is characterised by the presence of low grades of copper (<0.2 wt%) and elevated gold contents (>0.5 ppm). Native gold accompanied by electrum, mercury-bearing gold, haematite, covellite, chalcocite, bornite and chalcopyrite has been identified in the gold-bearing horizon. In some sections, Pd-arsenides, tetra-auricupride, Co-arsenides, clausthalite, tennantite, digenite, yarrowite, spionkopite and galena have also been noted.

Epirubicin, Cisplatin, and Capecitabine for Primary Platinum-Resistant or Platinum-Refractory Epithelial Ovarian Cancer

PubMed Central

Sayal, Karen; Gounaris, Ioannis; Basu, Bristi; Freeman, Sue; Moyle, Penny; Hosking, Karen; Iddawela, Mahesh; Jimenez-Linan, Mercedes; Abraham, Jean; Brenton, James; Hatcher, Helen; Earl, Helena; Parkinson, Christine

2015-01-01

Objective Primary platinum-resistant epithelial ovarian cancer (EOC) is an area of unmet medical need. There is limited evidence from small studies that platinum-based combinations can overcome “resistance” in a proportion of patients. We investigated the efficacy and toxicity of platinum-based combination chemotherapy in the platinum-resistant and platinum-refractory setting. Methods Epirubicin, cisplatin, and capecitabine (ECX) combination chemotherapy was used at our institution for the treatment of relapsed EOC. From the institutional database, we identified all patients with primary platinum-refractory or platinum-resistant relapse treated with ECX as second-line therapy between 2001 and 2012. We extracted demographic, clinical, treatment, and toxicity data and outcomes. We used logistic and Cox regression models to identify predictors of response and survival respectively. Results Thirty-four 34 patients (8 refractory, 26 resistant) were treated with ECX. Response Evaluation Criteria In Solid Tumors (RECIST) response rate was 45%, median progression-free survival (PFS) was 6.4 months, and overall survival (OS) was 10.6 months. Platinum-resistant patients had better outcomes than did platinum-refractory patients (response rate, 54% vs 0%, P = 0.047; PFS 7.2 vs 1.8 months, P < 0.0001; OS 14.4 vs 3 months, P < 0.001). In regression models, time to progression after first-line treatment and platinum-refractory status were the strongest predictors of response and PFS or OS, respectively. Patients with time to progression after first-line treatment longer than 3 months showed PFS and OS of 7.9 and 14.7 months, respectively. Toxicity was manageable, with only 13% of cycles administered at reduced doses. Conclusions Epirubicin, cisplatin, and capecitabine seems to be active in platinum-resistant relapsed EOC with manageable toxicity. Further prospective investigation of platinum-anthracycline combinations is warranted in patients who relapse 3 to 6 months after

Enhanced-wetting, boron-based liquid-metal ion source and method

DOEpatents

Bozack, Michael J.; Swanson, Lynwood W.; Bell, Anthony E.; Clark Jr., William M.; Utlaut, Mark W.; Storms, Edmund K.

1999-01-01

A binary, boron-based alloy as a source for field-emission-type, ion-beam generating devices, wherein boron predominates in the alloy, preferably with a presence of about 60 atomic percent. The other constituent in the alloy is selected from the group of elements consisting of nickel, palladium and platinum. Predominance of boron in these alloys, during operation, promotes combining of boron with trace impurities of carbon in the alloys to form B.sub.4 C and thus to promote wetting of an associated carbon support substrate.

Platinum-group element, Gold, Silver and Base Metal distribution in compositionally zoned sulfide droplets from the Medvezky Creek Mine, Noril'sk, Russia

USGS Publications Warehouse

Barnes, S.-J.; Cox, R.A.; Zientek, M.L.

2006-01-01

Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril'sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into

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.

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

PubMed

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

2016-10-07

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

Synthesis of Bimetallic Platinum Nanoparticles for Biosensors

PubMed Central

Leteba, Gerard M.; Lang, Candace I.

2013-01-01

The use of magnetic nanomaterials in biosensing applications is growing as a consequence of their remarkable properties; but controlling the composition and shape of metallic nanoalloys is problematic when more than one precursor is required for wet chemistry synthesis. We have developed a successful simultaneous reduction method for preparation of near-spherical platinum-based nanoalloys containing magnetic solutes. We avoided particular difficulties in preparing platinum nanoalloys containing Ni, Co and Fe by the identification of appropriate synthesis temperatures and chemistry. We used transmission electron microscopy (TEM) to show that our particles have a narrow size distribution, uniform size and morphology, and good crystallinity in the as-synthesized condition. Energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) confirms the coexistence of Pt with the magnetic solute in a face-centered cubic (FCC) solid solution. PMID:23941910

XAS analysis of iron and palladium bonded to a polysaccharide produced anaerobically by a strain of Klebsiella oxytoca.

PubMed

Arčon, Iztok; Paganelli, Stefano; Piccolo, Oreste; Gallo, Michele; Vogel-Mikuš, Katarina; Baldi, Franco

2015-09-01

Klebsiella oxytoca BAS-10 ferments citrate to acetic acid and CO2, and secretes a specific exopolysaccharide (EPS), which is able to bind different metallic species. These biomaterials may be used for different biotechnological purposes, including applications as innovative green biogenerated catalysts. In production of biogenerated Pd species, the Fe(III) as ferric citrate is added to anaerobic culture of K. oxytoca BAS-10, in the presence of palladium species, to increase the EPS secretion and improve Pd-EPS yield. In this process, bi-metallic (FePd-EPS) biomaterials were produced for the first time. The morphology of bi-metallic EPS, and the chemical state of the two metals in the FePd-EPS, are investigated by transmission electron microscopy, Fourier transform infra-red spectroscopy, micro-X-ray fluorescence, and X-ray absorption spectroscopy methods (XANES and EXAFS), and compared with mono-metallic Pd-EPS and Fe-EPS complexes. Iron in FePd-EPS is in the mineralized form of iron oxides/hydroxides, predominantly in the form of Fe(3+), with a small amount of Fe(2+) in the structure, most probably a mixture of different nano-crystalline iron oxides and hydroxides, as in mono-metallic Fe-EPS. Palladium is found as Pd(0) in the form of metallic nanoparticles with face-centred cubic structure in both bi-metallic (FePd-EPS) and mono-metallic (Pd-EPS) species. In bi-metallic species, Pd and Fe nanoparticles agglomerate in larger clusters, but they remain spatially separated. The catalytic ability of bi-metallic species (FePd-EPS) in a hydrodechlorination reaction is improved in comparison with mono-metallic Pd-EPS.

Living supramolecular polymerization achieved by collaborative assembly of platinum(II) complexes and block copolymers

PubMed Central

Zhang, Kaka; Yeung, Margaret Ching-Lam; Leung, Sammual Yu-Lut; Yam, Vivian Wing-Wah

2017-01-01

An important feature of biological systems to achieve complexity and precision is the involvement of multiple components where each component plays its own role and collaborates with other components. Mimicking this, we report living supramolecular polymerization achieved by collaborative assembly of two structurally dissimilar components, that is, platinum(II) complexes and poly(ethylene glycol)-b-poly(acrylic acid) (PEG-b-PAA). The PAA blocks neutralize the charges of the platinum(II) complexes, with the noncovalent metal–metal and π–π interactions directing the longitudinal growth of the platinum(II) complexes into 1D crystalline nanostructures, and the PEG blocks inhibiting the transverse growth of the platinum(II) complexes and providing the whole system with excellent solubility. The ends of the 1D crystalline nanostructures have been found to be active during the assembly and remain active after the assembly. One-dimensional segmented nanostructures with heterojunctions have been produced by sequential growth of two types of platinum(II) complexes. The PAA blocks act as adapters at the heterojunctions for lattice matching between chemically and crystallographically different platinum(II) complexes, achieving heterojunctions with a lattice mismatch as large as 21%. PMID:29078381

Metal hierarchical patterning by direct nanoimprint lithography

PubMed Central

Radha, Boya; Lim, Su Hui; Saifullah, Mohammad S. M.; Kulkarni, Giridhar U.

2013-01-01

Three-dimensional hierarchical patterning of metals is of paramount importance in diverse fields involving photonics, controlling surface wettability and wearable electronics. Conventionally, this type of structuring is tedious and usually involves layer-by-layer lithographic patterning. Here, we describe a simple process of direct nanoimprint lithography using palladium benzylthiolate, a versatile metal-organic ink, which not only leads to the formation of hierarchical patterns but also is amenable to layer-by-layer stacking of the metal over large areas. The key to achieving such multi-faceted patterning is hysteretic melting of ink, enabling its shaping. It undergoes transformation to metallic palladium under gentle thermal conditions without affecting the integrity of the hierarchical patterns on micro- as well as nanoscale. A metallic rice leaf structure showing anisotropic wetting behavior and woodpile-like structures were thus fabricated. Furthermore, this method is extendable for transferring imprinted structures to a flexible substrate to make them robust enough to sustain numerous bending cycles. PMID:23446801

Assessing Economic Modulation of Future Critical Materials Use: The Case of Automotive-Related Platinum Group Metals.

PubMed

Zhang, Jingshu; Everson, Mark P; Wallington, Timothy J; Field, Frank R; Roth, Richard; Kirchain, Randolph E

2016-07-19

Platinum-group metals (PGMs) are technological and economic enablers of many industrial processes. This important role, coupled with their limited geographic availability, has led to PGMs being labeled as "critical materials". Studies of future PGM flows have focused on trends within material flows or macroeconomic indicators. We complement the previous work by introducing a novel technoeconomic model of substitution among PGMs within the automotive sector (the largest user of PGMs) reflecting the rational response of firms to changing prices. The results from the model support previous conclusions that PGM use is likely to grow, in some cases strongly, by 2030 (approximately 45% for Pd and 5% for Pt), driven by the increasing sales of automobiles. The model also indicates that PGM-demand growth will be significantly influenced by the future Pt-to-Pd price ratio, with swings of Pt and Pd demand of as much as 25% if the future price ratio shifts higher or lower even if it stays within the historic range. Fortunately, automotive catalysts are one of the more effectively recycled metals. As such, with proper policy support, recycling can serve to meet some of this growing demand.

Resistivity and Resistivity Fluctuations of Thin Film Platinum-Aluminum Oxide Granular Metal-Insulator Composites

NASA Astrophysics Data System (ADS)

Mantese, Joseph Vito

Thin film metal-insulator composites were used to study how the resistivity and fluctuations in the resistivity were altered by changes in conduction mechanism so as to understand the source of the fluctuations and to better understand the conduction processes themselves. Metal-insulator composites were prepared by co -evaporation of platinum and aluminum oxide in a high vacuum system to create a series of films which had a range of metal volume fill fractions, p, from 23% to 100%. The samples were patterned using standard photolithographic techniques to form sample geometries of typical dimensions, length (TURN) 40(mu)m, width (TURN) 2(mu)m and thickness (TURN) 1500(ANGSTROM). The resistivity, (rho), and power spectral density of the resistivity fluctuations, S(,(rho))(f), were measured as a function of p and temperature, T. (rho)(p,T) was found to be a rapidly increasing function of decreasing p, rising monotonically by more than 7 orders of magnitude as p was decreased from 100% to 23%. For p (GREATERTHEQ) 59% the resistivity decreased linearly with decreasing temperature until limited by impurity scattering. The resistivities for the low metal fill fraction materials (p (LESSTHEQ) 50%) increased as the temperature was reduced as expected of thermally assisted tunneling conduction in metal-insulator composites. The transition from metallic conduction to thermally assisted tunneling occurred at a critical value, p(,c), between 59% and 50% Pt. For all samples at all p and T, S(,(rho))(f)(PROPORTIONAL)1/f('(alpha)) (1/f noise) with 0.8 (LESSTHEQ) (alpha) (LESSTHEQ) .1.2 and f the frequency in Hertz. No systematic dependence upon either p or T was found. The normalized noise intensity fS(,(rho))(f)/(rho)('2) (,1) (,Hz) was found to increase monotonically by 5 orders of magnitude with decreasing p then saturate at p(,c) where the conduction mechanism changed from metallic conduction to thermally assisted tunneling. Effective medium theory was used to analyze the role

Enzymatic Recovery of Elemental Palladium by Using Sulfate-Reducing Bacteria

PubMed Central

Lloyd, Jon R.; Yong, Ping; Macaskie, Lynne E.

1998-01-01

Worldwide usage of platinum group metals is increasing, prompting new recovery technologies. Resting cells of Desulfovibrio desulfuricans reduced soluble Pd2+ to elemental, cell-bound Pd0 supported by pyruvate, formate, or H2 as the electron donor without biochemical cofactors. Pd reduction was O2 insensitive, opening the way for recycling and recovery of Pd under oxic conditions. PMID:9797331

PLATINUM AND FUEL CELLS

EPA Science Inventory

Platinum requirements for fuel cell vehicles (FCVS) have been identified as a concern and possible problem with FCV market penetration. Platinum is a necessary component of the electrodes of fuel cell engines that power the vehicles. The platinum is deposited on porous electrodes...

Phenanthridine-Containing Pincer-like Amido Complexes of Nickel, Palladium, and Platinum.

PubMed

Mandapati, Pavan; Giesbrecht, Patrick K; Davis, Rebecca L; Herbert, David E

2017-03-20

Proligands based on bis(8-quinolinyl)amine (L1) were prepared containing one (L2) and two (L3) benzo-fused N-heterocyclic phenanthridinyl (3,4-benzoquinolinyl) units. Taken as a series, L1-L3 provides a ligand template for exploring systematic π-extension in the context of tridentate pincer-like amido complexes of group 10 metals (1-M, 2-M, and 3-M; M = Ni, Pd, Pt). Inclusion of phenanthridinyl units was enabled by development of a cross-coupling/condensation route to 6-unsubstituted, 4-substituted phenanthridines (4-Br, 4-NO 2 , 4-NH 2 ) suitable for elaboration into the target ligand frameworks. Complexes 1-M, 2-M, and 3-M are redox-active; electrochemistry and UV-vis absorption spectroscopy were used to investigate the impact of π-extension on the electronic properties of the metal complexes. Unlike what is typically observed for benzannulated ligand-metal complexes, extending the π-system in metal complexes 1-M to 2-M to 3-M led to only a moderate red shift in the relative highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap as estimated by electrochemistry and similarly subtle changes to the onset of the lowest-energy absorption observed by UV-vis spectroscopy. Time-dependent density functional theory calculations revealed that benzannulation significantly impacts the atomic contributions to the LUMO and LUMO+1 orbitals, altering the orbital contributions to the lowest-energy transition but leaving the energy of this transition essentially unchanged.

Gaseous fuel production from nonrecyclable paper wastes by using supported metal catalysts in high-temperature liquid water.

PubMed

Yamaguchi, Aritomo; Hiyoshi, Norihito; Sato, Osamu; Bando, Kyoko K; Shirai, Masayuki

2010-06-21

Paper wastes are used for the production of gaseous fuels over supported metal catalysts. The gasification of the nonrecyclable paper wastes, such as shredded documents and paper sludge, is carried out in high-temperature liquid water. The order of the catalytic activity for the gasification is found to be ruthenium>rhodium>platinum>palladium. A charcoal-supported ruthenium catalyst (Ru/C) is the most effective for the gasification of paper and cellulose. Paper wastes are gasified to a limited degree (32.6 carbon %) for 30 min in water at 523 K to produce methane and carbon dioxide, with a small amount of hydrogen. At 573 K, more complete gasification with almost 100 carbon % is achieved within 10 min in water. At 523 K, the gas yield of paper gasification over Ru/C is higher than that of cellulose powder. The gas yields are increased by ball-milling treatment of the recycled paper and cellulose powder. Printed paper wastes are also gasified at 523 K in water.

Enhanced-wetting, boron-based liquid-metal ion source and method

DOEpatents

Bozack, M.J.; Swanson, L.W.; Bell, A.E.; Clark, W.M. Jr.; Utlaut, M.W.; Storms, E.K.

1999-02-16

A binary, boron-based alloy as a source for field-emission-type, ion-beam generating devices, wherein boron predominates in the alloy, preferably with a presence of about 60 atomic percent is disclosed. The other constituent in the alloy is selected from the group of elements consisting of nickel, palladium and platinum. Predominance of boron in these alloys, during operation, promotes combining of boron with trace impurities of carbon in the alloys to form B{sub 4}C and thus to promote wetting of an associated carbon support substrate. 1 fig.

Influence of dose on particle size and optical properties of colloidal platinum nanoparticles.

PubMed

Gharibshahi, Elham; Saion, Elias

2012-11-12

Attempts to produce colloidal platinum nanoparticles by using steady absorption spectra with various chemical-based reduction methods often resulted in the fast disappearance of the absorption maxima leaving reduced platinum nanoparticles with little information on their optical properties. We synthesized colloidal platinum nanoparticles in an aqueous solution of polyvinyl pyrrolidone by gamma radiolytic reduction method, which produced steady absorption spectra of fully reduced and highly pure platinum nanoparticles free from by-product impurities or reducing agent contamination. The average particle size was found to be in the range of 3.4–5.3 nm and decreased with increasing dose due to the domination of nucleation over ion association in the formation of metal nanoparticles by the gamma radiolytic reduction method. The platinum nanoparticles exhibit optical absorption spectra with two absorption peaks centered at about 216 and 264 nm and the peaks blue shifted to lower wavelengths with decreasing particle size. The absorption spectra of platinum nanoparticles were also calculated using quantum mechanical treatment and coincidently a good agreement was obtained between the calculated and measured absorption peaks at various particle sizes. This indicates that the 216 and 264-nm absorption peaks of platinum nanoparticles conceivably originated from the intra-band transitions of conduction electrons of (n = 5, l = 2) and (n = 6, l = 0) energy states respectively to higher energy states. The absorption energies, i.e., conduction band energies of platinum nanoparticles derived from the absorption peaks increased with increasing dose and decreased with increasing particle size.

Influence of Dose on Particle Size and Optical Properties of Colloidal Platinum Nanoparticles

PubMed Central

Gharibshahi, Elham; Saion, Elias

2012-01-01

Attempts to produce colloidal platinum nanoparticles by using steady absorption spectra with various chemical-based reduction methods often resulted in the fast disappearance of the absorption maxima leaving reduced platinum nanoparticles with little information on their optical properties. We synthesized colloidal platinum nanoparticles in an aqueous solution of polyvinyl pyrrolidone by gamma radiolytic reduction method, which produced steady absorption spectra of fully reduced and highly pure platinum nanoparticles free from by-product impurities or reducing agent contamination. The average particle size was found to be in the range of 3.4–5.3 nm and decreased with increasing dose due to the domination of nucleation over ion association in the formation of metal nanoparticles by the gamma radiolytic reduction method. The platinum nanoparticles exhibit optical absorption spectra with two absorption peaks centered at about 216 and 264 nm and the peaks blue shifted to lower wavelengths with decreasing particle size. The absorption spectra of platinum nanoparticles were also calculated using quantum mechanical treatment and coincidently a good agreement was obtained between the calculated and measured absorption peaks at various particle sizes. This indicates that the 216 and 264-nm absorption peaks of platinum nanoparticles conceivably originated from the intra-band transitions of conduction electrons of (n = 5, l = 2) and (n = 6, l = 0) energy states respectively to higher energy states. The absorption energies, i.e., conduction band energies of platinum nanoparticles derived from the absorption peaks increased with increasing dose and decreased with increasing particle size. PMID:23203091

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

PubMed

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

2005-12-15

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

The Next Generation of Platinum Drugs: Targeted Pt(II) Agents, Nanoparticle Delivery, and Pt(IV) Prodrugs

PubMed Central

Johnstone, Timothy C.; Suntharalingam, Kogularamanan; Lippard, Stephen J.

2016-01-01

The platinum drugs, cisplatin, carboplatin, and oxaliplatin, prevail in the treatment of cancer,, but new platinum agents have been very slow to enter the clinic. Recently, however, there has been a surge of activity, based on a great deal of mechanistic information, aimed at developing non-classical platinum complexes that operate via mechanisms of action distinct from those of the approved drugs. The use of nanodelivery devices has also grown and many different strategies have been explored to incorporate platinum warheads into nanomedicine constructs. In this review, we discuss these efforts to create the next generation of platinum anticancer drugs. The introduction provides the reader with a brief overview of the use, development, and mechanism of action of the approved platinum drugs to provide the context in which more recent research has flourished. We then describe approaches that explore non-classical platinum(II) complexes with trans geometry and with a monofunctional coordination mode, polynuclear platinum(II) compounds, platinum(IV) prodrugs, dual-treat agents, and photoactivatable platinum(IV) complexes. Nanodelivery particles designed to deliver platinum(IV) complexes will also be discussed, including carbon nanotubes, carbon nanoparticles, gold nanoparticles, quantum dots, upconversion nanoparticles, and polymeric micelles. Additional nanoformulations including supramolecular self-assembled structures, proteins, peptides, metal-organic frameworks, and coordination polymers will then be described. Finally, the significant clinical progress made by nanoparticle formulations of platinum(II) agents will be reviewed. We anticipate that such a synthesis of disparate research efforts will not only help to generate new drug development ideas and strategies, but also reflect our optimism that the next generation of platinum cancer drugs is about to arrive. PMID:26865551

Influence of platinum nanoparticles orally administered to rats evaluated by systemic gene expression profiling.

PubMed

Katao, Kazuo; Honma, Reiko; Kato, Satoko; Watanabe, Shinya; Imai, Jun-ichi

2011-01-01

Platinum is recognized as a harmless metal and is widely used in many industrial products. Recent studies have proposed that platinum in the form of nanoparticles has antioxidant properties, suggesting potential uses for platinum nanoparticles as additives in foods and cosmetics, with direct exposure consequences for humans. However, the influence of platinum nanoparticles on humans has not been sufficiently evaluated, thus far. Therefore, to investigate the influence of platinum nanoparticles on a living body, we comprehensively examined the expression profiles of genes obtained from 25 organs and tissues of rats after oral administration of platinum nanoparticles by gavage. Comparative analysis revealed that the expression levels of 18 genes were altered in 12 organs and tissues after the administration (approximately 0.17% of all the genes examined). Of the tissues examined, those of the glandular stomach, which were most directly exposed to the orally administered platinum nanoparticles, showed altered expression levels of genes associated with inflammation. In subcutaneous adipose tissue, the expression levels of genes whose products exhibited ATPase activity were altered. Real-time reverse transcription polymerase chain reaction (real-time RT-PCR) analysis confirmed the alteration in the expression levels of these genes in these 2 different tissues. Our findings indicate that orally administered platinum nanoparticles do not have a marked effect on systemic gene expression levels, except on a small number of genes expressed in rat tissues, including peripheral tissues indirectly exposed to the orally administered nanoparticles.

Extraterrestrial platinum group nuggets in deep-sea sediments

NASA Technical Reports Server (NTRS)

Brownlee, D. E.; Bates, B. A.; Wheelock, M. M.

1984-01-01

A previously unrecognized property of iron cosmic spheres is reported. The most common spheres larger than 300 microns do not, in fact, contain FeNi metal cores, but instead contain a micrometer-sized nugget composed almost entirely of platinum group elements. These elements appear to have been concentrated by the oxidation of molten meteoritic metal during atmospheric entry. This process is critically dependent on the relative abundance of oxygen in the atmosphere, and the first appearance of the nuggets in the geological record may provide a marker indicating when the oxygen abundance attained half of its present level.

Enhancement of the reduction efficiency of soluble starch for platinum nanoparticles synthesis.

PubMed

Tongsakul, Duangta; Wongravee, Kanet; Thammacharoen, Chuchaat; Ekgasit, Sanong

2012-08-01

In this work, the efficiency of soluble starch as a reducing and a stabilizing agent in the synthesis of platinum nanoparticles under acidic-alkaline treatment is systematically studied. The degraded intermediates with reducing potential (i.e., small molecules containing aldehyde and α-hydroxy ketone moieties) are concomitantly generated when the alkaline concentration is greater than 0.025 M. The in situ generated species could completely reduce platinum ions (20 mM) and sufficiently stabilize the obtained platinum nanoparticles (5 mM) of uniform particle size (2-4 nm). The reduction is efficient and rapid as a complete conversion is achieved within 5 min. In a stronger alkaline condition, the platinum nanoparticles tend to aggregate and form a bigger domain because extensive degradation generates small starch fragments with less stabilization efficiency. This observation suggests that starch is a promising green material which could be chemically treated and transformed to a powerful reducing agent and stabilizer for the synthesis of metal nanoparticles. Copyright © 2012 Elsevier Ltd. All rights reserved.

Platinum-Induced Neurotoxicity and Preventive Strategies: Past, Present, and Future

PubMed Central

Avan, Abolfazl; Postma, Tjeerd J.; Ceresa, Cecilia; Avan, Amir; Cavaletti, Guido; Giovannetti, Elisa

2015-01-01

Neurotoxicity is a burdensome side effect of platinum-based chemotherapy that prevents administration of the full efficacious dosage and often leads to treatment withdrawal. Peripheral sensory neurotoxicity varies from paresthesia in fingers to ataxic gait, which might be transient or irreversible. Because the number of patients being treated with these neurotoxic agents is still increasing, the need for understanding the pathogenesis of this dramatic side effect is critical. Platinum derivatives, such as cisplatin and carboplatin, harm mainly peripheral nerves and dorsal root ganglia neurons, possibly because of progressive DNA-adduct accumulation and inhibition of DNA repair pathways (e.g., extracellular signal-regulated kinase 1/2, c-Jun N-terminal kinase/stress-activated protein kinase, and p38 mitogen-activated protein kinass), which finally mediate apoptosis. Oxaliplatin, with a completely different pharmacokinetic profile, may also alter calcium-sensitive voltage-gated sodium channel kinetics through a calcium ion immobilization by oxalate residue as a calcium chelator and cause acute neurotoxicity. Polymorphisms in several genes, such as voltage-gated sodium channel genes or genes affecting the activity of pivotal metal transporters (e.g., organic cation transporters, organic cation/carnitine transporters, and some metal transporters, such as the copper transporters, and multidrug resistance-associated proteins), can also influence drug neurotoxicity and treatment response. However, most pharmacogenetics studies need to be elucidated by robust evidence. There are supportive reports about the effectiveness of several neuroprotective agents (e.g., vitamin E, glutathione, amifostine, xaliproden, and venlafaxine), but dose adjustment and/or drug withdrawal seem to be the most frequently used methods in the management of platinum-induced peripheral neurotoxicity. To develop alternative options in the treatment of platinum-induced neuropathy, studies on in vitro

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.

Theoretical study of hydrogen storage in metal hydrides.

PubMed

Oliveira, Alyson C M; Pavão, A C

2018-05-04

Adsorption, absorption and desorption energies and other properties of hydrogen storage in palladium and in the metal hydrides AlH 3 , MgH 2 , Mg(BH 4 ) 2 , Mg(BH 4 )(NH 2 ) and LiNH 2 were analyzed. The DFT calculations on cluster models show that, at a low concentration, the hydrogen atom remains adsorbed in a stable state near the palladium surface. By increasing the hydrogen concentration, the tetrahedral and the octahedral sites are sequentially occupied. In the α phase the tetrahedral site releases hydrogen more easily than at the octahedral sites, but the opposite occurs in the β phase. Among the hydrides, Mg(BH 4 ) 2 shows the highest values for both absorption and desorption energies. The absorption energy of LiNH 2 is higher than that of the palladium, but its desorption energy is too high, a recurrent problem of the materials that have been considered for hydrogen storage. The release of hydrogen, however, can be favored by using transition metals in the material structure, as demonstrated here by doping MgH 2 with 3d and 4d-transition metals to reduce the hydrogen atomic charge and the desorption energy.

Synthesis of ultrasmall, homogeneously alloyed, bimetallic nanoparticles on silica supports

NASA Astrophysics Data System (ADS)

Wong, A.; Liu, Q.; Griffin, S.; Nicholls, A.; Regalbuto, J. R.

2017-12-01

Supported nanoparticles containing more than one metal have a variety of applications in sensing, catalysis, and biomedicine. Common synthesis techniques for this type of material often result in large, unalloyed nanoparticles that lack the interactions between the two metals that give the particles their desired characteristics. We demonstrate a relatively simple, effective, generalizable method to produce highly dispersed, well-alloyed bimetallic nanoparticles. Ten permutations of noble and base metals (platinum, palladium, copper, nickel, and cobalt) were synthesized with average particle sizes from 0.9 to 1.4 nanometers, with tight size distributions. High-resolution imaging and x-ray analysis confirmed the homogeneity of alloying in these ultrasmall nanoparticles.

In vitro permeation of palladium powders through intact and damaged human skin.

PubMed

Crosera, Matteo; Mauro, Marcella; Bovenzi, Massimo; Adami, Gianpiero; Baracchini, Elena; Maina, Giovanni; Larese Filon, Francesca

2018-05-01

The use of palladium (Pd) has grown in the last decades, commonly used in automotive catalytic converters, jewellery and dental restorations sectors. Both general and working population can be exposed to this metal, which may act as skin sensitizer. This study investigated in vitro palladium powders permeation through excised intact and damaged human skin using the Franz diffusion cell method and the effect of rapid skin decontamination using sodium laureth-sulphate. 1 mL of a 10 min sonicated suspension made of 2.5 g of Pd powder in 50 mL synthetic sweat at pH 4.5 and room temperature was applied to the outer surface of the skin membranes for 24 h. Pd permeation, assessed by ICP-MS, was higher when damaged skin was used (p = 0.03). Final flux permeation values and lag times were 0.02 ± 0.01 μg cm -2  h -1 and 6.00 ± 3.95 h for intact, and 0.10 ± 0.02 μg cm -2  h -1 and 2.05 ± 1.49 h for damaged skin samples, respectively. Damaged skin protocol enhances Pd skin penetration inside dermal layer (p = 0.04), thus making the metal available for systemic uptake. Pd penetration (p = 0.02) and permeation (p = 0.012) through intact skin decreased significantly when a cleaning procedure was applied. This study demonstrates that after skin exposure to Pd powders a small permeation of the metal happen both through intact and damaged skin and that an early decontamination with a common cleanser can significantly decrease the final amount of metal available forsystemic uptake. Copyright © 2018 Elsevier B.V. All rights reserved.

Tracing metal-silicate segregation and late veneer in the Earth and the ureilite parent body with palladium stable isotopes

NASA Astrophysics Data System (ADS)

Creech, J. B.; Moynier, F.; Bizzarro, M.

2017-11-01

Stable isotope studies of highly siderophile elements (HSE) have the potential to yield valuable insights into a range of geological processes. In particular, the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal-silicate segregation, making them sensitive tracers of planetary differentiation processes. We present the first techniques for the precise determination of palladium stable isotopes by MC-ICPMS using a 106Pd-110Pd double-spike to correct for instrumental mass fractionation. Results are expressed as the per mil (‰) difference in the 106Pd/105Pd ratio (δ106Pd) relative to an in-house solution standard (Pd_IPGP) in the absence of a certified Pd isotopic standard. Repeated analyses of the Pd isotopic composition of the chondrite Allende demonstrate the external reproducibility of the technique of ±0.032‰ on δ106Pd. Using these techniques, we have analysed Pd stable isotopes from a range of terrestrial and extraterrestrial samples. We find that chondrites define a mean δ106Pdchondrite = -0.19 ± 0.05‰. Ureilites reveal a weak trend towards heavier δ106Pd with decreasing Pd content, similar to recent findings based on Pt stable isotopes (Creech et al., 2017), although fractionation of Pd isotopes is significantly less than for Pt, possibly related to its weaker metal-silicate partitioning behaviour and the limited field shift effect. Terrestrial mantle samples have a mean δ106Pdmantle = -0.182 ± 0.130‰, which is consistent with a late-veneer of chondritic material after core formation.

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

NASA Astrophysics Data System (ADS)

Rudraswami, N. G.; Parashar, K.; Shyam Prasad, M.

2011-03-01

We examined 378 micrometeorites collected from deep-sea sediments of the Indian Ocean of which 175, 180, and 23 are I-type, S-type, and G-type, respectively. Of the 175 I-type spherules, 13 contained platinum group element nuggets (PGNs). The nuggets occur in two distinct sizes and have distinctly different elemental compositions: micrometer (μm)-sized nuggets that are >3 μm contain dominantly Ir, Os, and Ru (iridium-platinum group element or IPGE) and sub-μm (or nanometer)-sized (<1 μm) nuggets, which contain dominantly Pt, Rh, and Pd (palladium—PGE or PPGE). The μm-sized nuggets are found only one per spherule in the cross section observed and are usually found at the edge of the spherule. By contrast, there are hundreds of nanometer-sized nuggets distributed dominantly in the magnetite phases of the spherules, and rarely in the wüstite phases. Both the nugget types are found as separate entities in the same spherule and apparently, nugget formation is a common phenomenon among I-type micrometeorites. However, the μm-sized nuggets are seen in fewer specimens (˜2.5% of the observed I-type spherules). In all, we analyzed four nuggets of μm size and 213 nanometer-sized nuggets from 13 I-type spherules for platinum group elements. Chemically, the μm-sized PGNs contain chondritic ratios of Os/Ir, but are depleted in the more volatile PGE (Pt, Rh, and Pd) relative to chondritic ratios. On the other hand, the nanometer-sized nuggets contain dominantly Pt and Rh. Importantly, the refractory PGEs are conspicuous by their absence in these nanometer nuggets. Palladium, the most volatile PGE is highly depleted (<1.1%) with respect to chondritic ratios in the μm-sized PGNs, and is observed in only 17 of 213 nanometer nuggets with concentrations that are just above the detection limit (≥0.2%). Distinct fractionation of the PGE into IPGE (Ir, Os, Ru) and PPGE seems to take place during the short span of atmospheric entry. These observations suggest several

Process for recovery of palladium from nuclear fuel reprocessing wastes

DOEpatents

Campbell, D.O.; Buxton, S.R.

1980-06-16

Palladium is selectively removed from spent nuclear fuel reprocessing waste by adding sugar to a strong nitric acid solution of the waste to partially denitrate the solution and cause formation of an insoluble palladium compound. The process includes the steps of: (a) adjusting the nitric acid content of the starting solution to about 10 M; (b) adding 50% sucrose solution in an amount sufficient to effect the precipitation of the palladium compound; (c) heating the solution at reflux temperature until precipitation is complete; and (d) centrifuging the solution to separate the precipitated palladium compound from the supernatant liquid.

Process for recovery of palladium from nuclear fuel reprocessing wastes

DOEpatents

Campbell, David O.; Buxton, Samuel R.

1981-01-01

Palladium is selectively removed from spent nuclear fuel reprocessing waste by adding sugar to a strong nitric acid solution of the waste to partially denitrate the solution and cause formation of an insoluble palladium compound. The process includes the steps of: (a) adjusting the nitric acid content of the starting solution to about 10 M, (b) adding 50% sucrose solution in an amount sufficient to effect the precipitation of the palladium compound, (c) heating the solution at reflux temperature until precipitation is complete, and (d) centrifuging the solution to separate the precipitated palladium compound from the supernatant liquid.

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.

Fission product palladium-silicon carbide interaction in htgr fuel particles

NASA Astrophysics Data System (ADS)

Minato, Kazuo; Ogawa, Toru; Kashimura, Satoru; Fukuda, Kousaku; Shimizu, Michio; Tayama, Yoshinobu; Takahashi, Ishio

1990-07-01

Interaction of fission product palladium (Pd) with the silicon carbide (SiC) layer was observed in irradiated Triso-coated uranium dioxide particles for high temperature gas-cooled reactors (HTGR) with an optical microscope and electron probe microanalyzers. The SiC layers were attacked locally or the reaction product formed nodules at the attack site. Although the main element concerned with the reaction was palladium, rhodium and ruthenium were also detected at the corroded areas in some particles. Palladium was detected on both the hot and cold sides of the particles, but the corroded areas and the palladium accumulations were distributed particularly on the cold side of the particles. The observed Pd-SiC reaction depths were analyzed on the assumption that the release of palladium from the fuel kernel controls the whole Pd-SiC reaction.

Temperature- and composition-dependent hydrogen diffusivity in palladium from statistically-averaged molecular dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Xiaowang; Heo, Tae Wook; Wood, Brandon C.

Solid-state hydrogen storage materials undergo complex phase transformations whose kinetics is often limited by hydrogen diffusion. Among metal hydrides, palladium hydride undergoes a diffusional phase transformation upon hydrogen uptake, during which the hydrogen diffusivity varies with hydrogen composition and temperature. Here we perform robust statistically-averaged molecular dynamics simulations to obtain a well-converged analytical expression for hydrogen diffusivity in bulk palladium that is valid throughout all stages of the reaction. Our studies confirm significant dependence of the diffusivity on composition and temperature that elucidate key trends in the available experimental measurements. Whereas at low hydrogen compositions, a single process dominates, atmore » high hydrogen compositions, diffusion is found to exhibit behavior consistent with multiple hopping barriers. Further analysis, supported by nudged elastic band computations, suggests that the multi-barrier diffusion can be interpreted as two distinct mechanisms corresponding to hydrogen-rich and hydrogen-poor local environments.« less

Temperature- and composition-dependent hydrogen diffusivity in palladium from statistically-averaged molecular dynamics

DOE PAGES

Zhou, Xiaowang; Heo, Tae Wook; Wood, Brandon C.; ...

2018-03-09

Solid-state hydrogen storage materials undergo complex phase transformations whose kinetics is often limited by hydrogen diffusion. Among metal hydrides, palladium hydride undergoes a diffusional phase transformation upon hydrogen uptake, during which the hydrogen diffusivity varies with hydrogen composition and temperature. Here we perform robust statistically-averaged molecular dynamics simulations to obtain a well-converged analytical expression for hydrogen diffusivity in bulk palladium that is valid throughout all stages of the reaction. Our studies confirm significant dependence of the diffusivity on composition and temperature that elucidate key trends in the available experimental measurements. Whereas at low hydrogen compositions, a single process dominates, atmore » high hydrogen compositions, diffusion is found to exhibit behavior consistent with multiple hopping barriers. Further analysis, supported by nudged elastic band computations, suggests that the multi-barrier diffusion can be interpreted as two distinct mechanisms corresponding to hydrogen-rich and hydrogen-poor local environments.« less

Mechanical and spectroscopic properties of metal-containing polyimides

NASA Technical Reports Server (NTRS)

Taylor, L. T.; St.clair, A. K.

1983-01-01

The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymerization or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.

Mechanical and spectroscopic properties of metal containing polyimides

NASA Technical Reports Server (NTRS)

Taylor, L. T.; St. Clair, A. K.

1984-01-01

The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymermzation or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.

METAL COMPOSITIONS

DOEpatents

Seybolt, A.U.

1959-02-01

Alloys of uranium which are strong, hard, and machinable are presented, These alloys of uranium contain bctween 0.1 to 5.0% by weight of at least one noble metal such as rhodium, palladium, and gold. The alloys may be heat treated to obtain a product with iniproved tensile and compression strengths,

Non-Platinum Group Metal OER/ORR Catalysts for Alkaline Membrane Fuel Cells and Electrolyzers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Danilovic, Nemanja; Ayers, Katherine

Regenerative fuel cells (RFC) are energy storage devices that capture electrical energy in the form of hydrogen, with potential application for backup power and energy storage in remote locations, unmanned missions, and renewable energy capture. A unitized regenerative fuel cell (URFC) combines two separate electrochemical devices (fuel cell and electrolyzer) into one stack. The stack cost is driven by the platinum group metal (PGM) catalysts and the flow field components designed to withstand high potentials in acidic environments. Since the stack is the most expensive subcomponent of both the fuel cell and electrolyzer system, combining the two devices results inmore » substantial reduction in capital cost. However, in the past, combining the two stacks sacrificed device performance (operating cost) largely because the fuel cell had to operate with the thick electrolysis membranes in a URFC configuration, and due to water management issues in switching modes. Recent work in membrane-based electrolysis has resulted in more mechanically robust designs and materials that allow much thinner membranes, and work in flow cell design such as flow batteries has shown improved water transport through channel design and wet-proofing approaches. Therefore, the URFC concept is worth revisiting. At the same time, alkaline exchange membrane (AEM) devices are gathering attention due to the promise of PGM and valve metal elimination from the stack and a resulting strategic and capital cost benefit as compared with proton exchange membrane (PEM) systems. The result is a lower capital cost system that has half the precious metal group (PGM) catalysts, membrane and other stack component materials compared with discrete RFCs, although at the sacrifice of performance (operating cost). Proton has identified innovative AEM based RFC's to fulfill the role of low capital cost energy storage device owing to the use of non-precious metal containing electrodes, that enables certain markets

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

HYDRODEHALOGENATION OF 1- TO 3-CARBON HALOGENATED ORGANIC COMPOUNDS IN WATER USING A PALLADIUM CATALYST AND HYDROGEN GAS. (R825421)

EPA Science Inventory

Supported palladium (Pd) metal catalysts along with H₂ gas show
significant potential as a technology which can provide rapid, on-site
destruction of halogenated groundwater contaminants. Pd catalyzes the rapid
hydrodehalogenation of nine 1- to 3-carbon ...

Matrix elimination method for the determination of precious metals in ores using electrothermal atomic absorption spectrometry.

PubMed

Salih, Bekir; Celikbiçak, Omür; Döker, Serhat; Doğan, Mehmet

2007-03-28

Poly(N-(hydroxymethyl)methacrylamide)-1-allyl-2-thiourea) hydrogels, poly(NHMMA-ATU), were synthesized by gamma radiation using (60)Co gamma source in the ternary mixture of NHMMA-ATU-H(2)O. These hydrogels were used for the specific gold, silver, platinum and palladium recovery, pre-concentration and matrix elimination from the solutions containing trace amounts of precious metal ions. Elimination of inorganic matrices such as different transition and heavy metal ions, and anions was performed by adjusting the solution pH to 0.5 that was the selective adsorption pH of the precious metal ions. Desorption of the precious metal ions was performed by using 0.8 M thiourea in 3M HCl as the most efficient desorbing agent with recovery values more than 95%. In the desorption medium, thiourea effect on the atomic signal was eliminated by selecting proper pyrolysis and atomization temperatures for all precious metal ions. Precision and the accuracy of the results were improved in the graphite furnace-atomic absorption spectrometer (GFAAS) measurements by applying the developed matrix elimination method performing the adsorption at pH 0.5. Pre-concentration factors of the studied precious metal ions were found to be at least 1000-fold. Detection limits of the precious metal ions were found to be less than 10 ng L(-1) of the all studied precious metal ions by using the proposed pre-concentration method. Determination of trace levels of the precious metals in the sea-water, anode slime, geological samples and photographic fixer solutions were performed using GFAAS clearly after applying the adsorption-desorption cycle onto the poly(NHMMA-UTU) hydrogels.

Recovery of cesium and palladium from nuclear reactor fuel processing waste

DOEpatents

Campbell, David O.

1976-01-01

A method of recovering cesium and palladium values from nuclear reactor fission product waste solution involves contacting the solution with a source of chloride ions and oxidizing palladium ions present in the solution to precipitate cesium and palladium as Cs.sub.2 PdCl.sub.6.

External-beam PIXE spectrometry for the study of Punic jewellery (SW Spain): The geographical provenance of the palladium-bearing gold

NASA Astrophysics Data System (ADS)

Ontalba Salamanca, M. Á.; Gómez-Tubío, B.; Ortega-Feliu, I.; Respaldiza, M. Á.; Luisa de la Bandera, M.; Ovejero Zappino, G.; Bouzas, A.; Gómez-Morón, A.

2006-08-01

This paper presents the study of a set of Punic gold items (400 B.C.), from the Museum of Cádiz (Spain). An external beam set-up has been employed for the absolutely non-destructive analysis of the objects. PIXE spectrometry has been performed in order to characterize the metallic alloys and the manufacturing techniques. Compositional differences have been found and soldering procedures have been identified. By comparison with the rings and other coetaneous jewellery, the presence of palladium in the bulk alloy of the earrings can be pointed out. The geographical provenance of the palladium-bearing gold is discussed based on geological and archaeological considerations.

Detection of platinum species in plant material.

PubMed

Messerschmidt, J; Alt, F; Tölg, G

1995-05-01

Model experiments for the detection of platinum species in extracts from native and platinum-treated grass cultivations are described. The procedural steps are cultivation of the grass samples, extraction and concentration of the platinum species by ultrafiltration and freeze-drying, preparative separation of the species by gel chromatography followed by isotachophoresis, and sequential analytical detection of the separated platinum species by adsorptive voltammetry. After isotachophoresis, sharp peaks of platinum species could be detected. In the native grass extract only one platinum species (160-200 kDa) was found. In the platinum-treated grass extracts several platinum species were observed in the molecular mass range from 1 to > 1000 kDa. By an extremely sensitive platinum determination method (adsorptive voltammetry; detection limit, 2 pg Pt abs.) it was possible to detect platinum even in stained protein bands from horizontal gel electrophoresis of platinum containing fractions obtained after isotachophoresis.

Palladium coupling catalysts for pharmaceutical applications.

PubMed

Doucet, Henri; Hierso, Jean-Cyrille

2007-11-01

This review discusses recent advances made in the area of palladium-catalyzed coupling reactions and describes a selection of the catalytic systems that are useful in the preparation of valuable compounds for the pharmaceutical industry. Most of these types of syntheses have used either simple palladium salts or palladium precursors associated with electron-rich mono- or bidentate phosphine ligands as catalysts. For some reactions, ligands such as triphenyl phosphine, 1,1'-bis(diphenylphosphino)ferrocene, a carbene or a bipyridine have also been employed. Several new procedures for the Suzuki cross-coupling reaction, the activation of aryl chlorides, the functionalization of aromatics and the synthesis of heteroaromatics are discussed. The C-H activation/ functionalization reactions of aryl and heteroaryl derivatives have emerged as powerful tools for the preparation of biaryl compounds, and the recent procedures and catalysts employed in this promising field are also highlighted herein.

Palladium catalyzed hydrogenation of bio-oils and organic compounds

DOEpatents

Elliott, Douglas C [Kennewick, WA; Hu, Jianli [Richland, WA; Hart,; Todd, R [Kennewick, WA; Neuenschwander, Gary G [Burbank, WA

2011-06-07

The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

Palladium catalyzed hydrogenation of bio-oils and organic compounds

DOEpatents

Elliott, Douglas C [Richland, WA; Hu, Jianli [Kennewick, WA; Hart, Todd R [Kennewick, WA; Neuenschwander, Gary G [Burbank, WA

2008-09-16

The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

Permeation of platinum and rhodium nanoparticles through intact and damaged human skin

NASA Astrophysics Data System (ADS)

Mauro, Marcella; Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo; Jaganjac, Morana; Bovenzi, Massimo; Filon, Francesca Larese

2015-06-01

The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na2PtCl6 and RhCl3·3H2O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm-2 h-1 and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration.

Catalytic Palladium Film Deposited by Scalable Low-Temperature Aqueous Combustion.

PubMed

Voskanyan, Albert A; Li, Chi-Ying Vanessa; Chan, Kwong-Yu

2017-09-27

This article describes a novel method for depositing a dense, high quality palladium thin film via a one-step aqueous combustion process which can be easily scaled up. Film deposition of Pd from aqueous solutions by conventional chemical or electrochemical methods is inhibited by hydrogen embrittlement, thus resulting in a brittle palladium film. The method outlined in this work allows a direct aqueous solution deposition of a mirror-bright, durable Pd film on substrates including glass and glassy carbon. This simple procedure has many advantages including a very high deposition rate (>10 cm 2 min -1 ) and a relatively low deposition temperature (250 °C), which makes it suitable for large-scale industrial applications. Although preparation of various high-quality oxide films has been successfully accomplished via solution combustion synthesis (SCS) before, this article presents the first report on direct SCS production of a metallic film. The mechanism of Pd film formation is discussed with the identification of a complex formed between palladium nitrate and glycine at low temperature. The catalytic properties and stability of films are successfully tested in alcohol electrooxidation and electrochemical oxygen reduction reaction. It was observed that combustion deposited Pd film on a glassy carbon electrode showed excellent catalytic activity in ethanol oxidation without using any binder or additive. We also report for the first time the concept of a reusable "catalytic flask" as illustrated by the Suzuki-Miyaura cross-coupling reaction. The Pd film uniformly covers the inner walls of the flask and eliminates the catalyst separation step. We believe the innovative concept of a reusable catalytic flask is very promising and has the required features to become a commercial product in the future.

Fabrication of Nitrogen-Doped Mesoporous-Carbon-Coated Palladium Nanoparticles: An Intriguing Electrocatalyst for Methanol and Formic Acid Oxidation.

PubMed

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

2016-05-20

Inspired by the attractive catalytic properties of palladium and the inert nature of carbon supports in catalysis, a concise and simple methodology for in situ nitrogen-doped mesoporous-carbon-supported palladium nanoparticles (Pd/N-C) has been developed by carbonizing a palladium dimethylglyoximate complex. The as-synthesized Pd/N-C has been exfoliated as a fuel cell catalyst by studying the electro-oxidation of methanol and formic acid. The material synthesized at 400 °C,namely, Pd/N-C-400,exhibitssuperior mass activity and stability among catalysts synthesized under different carbonization temperaturesbetween300 and 500 °C. The unique 1D porous structure in Pd/N-C-400 helps better electron transport at the electrode surface, which eventually leads to about five times better catalytic activity and about two times higher stability than that of commercial Pd/C. Thus, our designed sacrificial metal-organic templatedirected pathway becomes a promising technique for Pd/N-C synthesis with superior catalytic performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of bactericidal properties of carbohydrate-stabilized platinum oxide nanoparticles

NASA Astrophysics Data System (ADS)

Rezaei-Zarchi, Saeed; Imani, Saber; mohammad Zand, Ali; Saadati, Mojtaba; Zaghari, Zahra

2012-09-01

Platinum oxide nanoparticles were prepared by a simple hydrothermal route and chemical reduction using carbohydrates (fructose and sucrose) as the reducing and stabilizing agents. In comparison with other metals, platinum oxide has less environmental pollution. Therefore, Pt is considered an appropriate candidate to deal with environmental pathogens. The crystallite size of these nanoparticles was evaluated from X-ray diffraction, atomic force microscopy, and transmission electron microscopy (TEM) and was found to be 10 nm, which is the demonstration of EM bright field and transmission electron microscopy. The effect of carbohydrates on the morphology of the nanoparticles was studied using TEM. The nanoparticles were administered to the Pseudomonas stutzeri and Lactobacillus cultures, and the incubation was done at 37°C for 24 h. The nanocomposites exhibited interesting inhibitory as well as bactericidal activity against P. stutzeri and Lactobacillus species. Incorporation of nanoparticles also increased the thermal stability of the carbohydrates. The results of this paper showed that carbohydrates can serve as a carrier for platinum oxide nanoparticles, and nanocomposites can have potential biological applications.

The nature of thrombosis induced by platinum and tungsten coils in saccular aneurysms.

PubMed

Byrne, J V; Hope, J K; Hubbard, N; Morris, J H

1997-01-01

To compare the efficacy and biocompatability of electrolytic and mechanically detachable embolization coils of two metal types. Experimental saccular aneurysms in pigs were used to assess embolization induced by platinum or tungsten coils. Longitudinal angiographic and histologic studies were performed on treated and untreated (control) aneurysms to compare thrombosis and cellular responses after embolization with electrolytically detachable platinum coils and with mechanically detached tungsten coils. Fewer tungsten than platinum coils were needed to induce thrombosis. The inflammatory response within the aneurysmal lumen was more florid in embolized aneurysms than in control aneurysms. No difference was found in the timing or extent of accumulation of eosinophils, lymphocytes, or polymorphs between the two coils used. Giant cell responses were more marked in treated aneurysms; tungsten coils more than platinum coils. The amount of collagen and fibrosis present increased over the study period and was similar in treated and control aneurysms. The coil type influenced the initial cellular response but had little effect on the rate or degree to which blood clot within the aneurysm was replaced by fibrous tissue.

Carbon Nanotubes as Support in the Platinum-Catalyzed Hydrolytic Dehydrogenation of Ammonia Borane.

PubMed

Chen, Wenyao; Duan, Xuezhi; Qian, Gang; Chen, De; Zhou, Xinggui

2015-09-07

We report remarkable support effects for carbon nanotubes (CNTs) in the Pt/CNT-catalyzed hydrolytic dehydrogenation of ammonia borane. The origin of the support-dependent activity and durability is elucidated by combining the catalytic and durability testing with characterization by a range of spectroscopy and high-angle annular dark-field scanning transmission electron microscopy techniques and ICP analysis. The effects mainly arise from different electronic properties and different abilities for the adsorption of boron-containing species on platinum surfaces and changes in size and shape of the platinum particles during the reaction. Defect-rich CNTs in particular are a promising support material, as it not only enhances the platinum binding energy, leading to the highest hydrogen generation rate, but also inhibits the adsorption of boron-containing species and stabilizes the platinum nanoparticles to resist the agglomeration during the reaction, leading to the highest durability. The insights revealed herein may pave the way for the rational design of highly active and durable metal/carbon catalysts for the hydrolytic dehydrogenation of ammonia borane. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of platinum nanoparticle electrocatalysts by atomic layer deposition

NASA Astrophysics Data System (ADS)

Lubers, Alia Marie

Demand for energy continues to increase, and without alternatives to fossil fuel combustion the effects on our environment will become increasingly severe. Fuel cells offer a promising improvement on current methods of energy generation; they are able to convert hydrogen fuel into electricity with a theoretical efficiency of up to 83% and interface smoothly with renewable hydrogen production. Fuel cells can replace internal combustion engines in vehicles and are used in stationary applications to power homes and businesses. The efficiency of a fuel cell is maximized by its catalyst, which is often composed of platinum nanoparticles supported on carbon. Economical production of fuel cell catalysts will promote adoption of this technology. Atomic layer deposition (ALD) is a possible method for producing catalysts at a large scale when employed in a fluidized bed. ALD relies on sequential dosing of gas-phase precursors to grow a material layer by layer. We have synthesized platinum nanoparticles on a carbon particle support (Pt/C) by ALD for use in proton exchange membrane fuel cells (PEMFCs) and electrochemical hydrogen pumps. Platinum nanoparticles with different characteristics were deposited by changing two chemistries: the carbon substrate through functionalization; and the deposition process by use of either oxygen or hydrogen as ligand removing reactants. The metal depositing reactant was trimethyl(methylcyclopentadienyl)platinum(IV). Functionalizing the carbon substrate increased nucleation during deposition resulting in smaller and more dispersed nanoparticles. Use of hydrogen produced smaller nanoparticles than oxygen, due to a gentler hydrogenation reaction compared to using oxygen's destructive combustion reaction. Synthesized Pt/C materials were used as catalysts in an electrochemical hydrogen pump, a device used to separate hydrogen fuel from contaminants. Catalysts deposited by ALD on functionalized carbon using a hydrogen chemistry were the most

Catalytic method for synthesizing hydrocarbons