Science.gov

Sample records for cell noble metal

  1. Noble metals in oncology

    PubMed Central

    Markowska, Anna; Jaszczyńska-Nowinka, Karolina; Lubin, Jolanta; Markowska, Janina

    2015-01-01

    Worldwide research groups are searching for anticancer compounds, many of them are organometalic complexes having platinum group metals as their active centers. Most commonly used cytostatics from this group are cisplatin, carboplatin and oxaliplatin. Cisplatin was used fot the first time in 1978, from this time many platinum derivatives were created. In this review we present biological properties and probable future clinical use of platinum, gold, silver, iridium and ruthenium derivatives. Gold derivative Auranofin has been studied extensively. Action of silver nanoparticles on different cell lines was analysed. Iridium isotopes are commonly used in brachyterapy. Ruthenium compound new anti-tumour metastasis inhibitor (NAMI-A) is used in managing lung cancer metastases. Electroporation of another ruthenium based compound KP1339 was also studied. Most of described complexes have antiproliferative and proapoptotic properties. Further studies need to be made. Nevertheless noble metal based chemotherapheutics and compounds seem to be an interesting direction of research. PMID:26557773

  2. Noble metal ionic catalysts.

    PubMed

    Hegde, M S; Madras, Giridhar; Patil, K C

    2009-06-16

    Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NO(x), and unburned hydrocarbons-need to be fully converted to CO(2), N(2), and H(2)O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al(2)O(3) or SiO(2) promoted by CeO(2). However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce(1-x)M(x)O(2-delta) and Ce(1-x-y)Ti(y)M(x)O(2-delta) (M = Pt, Pd, Rh; x = 0.01-0.02, delta approximately x, y = 0.15-0.25) oxides in fluorite structure. In these oxide catalysts, Pt(2+), Pd(2+), or Rh(3+) ions are substituted only to the extent of 1-2% of Ce(4+) ion. Lower-valent noble metal ion substitution in CeO(2) creates oxygen vacancies. Reducing molecules (CO, H(2), NH(3)) are adsorbed onto electron-deficient noble metal ions, while oxidizing (O(2), NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NO(x) reduction (with >80% N(2) selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO(2) or Ce(1-x)Ti(x)O(2) were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the

  3. Alkaline polymer electrolyte fuel cells completely free from noble metal catalysts

    PubMed Central

    Lu, Shanfu; Pan, Jing; Huang, Aibin; Zhuang, Lin; Lu, Juntao

    2008-01-01

    In recent decades, fuel cell technology has been undergoing revolutionary developments, with fundamental progress being the replacement of electrolyte solutions with polymer electrolytes, making the device more compact in size and higher in power density. Nowadays, acidic polymer electrolytes, typically Nafion, are widely used. Despite great success, fuel cells based on acidic polyelectrolyte still depend heavily on noble metal catalysts, predominantly platinum (Pt), thus increasing the cost and hampering the widespread application of fuel cells. Here, we report a type of polymer electrolyte fuel cells (PEFC) employing a hydroxide ion-conductive polymer, quaternary ammonium polysulphone, as alkaline electrolyte and nonprecious metals, chromium-decorated nickel and silver, as the catalyst for the negative and positive electrodes, respectively. In addition to the development of a high-performance alkaline polymer electrolyte particularly suitable for fuel cells, key progress has been achieved in catalyst tailoring: The surface electronic structure of nickel has been tuned to suppress selectively the surface oxidative passivation with retained activity toward hydrogen oxidation. This report of a H2–O2 PEFC completely free from noble metal catalysts in both the positive and negative electrodes represents an important advancement in the research and development of fuel cells.

  4. Fluorescent noble metal nanoclusters

    NASA Astrophysics Data System (ADS)

    Zheng, Jie

    Water-soluble fluorescent metallic clusters at sizes comparable to the Fermi wavelength of an electron (˜0.5 nm for gold and silver) were created and their photophysical properties were investigated at the bulk and single molecule levels. We employed biocompatible dendrimer and peptide to prepare a series of strong fluorescent gold and silver clusters with chemical or photo reduction methods. Facilitated by the well-defined dendrimer size, electrospray ionization mass spectrometry indicates that the fluorescent silver nanocluster size ranges from 2 to 8 Ag atoms. The correlation of emission energy with the number of atoms, N, in each gold nanocluster is quantitatively fit for the smallest nanoclusters with no adjustable parameters by the simple scaling relation of EFermi/N1/3, in which EFermi is the Fermi energy of bulk gold. The transition energy scaling inversely with cluster radius indicates that electronic structure can be well described with the spherical jellium model and further demonstrates that these nanomaterials are "multi-electron artificial atoms". Fluorescence from these small metal clusters can be considered protoplasmonic, molecular transitions of the free conduction electrons before the onset of collective dipole oscillations occurring when a continuous density of states is reached. In addition, very strong single molecular Stokes and anti-Stokes Raman enhancement by fluorescent silver clusters was observed. Pushing to larger sizes, we also created ˜2nm diameter glutathione encapsulated luminescent gold nanoparticles. Distinct from similarly sized but nonluminescent gold nanoparticles, these 2 nm gold nanoparticles show bright, long lifetime emission but no plasmon absorption. The emission might arise from charge transfer between gold atoms and the thiol ligand. Providing the "missing link" between atomic and nanoparticle behavior in noble metals, these highly fluorescent, water-soluble gold and silver nanoclusters offer complementary transition

  5. Environmentally Friendly Carbon-Preserving Recovery of Noble Metals From Supported Fuel Cell Catalysts.

    PubMed

    Latsuzbaia, R; Negro, E; Koper, G J M

    2015-06-01

    The dissolution of noble-metal catalysts under mild and carbon-preserving conditions offers the possibility of in situ regeneration of the catalyst nanoparticles in fuel cells or other applications. Here, we report on the complete dissolution of the fuel cell catalyst, platinum nanoparticles, under very mild conditions at room temperature in 0.1 M HClO4 and 0.1 M HCl by electrochemical potential cycling between 0.5-1.1 V at a scan rate of 50 mV s(-1) . Dissolution rates as high as 22.5 μg cm(-2) per cycle were achieved, which ensured a relatively short dissolution timescale of 3-5 h for a Pt loading of 0.35 mg cm(-2) on carbon. The influence of chloride ions and oxygen in the electrolyte on the dissolution was investigated, and a dissolution mechanism is proposed on the basis of the experimental observations and available literature results. During the dissolution process, the corrosion of the carbon support was minimal, as observed by X-ray photoelectron spectroscopy (XPS).

  6. Environmentally Friendly Carbon-Preserving Recovery of Noble Metals From Supported Fuel Cell Catalysts.

    PubMed

    Latsuzbaia, R; Negro, E; Koper, G J M

    2015-06-01

    The dissolution of noble-metal catalysts under mild and carbon-preserving conditions offers the possibility of in situ regeneration of the catalyst nanoparticles in fuel cells or other applications. Here, we report on the complete dissolution of the fuel cell catalyst, platinum nanoparticles, under very mild conditions at room temperature in 0.1 M HClO4 and 0.1 M HCl by electrochemical potential cycling between 0.5-1.1 V at a scan rate of 50 mV s(-1) . Dissolution rates as high as 22.5 μg cm(-2) per cycle were achieved, which ensured a relatively short dissolution timescale of 3-5 h for a Pt loading of 0.35 mg cm(-2) on carbon. The influence of chloride ions and oxygen in the electrolyte on the dissolution was investigated, and a dissolution mechanism is proposed on the basis of the experimental observations and available literature results. During the dissolution process, the corrosion of the carbon support was minimal, as observed by X-ray photoelectron spectroscopy (XPS). PMID:25959077

  7. Mesoporous nano/micro noble metal particles: synthesis and applications.

    PubMed

    Yang, Shengchun; Luo, Xiao

    2014-05-01

    The morphology, size and composition often govern the physical and chemical properties of noble metal units with a size in the nano or micro scale. Thus, the controlled growth of noble metal crystals would help to tailor their unique properties and this would be followed by their practical application. Mesoporous nano/micro noble metal units are types of nanostructured material that have fascinating properties that can generate great potential for various applications. This review presents a general view on the growth mechanisms of porous noble metal units and is focused on recent progresses in their synthetic approaches. Then, their potential applications in the field of drug delivery, cell imaging and SERS substrates, as well as fuel cell catalysts are overviewed.

  8. 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.

  9. Incorporation of noble metals into aerogels

    DOEpatents

    Hair, Lucy M.; Sanner, Robert D.; Coronado, Paul R.

    1998-01-01

    Aerogels or xerogels containing atomically dispersed noble metals for applications such environmental remediation. New noble metal precursors, such as Pt--Si or Pd(Si--P).sub.2, have been created to bridge the incompatibility between noble metals and oxygen, followed by their incorporation into the aerogel or xerogel through sol-gel chemistry and processing. Applications include oxidation of hydrocarbons and reduction of nitrogen oxide species, complete oxidation of volatile organic carbon species, oxidative membranes for photocatalysis and partial oxidation for synthetic applications.

  10. Incorporation of noble metals into aerogels

    DOEpatents

    Hair, L.M.; Sanner, R.D.; Coronado, P.R.

    1998-12-22

    Aerogels or xerogels containing atomically dispersed noble metals for applications such as environmental remediation are disclosed. New noble metal precursors, such as Pt--Si or Pd(Si--P){sub 2}, have been created to bridge the incompatibility between noble metals and oxygen, followed by their incorporation into the aerogel or xerogel through sol-gel chemistry and processing. Applications include oxidation of hydrocarbons and reduction of nitrogen oxide species, complete oxidation of volatile organic carbon species, oxidative membranes for photocatalysis and partial oxidation for synthetic applications.

  11. 21 CFR 872.3060 - Noble metal alloy.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

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

  12. 21 CFR 872.3060 - Noble metal alloy.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

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

  13. 21 CFR 872.3060 - Noble metal alloy.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 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,...

  14. Noble metal superparticles and methods of preparation thereof

    DOEpatents

    Sun, Yugang; Hu, Yongxing

    2016-07-12

    A method comprises heating an aqueous solution of colloidal silver particles. A soluble noble metal halide salt is added to the aqueous solution which undergoes a redox reaction on a surface of the silver particles to form noble metal/silver halide SPs, noble metal halide/silver halide SPs or noble metal oxide/silver halide SPs on the surface of the silver particles. The heat is maintained for a predetermined time to consume the silver particles and release the noble metal/silver halide SPs, the noble metal halide/silver halide SPs or the noble metal oxide/silver halide SPs into the aqueous solution. The aqueous solution is cooled. The noble metal/silver halide SPs, the noble metal halide/silver halide SPs or noble metal oxide/silver halide SPs are separated from the aqueous solution. The method optionally includes adding a soluble halide salt to the aqueous solution.

  15. Inert electrode containing metal oxides, copper and noble metal

    DOEpatents

    Ray, Siba P.; Woods, Robert W.; Dawless, Robert K.; Hosler, Robert B.

    2000-01-01

    A cermet composite material is made by treating at an elevated temperature a mixture comprising a compound of iron and a compound of at least one other metal, together with an alloy or mixture of copper and a noble metal. The alloy or mixture preferably comprises particles having an interior portion containing more copper than noble metal and an exterior portion containing more noble metal than copper. The noble metal is preferably silver. The cermet composite material preferably includes alloy phase portions and a ceramic phase portion. At least part of the ceramic phase portion preferably has a spinel structure.

  16. Inert electrode containing metal oxides, copper and noble metal

    DOEpatents

    Ray, Siba P.; Woods, Robert W.; Dawless, Robert K.; Hosler, Robert B.

    2001-01-01

    A cermet composite material is made by treating at an elevated temperature a mixture comprising a compound of iron and a compound of at least one other metal, together with an alloy or mixture of copper and a noble metal. The alloy or mixture preferably comprises particles having an interior portion containing more copper than noble metal and an exterior portion containing more noble metal than copper. The noble metal is preferably silver. The cermet composite material preferably includes alloy phase portions and a ceramic phase portion. At least part of the ceramic phase portion preferably has a spinel structure.

  17. A direct borohydride fuel cell with a polymer fiber membrane and non-noble metal catalysts.

    PubMed

    Yang, Xiaodong; Liu, Yongning; Li, Sai; Wei, Xiaozhu; Wang, Li; Chen, Yuanzhen

    2012-01-01

    Polymer electrolyte membranes (PEM) and Pt-based catalysts are two crucial components which determine the properties and price of fuel cells. Even though, PEM faces problem of fuel crossover in liquid fuel cells such as direct methanol fuel cell (DMFC) and direct borohydride fuel cell (DBFC), which lowers power output greatly. Here, we report a DBFC in which a polymer fiber membrane (PFM) was used, and metal oxides, such as LaNiO₃ and MnO₂, were used as cathode catalysts, meanwhile CoO was used as anode catalyst. Peak power density of 663 mW·cm⁻² has been achieved at 65°C, which increases by a factor of 1.7-3.7 compared with classic DBFCs. This fuel cell structure can also be extended to other liquid fuel cells, such as DMFC.

  18. A direct borohydride fuel cell with a polymer fiber membrane and non-noble metal catalysts

    PubMed Central

    Yang, Xiaodong; Liu, Yongning; Li, Sai; Wei, Xiaozhu; Wang, Li; Chen, Yuanzhen

    2012-01-01

    Polymer electrolyte membranes (PEM) and Pt-based catalysts are two crucial components which determine the properties and price of fuel cells. Even though, PEM faces problem of fuel crossover in liquid fuel cells such as direct methanol fuel cell (DMFC) and direct borohydride fuel cell (DBFC), which lowers power output greatly. Here, we report a DBFC in which a polymer fiber membrane (PFM) was used, and metal oxides, such as LaNiO3 and MnO2, were used as cathode catalysts, meanwhile CoO was used as anode catalyst. Peak power density of 663 mW·cm−2 has been achieved at 65°C, which increases by a factor of 1.7–3.7 compared with classic DBFCs. This fuel cell structure can also be extended to other liquid fuel cells, such as DMFC. PMID:22880160

  19. Noble Metal Nanoparticles Applications in Cancer

    PubMed Central

    Conde, João; Doria, Gonçalo; Baptista, Pedro

    2012-01-01

    Nanotechnology has prompted new and improved materials for biomedical applications with particular emphasis in therapy and diagnostics. Special interest has been directed at providing enhanced molecular therapeutics for cancer, where conventional approaches do not effectively differentiate between cancerous and normal cells; that is, they lack specificity. This normally causes systemic toxicity and severe and adverse side effects with concomitant loss of quality of life. Because of their small size, nanoparticles can readily interact with biomolecules both at surface and inside cells, yielding better signals and target specificity for diagnostics and therapeutics. This way, a variety of nanoparticles with the possibility of diversified modification with biomolecules have been investigated for biomedical applications including their use in highly sensitive imaging assays, thermal ablation, and radiotherapy enhancement as well as drug and gene delivery and silencing. Here, we review the available noble metal nanoparticles for cancer therapy, with particular focus on those already being translated into clinical settings. PMID:22007307

  20. Noble Metal Nanoparticles for Biosensing Applications

    PubMed Central

    Doria, Gonçalo; Conde, João; Veigas, Bruno; Giestas, Leticia; Almeida, Carina; Assunção, Maria; Rosa, João; Baptista, Pedro V.

    2012-01-01

    In the last decade the use of nanomaterials has been having a great impact in biosensing. In particular, the unique properties of noble metal nanoparticles have allowed for the development of new biosensing platforms with enhanced capabilities in the specific detection of bioanalytes. Noble metal nanoparticles show unique physicochemical properties (such as ease of functionalization via simple chemistry and high surface-to-volume ratios) that allied with their unique spectral and optical properties have prompted the development of a plethora of biosensing platforms. Additionally, they also provide an additional or enhanced layer of application for commonly used techniques, such as fluorescence, infrared and Raman spectroscopy. Herein we review the use of noble metal nanoparticles for biosensing strategies—from synthesis and functionalization to integration in molecular diagnostics platforms, with special focus on those that have made their way into the diagnostics laboratory. PMID:22438731

  1. The Colour of the Noble Metals.

    ERIC Educational Resources Information Center

    Poole, R. T.

    1983-01-01

    Examines the physical basis for colors of noble metals (copper, silver, gold) developed from energy conservation/quantum mechanical view of free electron photoabsorption. Describes production of absorption edges produced by change in density of occupied valence electron states in the d-band, which allows stronger absorption in the visible photon…

  2. 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.

  3. Strategic role of selected noble metal nanoparticles in medicine.

    PubMed

    Rai, Mahendra; Ingle, Avinash P; Birla, Sonal; Yadav, Alka; Santos, Carolina Alves Dos

    2016-09-01

    Noble metals and their compounds have been used as therapeutic agents from the ancient time in medicine for the treatment of various infections. Recently, much progress has been made in the field of nanobiotechnology towards the development of different kinds of nanomaterials with a wide range of applications. Among the metal nanoparticles, noble metal nanoparticles have demonstrated potential biomedical applications. Due to the small size, nanoparticles can easily interact with biomolecules both at surface and inside cells, yielding better signals and target specificity for diagnostics and therapeutics. Noble metal nanoparticles inspired the researchers due to their remarkable role in detection and treatment of dreadful diseases. In this review, we have attempted to focus on the biomedical applications of noble metal nanoparticles particularly, silver, gold, and platinum in diagnosis and treatment of dreaded diseases such as cancer, human immunodeficiency virus (HIV), tuberculosis (TB), and Parkinson disease. In addition, the role of silver nanoparticles (AgNPs) such as novel antimicrobials, gold nanoparticles (AuNPs) such as efficient drug carrier, uses of platinum nanoparticles (PtNPs) in bone allograft, dentistry, etc. have been critically reviewed. Moreover, the toxicity due to the use of metal nanoparticles and some unsolved challenges in the field have been discussed with their possible solutions. PMID:26089024

  4. 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 and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3060 Noble metal alloy. (a) Identification. A noble...

  5. 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 and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Prosthetic Devices § 872.3060 Noble metal alloy. (a) Identification. A noble...

  6. Oxygen adsorption at noble metal/TiO2 junctions

    NASA Astrophysics Data System (ADS)

    Hossein-Babaei, F.; Alaei-Sheini, Navid; Lajvardi, Mehdi M.

    2016-03-01

    Electric conduction in titanium dioxide is known to be oxygen sensitive and the conductivity of a TiO2 ceramic body is determined mainly by the concentration of its naturally occurring oxygen vacancy. Recently, fabrications and electronic features of a number of noble metal/TiO2-based electronic devices, such as solar cells, UV detectors, gas sensors and memristive devices have been demonstrated. Here, we investigate the effect of oxygen adsorption at the noble metal/TiO2 junction in such devices, and show the potentials of these junctions in chemical sensor fabrication. The polycrystalline, poly-phase TiO2 layers are grown by the selective and controlled oxidation of titanium thin films vacuum deposited on silica substrates. Noble metal thin films are deposited on the oxide layers by physical vapor deposition. Current-voltage (I-V) diagrams of the fabricated devices are studied for Ag/, Au/, and Pt/TiO2 samples. The raw samples show no junction energy barrier. After a thermal annealing in air at 250° C, I-V diagrams change drastically. The annealed samples demonstrate highly non-linear I-V indicating the formation of high Schottky energy barriers at the noble metal/TiO2 junctions. The phenomenon is described based on the effect of the oxygen atoms adsorbed at the junction.

  7. Noble Metals Would Prevent Hydrogen Embrittlement

    NASA Technical Reports Server (NTRS)

    Paton, N. E.; Frandsen, J. D.

    1987-01-01

    According to proposal, addition of small amounts of noble metals makes iron- and nickel-based alloys less susceptible to embrittlement by hydrogen. Metallurgists demonstrated adding 0.6 to 1.0 percent by weight of Pd or Pt eliminates stress/corrosion cracking in type 4130 steel. Proposal based on assumption that similar levels (0.5 to 1.0 weight percent) of same elements effective against hydrogen embrittlement.

  8. Engineering noble metal nanomaterials for environmental applications

    NASA Astrophysics Data System (ADS)

    Li, Jingguo; Zhao, Tingting; Chen, Tiankai; Liu, Yanbiao; Ong, Choon Nam; Xie, Jianping

    2015-04-01

    Besides being valuable assets in our daily lives, noble metals (namely, gold, silver, and platinum) also feature many intriguing physical and chemical properties when their sizes are reduced to the nano- or even subnano-scale; such assets may significantly increase the values of the noble metals as functional materials for tackling important societal issues related to human health and the environment. Among which, designing/engineering of noble metal nanomaterials (NMNs) to address challenging issues in the environment has attracted recent interest in the community. In general, the use of NMNs for environmental applications is highly dependent on the physical and chemical properties of NMNs. Such properties can be readily controlled by tailoring the attributes of NMNs, including their size, shape, composition, and surface. In this feature article, we discuss recent progress in the rational design and engineering of NMNs with particular focus on their applications in the field of environmental sensing and catalysis. The development of functional NMNs for environmental applications is highly interdisciplinary, which requires concerted efforts from the communities of materials science, chemistry, engineering, and environmental science.

  9. Making A Noble-Metal-On-Metal-Oxide Catalyst

    NASA Technical Reports Server (NTRS)

    Miller, Irvin M.; Davis, Patricia P.; Upchurch, Billy T.

    1989-01-01

    Catalyst exhibits superior performance in oxidation of CO in CO2 lasers. Two-step process developed for preparing platinum- or palladium-on-tin-oxide catalyst for recombination of CO and O2, decomposition products that occur in high-voltage discharge region of closed-cycle CO2 laser. Process also applicable to other noble-metal/metal-oxide combinations.

  10. High temperature, oxidation resistant noble metal-Al alloy thermocouple

    NASA Technical Reports Server (NTRS)

    Smialek, James L. (Inventor); Gedwill, Michael G. (Inventor)

    1994-01-01

    A thermocouple is disclosed. The thermocouple is comprised of an electropositive leg formed of a noble metal-Al alloy and an electronegative leg electrically joined to form a thermocouple junction. The thermocouple provides for accurate and reproducible measurement of high temperatures (600 - 1300 C) in inert, oxidizing or reducing environments, gases, or vacuum. Furthermore, the thermocouple circumvents the need for expensive, strategic precious metals such as rhodium as a constituent component. Selective oxidation of rhodium is also thereby precluded.

  11. Noble-metal-free plasmonic photocatalyst: hydrogen doped semiconductors

    PubMed Central

    Ma, Xiangchao; Dai, Ying; Yu, Lin; Huang, Baibiao

    2014-01-01

    The unique capacity of localized surface plasmon resonance (LSPR) offers a new opportunity to overcome the limited efficiency of semiconductor photocatalyst. Here we unravel that LSPR, which usually occurs in noble metal nanoparticles, can be realized by hydrogen doping in noble-metal-free semiconductor using TiO2 as a model photocatalyst. Moreover, its LSPR is located in infrared region, which supplements that of noble metal whose LSPR is generally in the visible region, making it possible to extend the light response of photocatalyst to infrared region. The near field enhancement is shown to be comparable with that of noble-metal nanoparticles, indicating that highly enhanced light absorption rate can be expected. The present work can provide a key guideline for the creation of highly efficient noble-metal-free plasmonic photocatalysts and have a much wider impact in infrared bioimaging and spectroscopy where infrared LSPR is essential. PMID:24496400

  12. Noble metal chain adsorption on graphene sheet

    NASA Astrophysics Data System (ADS)

    Salehi, Hamdollah; Moaddeli, Mohammad; Amiri, Peiman

    2016-05-01

    Van-der-Waals dispersion force plays a crucial role in physisorption mechanisms. Using density functional theory, the adsorption of noble metal (Cu, Ag, and Au) chains on graphene sheet was studied within two possible adsorption geometries, the zig-zag and the preferred armchair one. In order to take the portion of non-local correlations into account, we applied both semi-empirical and ab-initio van-der-Waals functionals in our calculations. The interaction leads to a charge transfer at the physisorption interface and makes graphene p-doped. Not only does the Fermi level shifts with respect to the Dirac point, but also a small band gap opening is predicted. Work function calculations confirm the presence of physisorption mechanism at the interface.

  13. Selective Growth of Noble Gases at Metal/Oxide Interface.

    PubMed

    Takahashi, Keisuke; Oka, Hiroshi; Ohnuki, Somei

    2016-02-17

    The locations and roles of noble gases at an oxide/metal interface in oxide dispersed metal are theoretically and experimentally investigated. Oxide dispersed metal consisting of FCC Fe and Y2Hf2O7 (Y2Ti2O7) is synthesized by mechanical alloying under a saturated Ar gas environment. Transmission electron microscopy and density functional theory observes the strain field at the interface of FCC Fe {111} and Y2Hf2O7 {111} whose physical origin emerges from surface reconstruction due to charge transfer. Noble gases are experimentally observed at the oxide (Y2Ti2O7) site and calculations reveal that the noble gases segregate the interface and grow toward the oxide site. In general, the interface is defined as the trapping site for noble gases; however, transmission electron microscopy and density functional theory found evidence which shows that noble gases grow toward the oxide, contrary to the generally held idea that the interface is the final trapping site for noble gases. Furthermore, calculations show that the inclusion of He/Ar hardens the oxide, suggesting that material fractures could begin from the noble gas bubble within the oxides. Thus, experimental and theoretical results demonstrate that noble gases grow from the interface toward the oxide and that oxides behave as a trapping site for noble gases. PMID:26840881

  14. Ferromagnetism exhibited by nanoparticles of noble metals.

    PubMed

    Maitra, Urmimala; Das, Barun; Kumar, Nitesh; Sundaresan, Athinarayanan; Rao, C N R

    2011-08-22

    Gold nanoparticles with average diameters in the range 2.5-15 nm, prepared at the organic/aqueous interface by using tetrakis(hydroxymethyl)phosphonium chloride (THPC) as reducing agent, exhibit ferromagnetism whereby the saturation magnetization M(S) increases with decreasing diameter and varies linearly with the fraction of surface atoms. The value of M(S) is higher when the particles are present as a film instead of as a sol. Capping with strongly interacting ligands such as alkane thiols results in a higher M(S) value, which varies with the strength of the metal-sulfur bond. Ferromagnetism is also found in Pt and Ag nanoparticles prepared as sols, and the M(S) values vary as Pt>Au>Ag. A careful study of the temperature variation of the magnetization of Au nanoparticles, along with certain other observations, suggests that small bare nanoparticles of noble metals could indeed possess ferromagnetism, albeit weak, which is accentuated in the presence of capping agents, specially alkane thiols which form strong metal-sulfur bonds.

  15. Electrochemical Synthesis of Nanostructured Noble Metal Films for Biosensing

    NASA Astrophysics Data System (ADS)

    Bhattarai, Jay K.

    electrochemical biosensing. We have also discovered a facile electrochemical method to synthesize novel plasmonic noble metal nanostructured films. Plasmonic noble metal nanostructures have promising applications in photovoltaic solar cells, cloaking, and molecular sensing. Here, we used plasmonic noble metal nanostructures as a transducer for biosensing using localized surface plasmon resonance (LSPR) spectroscopy, a label-free biosensing technique. The prepared nanostructured films are not only sensitive for detecting biomolecules, but are stable chemically and physically, and can be easily regenerated. We have compared the sensitivity of three different types of nanostructured films, namely; nanostructured gold film (NGF), nanostructured silver film (NSF), and NPG film, and discussed the advantages and disadvantages of the prepared structures. Finally, we report carbohydrate--lectin, lectin--protein, and layer-by-layer interactions of molecules using LSPR spectroscopy. We have also performed real-time interactions and concentration dependent studies to find the equilibrium dissociation constant of the interactions. The results from these experiments could contribute to the development of cheap and sensitive biosensors that can be used for diagnostic purposes.

  16. Inert anode containing base metal and noble metal useful for the electrolytic production of aluminum

    DOEpatents

    Ray, Siba P.; Liu, Xinghua

    2000-01-01

    An inert anode for production of metals such as aluminum is disclosed. The inert anode comprises a base metal selected from Cu and Ag, and at least one noble metal selected from Ag, Pd, Pt, Au, Rh, Ru, Ir and Os. The inert anode may optionally be formed of sintered particles having interior portions containing more base metal than noble metal and exterior portions containing more noble metal than base metal. In a preferred embodiment, the base metal comprises Cu, and the noble metal comprises Ag, Pd or a combination thereof.

  17. DWPF Hydrogen Generation Study-Form of Noble Metal SRAT Testing

    SciTech Connect

    Bannochie, C

    2005-09-01

    The Defense Waste Processing Facility, DWPF, has requested that the Savannah River National Laboratory, SRNL, investigate the factors that contribute to hydrogen generation to determine if current conservatism in setting the DWPF processing window can be reduced. A phased program has been undertaken to increase understanding of the factors that influence hydrogen generation in the DWPF Chemical Process Cell, CPC. The hydrogen generation in the CPC is primarily due to noble metal catalyzed decomposition of formic acid with a minor contribution from radiolytic processes. Noble metals have historically been added as trim chemicals to process simulations. The present study investigated the potential conservatism that might be present from adding the catalytic species as trim chemicals to the final sludge simulant versus co-precipitating the noble metals into the insoluble sludge solids matrix. Two sludge simulants were obtained, one with co-precipitated noble metals and one without noble metals. Co-precipitated noble metals were expected to better match real waste behavior than using trimmed noble metals during CPC simulations. Portions of both sludge simulants were held at 97 C for about eight hours to qualitatively simulate the effects of long term storage on particle morphology and speciation. The two original and two heat-treated sludge simulants were then used as feeds to Sludge Receipt and Adjustment Tank, SRAT, process simulations. Testing was done at relatively high acid stoichiometries, {approx}175%, and without mercury in order to ensure significant hydrogen generation. Hydrogen generation rates were monitored during processing to assess the impact of the form of noble metals. The following observations were made on the data: (1) Co-precipitated noble metal simulant processed similarly to trimmed noble metal simulant in most respects, such as nitrite to nitrate conversion, formate destruction, and pH, but differently with respect to hydrogen generation: (A

  18. DEVELOPMENT OF A NON-NOBLE METAL HYDROGEN PURIFICATION SYSTEM

    SciTech Connect

    Korinko, P; Kyle Brinkman, K; Thad Adams, T; George Rawls, G

    2008-11-25

    Development of advanced hydrogen separation membranes in support of hydrogen production processes such as coal gasification and as front end gas purifiers for fuel cell based system is paramount to the successful implementation of a national hydrogen economy. Current generation metallic hydrogen separation membranes are based on Pd-alloys. Although the technology has proven successful, at issue is the high cost of palladium. Evaluation of non-noble metal based dense metallic separation membranes is currently receiving national and international attention. The focus of the reported work was to develop a scaled reactor with a VNi-Ti alloy membrane to replace a production Pd-alloy tube-type purification/diffuser system.

  19. Engineering interface and surface of noble metal nanoparticle nanotubes toward enhanced catalytic activity for fuel cell applications.

    PubMed

    Cui, Chun-Hua; Yu, Shu-Hong

    2013-07-16

    In order for fuel cells to have commercial viability as alternative fuel sources, researchers need to develop highly active and robust fuel cell electrocatalysts. In recent years, the focus has been on the design and synthesis of novel catalytic materials with controlled interface and surface structures. Another goal is to uncover potential catalytic activity and selectivity, as well as understand their fundamental catalytic mechanisms. Scientists have achieved great progress in the experimental and theoretical investigation due to the urgent demand for broad commercialization of fuel cells in automotive applications. However, there are still three main problems: cost, performance, and stability. To meet these targets, the catalyst needs to have multisynergic functions. In addition, the composition and structure changes of the catalysts during the reactions still need to be explored. Activity in catalytic nanomaterials is generally controlled by the size, shape, composition, and interface and surface engineering. As such, one-dimensional nanostructures such as nanowires and nanotubes are of special interest. However, these structures tend to lose the nanoparticle morphology and inhibit the use of catalysts in both fuel cell anodes and cathodes. In 2003, Rubinstein and co-workers proposed the idea of nanoparticle nanotubes (NNs), which combine the geometry of nanotubes and the morphology of nanoparticles. This concept gives both the high surface-to-volume ratio and the size effect, which are both appealing in electrocatalyst design. In this Account, we describe our developments in the construction of highly active NNs with unique surface and heterogeneous interface structures. We try to clarify enhanced activity and stability in catalytic systems by taking into account the activity impact factors. We briefly introduce material structural effects on the electrocatalytic reactivity including metal oxide/metal and metal/metal interfaces, dealloyed pure Pt, and mixed Pt

  20. Engineering interface and surface of noble metal nanoparticle nanotubes toward enhanced catalytic activity for fuel cell applications.

    PubMed

    Cui, Chun-Hua; Yu, Shu-Hong

    2013-07-16

    In order for fuel cells to have commercial viability as alternative fuel sources, researchers need to develop highly active and robust fuel cell electrocatalysts. In recent years, the focus has been on the design and synthesis of novel catalytic materials with controlled interface and surface structures. Another goal is to uncover potential catalytic activity and selectivity, as well as understand their fundamental catalytic mechanisms. Scientists have achieved great progress in the experimental and theoretical investigation due to the urgent demand for broad commercialization of fuel cells in automotive applications. However, there are still three main problems: cost, performance, and stability. To meet these targets, the catalyst needs to have multisynergic functions. In addition, the composition and structure changes of the catalysts during the reactions still need to be explored. Activity in catalytic nanomaterials is generally controlled by the size, shape, composition, and interface and surface engineering. As such, one-dimensional nanostructures such as nanowires and nanotubes are of special interest. However, these structures tend to lose the nanoparticle morphology and inhibit the use of catalysts in both fuel cell anodes and cathodes. In 2003, Rubinstein and co-workers proposed the idea of nanoparticle nanotubes (NNs), which combine the geometry of nanotubes and the morphology of nanoparticles. This concept gives both the high surface-to-volume ratio and the size effect, which are both appealing in electrocatalyst design. In this Account, we describe our developments in the construction of highly active NNs with unique surface and heterogeneous interface structures. We try to clarify enhanced activity and stability in catalytic systems by taking into account the activity impact factors. We briefly introduce material structural effects on the electrocatalytic reactivity including metal oxide/metal and metal/metal interfaces, dealloyed pure Pt, and mixed Pt

  1. Noble metal aerogels-synthesis, characterization, and application as electrocatalysts.

    PubMed

    Liu, Wei; Herrmann, Anne-Kristin; Bigall, Nadja C; Rodriguez, Paramaconi; Wen, Dan; Oezaslan, Mehtap; Schmidt, Thomas J; Gaponik, Nikolai; Eychmüller, Alexander

    2015-02-17

    CONSPECTUS: Metallic and catalytically active materials with high surface area and large porosity are a long-desired goal in both industry and academia. In this Account, we summarize the strategies for making a variety of self-supported noble metal aerogels consisting of extended metal backbone nanonetworks. We discuss their outstanding physical and chemical properties, including their three-dimensional network structure, the simple control over their composition, their large specific surface area, and their hierarchical porosity. Additionally, we show some initial results on their excellent performance as electrocatalysts combining both high catalytic activity and high durability for fuel cell reactions such as ethanol oxidation and the oxygen reduction reaction (ORR). Finally, we give some hints on the future challenges in the research area of metal aerogels. We believe that metal aerogels are a new, promising class of electrocatalysts for polymer electrolyte fuel cells (PEFCs) and will also open great opportunities for other electrochemical energy systems, catalysis, and sensors. The commercialization of PEFCs encounters three critical obstacles, viz., high cost, insufficient activity, and inadequate long-term durability. Besides others, the sluggish kinetics of the ORR and alcohol oxidation and insufficient catalyst stability are important reasons for these obstacles. Various approaches have been taken to overcome these obstacles, e.g., by controlling the catalyst particle size in an optimized range, forming multimetallic catalysts, controlling the surface compositions, shaping the catalysts into nanocrystals, and designing supportless catalysts with extended surfaces such as nanostructured thin films, nanotubes, and porous nanostructures. These efforts have produced plenty of excellent electrocatalysts, but the development of multisynergetic functional catalysts exhibiting low cost, high activity, and high durability still faces great challenges. In this

  2. Noble Metal Aerogels—Synthesis, Characterization, and Application as Electrocatalysts

    PubMed Central

    2015-01-01

    Conspectus Metallic and catalytically active materials with high surface area and large porosity are a long-desired goal in both industry and academia. In this Account, we summarize the strategies for making a variety of self-supported noble metal aerogels consisting of extended metal backbone nanonetworks. We discuss their outstanding physical and chemical properties, including their three-dimensional network structure, the simple control over their composition, their large specific surface area, and their hierarchical porosity. Additionally, we show some initial results on their excellent performance as electrocatalysts combining both high catalytic activity and high durability for fuel cell reactions such as ethanol oxidation and the oxygen reduction reaction (ORR). Finally, we give some hints on the future challenges in the research area of metal aerogels. We believe that metal aerogels are a new, promising class of electrocatalysts for polymer electrolyte fuel cells (PEFCs) and will also open great opportunities for other electrochemical energy systems, catalysis, and sensors. The commercialization of PEFCs encounters three critical obstacles, viz., high cost, insufficient activity, and inadequate long-term durability. Besides others, the sluggish kinetics of the ORR and alcohol oxidation and insufficient catalyst stability are important reasons for these obstacles. Various approaches have been taken to overcome these obstacles, e.g., by controlling the catalyst particle size in an optimized range, forming multimetallic catalysts, controlling the surface compositions, shaping the catalysts into nanocrystals, and designing supportless catalysts with extended surfaces such as nanostructured thin films, nanotubes, and porous nanostructures. These efforts have produced plenty of excellent electrocatalysts, but the development of multisynergetic functional catalysts exhibiting low cost, high activity, and high durability still faces great challenges. In this

  3. Supported noble metals on hydrogen-treated TiO2 nanotube arrays as highly ordered electrodes for fuel cells.

    PubMed

    Zhang, Changkun; Yu, Hongmei; Li, Yongkun; Gao, Yuan; Zhao, Yun; Song, Wei; Shao, Zhigang; Yi, Baolian

    2013-04-01

    Hydrogen-treated TiO2 nanotube (H-TNT) arrays serve as highly ordered nanostructured electrode supports, which are able to significantly improve the electrochemical performance and durability of fuel cells. The electrical conductivity of H-TNTs increases by approximately one order of magnitude in comparison to air-treated TNTs. The increase in the number of oxygen vacancies and hydroxyl groups on the H-TNTs help to anchor a greater number of Pt atoms during Pt electrodeposition. The H-TNTs are pretreated by using a successive ion adsorption and reaction (SIAR) method that enhances the loading and dispersion of Pt catalysts when electrodeposited. In the SIAR method a Pd activator can be used to provide uniform nucleation sites for Pt and leads to increased Pt loading on the H-TNTs. Furthermore, fabricated Pt nanoparticles with a diameter of 3.4 nm are located uniformly around the pretreated H-TNT support. The as-prepared and highly ordered electrodes exhibit excellent stability during accelerated durability tests, particularly for the H-TNT-loaded Pt catalysts that have been annealed in ultrahigh purity H2 for a second time. There is minimal decrease in the electrochemical surface area of the as-prepared electrode after 1000 cycles compared to a 68 % decrease for the commercial JM 20 % Pt/C electrode after 800 cycles. X-ray photoelectron spectroscopy shows that after the H-TNT-loaded Pt catalysts are annealed in H2 for the second time, the strong metal-support interaction between the H-TNTs and the Pt catalysts enhances the electrochemical stability of the electrodes. Fuel-cell testing shows that the power density reaches a maximum of 500 mWcm(-2) when this highly ordered electrode is used as the anode. When used as the cathode in a fuel cell with extra-low Pt loading, the new electrode generates a specific power density of 2.68 kWg(Pt) (-1) . It is indicated that H-TNT arrays, which have highly ordered nanostructures, could be used as ordered electrode supports.

  4. Size control of noble metal clusters and metallic heterostructures through the reduction kinetics of metal precursors

    NASA Astrophysics Data System (ADS)

    Sevonkaev, Igor V.; Herein, Daniel; Jeske, Gerald; Goia, Dan V.

    2014-07-01

    Eight precious metal salts/complexes were reduced in propylene glycol at temperatures ranging between 110 and 170 °C. We found that the reduction temperature and the size of precipitated metallic nanoparticles formed were significantly affected by the structure and reactivity of the metal precursors. The choice of noble metal precursor offers flexibility for designing, fabricating and controlling the size of metallic heterostructures with tunable properties.Eight precious metal salts/complexes were reduced in propylene glycol at temperatures ranging between 110 and 170 °C. We found that the reduction temperature and the size of precipitated metallic nanoparticles formed were significantly affected by the structure and reactivity of the metal precursors. The choice of noble metal precursor offers flexibility for designing, fabricating and controlling the size of metallic heterostructures with tunable properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03045a

  5. Measuring the noble metal and iodine composition of extracted noble metal phase from spent nuclear fuel using instrumental neutron activation analysis.

    PubMed

    Palomares, R I; Dayman, K J; Landsberger, S; Biegalski, S R; Soderquist, C Z; Casella, A J; Brady Raap, M C; Schwantes, J M

    2015-04-01

    Masses of noble metal and iodine nuclides in the metallic noble metal phase extracted from spent fuel are measured using instrumental neutron activation analysis. Nuclide presence is predicted using fission yield analysis, and radionuclides are identified and the masses quantified using neutron activation analysis. The nuclide compositions of noble metal phase derived from two dissolution methods, UO2 fuel dissolved in nitric acid and UO2 fuel dissolved in ammonium-carbonate and hydrogen-peroxide solution, are compared. PMID:25644079

  6. Atomic Layer Deposition Route To Tailor Nanoalloys of Noble and Non-noble Metals.

    PubMed

    Ramachandran, Ranjith K; Dendooven, Jolien; Filez, Matthias; Galvita, Vladimir V; Poelman, Hilde; Solano, Eduardo; Minjauw, Matthias M; Devloo-Casier, Kilian; Fonda, Emiliano; Hermida-Merino, Daniel; Bras, Wim; Marin, Guy B; Detavernier, Christophe

    2016-09-27

    Since their early discovery, bimetallic nanoparticles have revolutionized various fields, including nanomagnetism and optics as well as heterogeneous catalysis. Knowledge buildup in the past decades has witnessed that the nanoparticle size and composition strongly impact the nanoparticle's properties and performance. Yet, conventional synthesis strategies lack proper control over the nanoparticle morphology and composition. Recently, atomically precise synthesis of bimetallic nanoparticles has been achieved by atomic layer deposition (ALD), alleviating particle size and compositional nonuniformities. However, this bimetal ALD strategy applies to noble metals only, a small niche within the extensive class of bimetallic alloys. We report an ALD-based approach for the tailored synthesis of bimetallic nanoparticles containing both noble and non-noble metals, here exemplified for Pt-In. First, a Pt/In2O3 bilayer is deposited by ALD, yielding precisely defined Pt-In nanoparticles after high-temperature H2 reduction. The nanoparticles' In content can be accurately controlled over the whole compositional range, and the particle size can be tuned from micrometers down to the nanometer scale. The size and compositional flexibility provided by this ALD-approach will trigger the fabrication of fully tailored bimetallic nanomaterials, including superior nanocatalysts. PMID:27585708

  7. Atomic Layer Deposition Route To Tailor Nanoalloys of Noble and Non-noble Metals.

    PubMed

    Ramachandran, Ranjith K; Dendooven, Jolien; Filez, Matthias; Galvita, Vladimir V; Poelman, Hilde; Solano, Eduardo; Minjauw, Matthias M; Devloo-Casier, Kilian; Fonda, Emiliano; Hermida-Merino, Daniel; Bras, Wim; Marin, Guy B; Detavernier, Christophe

    2016-09-27

    Since their early discovery, bimetallic nanoparticles have revolutionized various fields, including nanomagnetism and optics as well as heterogeneous catalysis. Knowledge buildup in the past decades has witnessed that the nanoparticle size and composition strongly impact the nanoparticle's properties and performance. Yet, conventional synthesis strategies lack proper control over the nanoparticle morphology and composition. Recently, atomically precise synthesis of bimetallic nanoparticles has been achieved by atomic layer deposition (ALD), alleviating particle size and compositional nonuniformities. However, this bimetal ALD strategy applies to noble metals only, a small niche within the extensive class of bimetallic alloys. We report an ALD-based approach for the tailored synthesis of bimetallic nanoparticles containing both noble and non-noble metals, here exemplified for Pt-In. First, a Pt/In2O3 bilayer is deposited by ALD, yielding precisely defined Pt-In nanoparticles after high-temperature H2 reduction. The nanoparticles' In content can be accurately controlled over the whole compositional range, and the particle size can be tuned from micrometers down to the nanometer scale. The size and compositional flexibility provided by this ALD-approach will trigger the fabrication of fully tailored bimetallic nanomaterials, including superior nanocatalysts.

  8. Method for low temperature preparation of a noble metal alloy

    DOEpatents

    Even, Jr., William R.

    2002-01-01

    A method for producing fine, essentially contamination free, noble metal alloys is disclosed. The alloys comprise particles in a size range of 5 to 500 nm. The method comprises 1. A method for preparing a noble metal alloy at low temperature, the method comprising the steps of forming solution of organometallic compounds by dissolving the compounds into a quantity of a compatible solvent medium capable of solvating the organometallic, mixing a portion of each solution to provide a desired molarity ratio of ions in the mixed solution, adding a support material, rapidly quenching droplets of the mixed solution to initiate a solute-solvent phase separation as the solvent freezes, removing said liquid cryogen, collecting and freezing drying the frozen droplets to produce a dry powder, and finally reducing the powder to a metal by flowing dry hydrogen over the powder while warming the powder to a temperature of about 150.degree. C.

  9. Noble metal alloy complex nanostructures: controllable synthesis and their electrochemical property.

    PubMed

    Liu, Hui-ling; Nosheen, Farhat; Wang, Xun

    2015-05-21

    Noble metal nanocrystals have been extensively utilized as promising catalysts for chemical transformations and energy conversion. One of their significant applications lies in electrode materials in fuel cells (FCs) due to their superior electrocatalytic performance towards the reactions both on anode and cathode. Nowadays, tremendous efforts have been devoted to improve the catalytic performance and minimize the usage of precious metals. Constructing multicomponent noble metal nanocrystals with complex structures provides the opportunity to reach this goal due to their highly tunable compositions and morphologies, leading to the modification of the related electrochemical properties. In this review, we first highlight the recent advances in the controllable synthesis of noble metal alloy complex nanostructures including nanoframes/nanocages, branched structures, concave/convex structures, core-shell structures and ultrathin structures. Then the effects of the well-defined nanocrystals on the modified and improved electrochemical properties are outlined. Finally, we make a conclusion with the points on the challenges and perspectives of the controllable synthesis of noble metal alloy complex nanostructures and their electrocatalytic performance.

  10. Noble Metal-Membrane Composites for Electrochemical Applications

    NASA Astrophysics Data System (ADS)

    Millet, Pierre

    1999-01-01

    Composite materials are a new class of materials that combine two or more separate components into a form suitable for structural applications. While each component retains its identity, the new composite material displays macroscopic properties superior to its parent constituents, particularly in terms of mechanical properties and economic value. Perhaps best known for their use in aerospace applications, advanced composites are also used by the automotive, biomedical, and sporting goods markets. In addition, these strong, stiff, lightweight materials are seeing increased use in the rehabilitation, repair, and retrofit of civil infrastructure, including, for example, as replacement bridge decks and wrapping for concrete columns. New composite materials presenting some interesting features which are not directly related to their mechanical properties are appearing. This is the case of noble metal-based polymeric composites, the preparation and characterization of which are considered in this article with regard to their electrochemical properties. These composites are of great practical interest because of potential applications in water electrolysis and H2-O2 fuel cells. Electrolyzers and fuel cells can be used for terrestrial transportation, oxygen generation in submarines, and energy conversion in spacecraft.

  11. Silicon nanocrystal-noble metal hybrid nanoparticles.

    PubMed

    Sugimoto, H; Fujii, M; Imakita, K

    2016-06-01

    We report a novel and facile self-limiting synthesis route of silicon nanocrystal (Si NC)-based colloidally stable semiconductor-metal (gold, silver and platinum) hybrid nanoparticles (NPs). For the formation of hybrid NPs, we employ ligand-free colloidal Si NCs with heavily boron (B) and phosphorus (P) doped shells. By simply mixing B and P codoped colloidal Si NCs with metal salts, hybrid NPs consisting of metal cores and Si NC shells are spontaneously formed. We demonstrate the synthesis of highly uniform and size controllable hybrid NPs. It is shown that codoped Si NCs act as a reducing agent for metal salts and also as a protecting layer to stop metal NP growth. The process is thus self-limiting. The development of a variety of Si NC-based hybrid NPs is a promising first step for the design of biocompatible multifunctional NPs with broad material choices for biosensing, bioimaging and solar energy conversion. PMID:27121127

  12. Preparation and Heat-Treatment of DWPF Simulants With and Without Co-Precipitated Noble Metals

    SciTech Connect

    Koopman, David C.:Eibling, Russel E

    2005-08-01

    The Savannah River National Laboratory is in the process of investigating factors suspected of impacting catalytic hydrogen generation in the Chemical Process Cell of the Defense Waste Processing Facility, DWPF. Noble metal catalyzed hydrogen generation in simulation work constrains the allowable acid addition operating window in DWPF. This constraint potentially impacts washing strategies during sludge batch preparation. It can also influence decisions related to the addition of secondary waste streams to a sludge batch. Noble metals have historically been added as trim chemicals to process simulations. The present study investigated the potential conservatism that might be present from adding the catalytic species as trim chemicals to the final sludge simulant versus co-precipitating the noble metals into the insoluble sludge solids matrix. Parallel preparations of two sludge simulants targeting the composition of Sludge Batch 3 were performed in order to evaluate the impact of the form of noble metals. Identical steps were used except that one simulant had dissolved palladium, rhodium, and ruthenium present during the precipitation of the insoluble solids. Noble metals were trimmed into the other stimulant prior to process tests. Portions of both sludge simulants were held at 97 C for about eight hours to qualitatively simulate the effects of long term storage on particle morphology and speciation. The simulants were used as feeds for Sludge Receipt and Adjustment Tank, SRAT, process simulations. The following conclusions were drawn from the simulant preparation work: (1) The first preparation of a waste slurry simulant with co-precipitated noble metals was successful, based on the data obtained. It appears that 99+% of the noble metals were retained in the simulant. (2) Better control of carbonate, hydroxide, and post-wash trim chemical additions is needed before the new method of simulant preparation will be as reproducible as the old method. (3) The two new

  13. Noble metal-free hydrogen evolution catalysts for water splitting.

    PubMed

    Zou, Xiaoxin; Zhang, Yu

    2015-08-01

    Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.

  14. Ultrafast Hot Carrier Scattering and Generation from Surface Plasmons in Noble Metals

    NASA Astrophysics Data System (ADS)

    Bernardi, Marco; Mustafa, Jamal; Neaton, Jeffrey B.; Louie, Steven G.

    2015-03-01

    Non-equilibrium ``hot''carriers in materials are challenging to study experimentally as they thermalize at subpicosecond time and nanometer length scale. Recent experiments employed hot carriers generated by light absorption or surface plasmon annihilation in noble metals (e.g., Au and Ag) for catalysis and solar cells. The energy distribution and transport of the generated hot carriers play a key role in these experiments. We present ab initio calculations of the energy distribution of hot carriers generated by surface plasmons in noble metals, and the relaxation time and mean free path of the hot carriers along different crystal directions within 5 eV of the Fermi energy. Our calculations show the interplay of the noble metal s and d bands in determining the damping rate of the plasmon and the mean free path of the hot carriers. The trends we find as a function of surface plasmon momentum and frequency allow us to define optimal experimental conditions for hot carrier generation and extraction. Our approach combines density functional theory, GW, and electron-phonon calculations. Our work provides microscopic insight into hot carriers in noble metals, and their ultrafast dynamics in the presence of surface plasmons.

  15. Silicon nanocrystal-noble metal hybrid nanoparticles

    NASA Astrophysics Data System (ADS)

    Sugimoto, H.; Fujii, M.; Imakita, K.

    2016-05-01

    We report a novel and facile self-limiting synthesis route of silicon nanocrystal (Si NC)-based colloidally stable semiconductor-metal (gold, silver and platinum) hybrid nanoparticles (NPs). For the formation of hybrid NPs, we employ ligand-free colloidal Si NCs with heavily boron (B) and phosphorus (P) doped shells. By simply mixing B and P codoped colloidal Si NCs with metal salts, hybrid NPs consisting of metal cores and Si NC shells are spontaneously formed. We demonstrate the synthesis of highly uniform and size controllable hybrid NPs. It is shown that codoped Si NCs act as a reducing agent for metal salts and also as a protecting layer to stop metal NP growth. The process is thus self-limiting. The development of a variety of Si NC-based hybrid NPs is a promising first step for the design of biocompatible multifunctional NPs with broad material choices for biosensing, bioimaging and solar energy conversion.We report a novel and facile self-limiting synthesis route of silicon nanocrystal (Si NC)-based colloidally stable semiconductor-metal (gold, silver and platinum) hybrid nanoparticles (NPs). For the formation of hybrid NPs, we employ ligand-free colloidal Si NCs with heavily boron (B) and phosphorus (P) doped shells. By simply mixing B and P codoped colloidal Si NCs with metal salts, hybrid NPs consisting of metal cores and Si NC shells are spontaneously formed. We demonstrate the synthesis of highly uniform and size controllable hybrid NPs. It is shown that codoped Si NCs act as a reducing agent for metal salts and also as a protecting layer to stop metal NP growth. The process is thus self-limiting. The development of a variety of Si NC-based hybrid NPs is a promising first step for the design of biocompatible multifunctional NPs with broad material choices for biosensing, bioimaging and solar energy conversion. Electronic supplementary information (ESI) available: Additional TEM images and extinction spectra of Si-metal hybrid NPs are shown in Fig. S1

  16. Hierarchical nanostructured noble metal/metal oxide/graphene-coated carbon fiber: in situ electrochemical synthesis and use as microelectrode for real-time molecular detection of cancer cells.

    PubMed

    Abdurhman, Abduraouf Alamer Mohamed; Zhang, Yan; Zhang, Guoan; Wang, Shuai

    2015-10-01

    We report the design and fabrication of a new type of nanohybrid microelectrode based on a hierarchical nanostructured Au/MnO2/graphene-modified carbon fiber (CF) via in situ electrochemical synthesis, which leads to better structural integration of different building blocks into the CF microelectrode. Our finding demonstrates that wrapping CF with graphene nanosheets has dramatically increased the surface area and electrical conductivity of the CF microelectrode. The subsequent template-free electrodeposition of MnO2 on graphene-wrapped CF gives rise to a porous nanonest architecture built up from twisted and intersectant MnO2 nanowires, which serves as an ideal substrate for the direct growth of Au nanoparticles. Owing to the structural merit and synergy effect between different components, the hierarchical nanostructured noble metal/metal oxide/graphene-coated CF demonstrates dramatically enhanced electrocatalytic activity. When used for nonenzymatic H2O2 sensing, the resultant modified microelectrode exhibits acceptable sensitivity, reproducibility, stability, and selectivity, which enable it to be used for real-time tracking H2O2 secretion in human cervical cancer cells. Graphical abstract A schematic illustration of preparation of hierarchical Au/MnO2/ERGO/CF nanohybrid electrode for real-time molecular detection of cancer cells.

  17. Preparation, Functionality, and Application of Metal Oxide-coated Noble Metal Nanoparticles.

    PubMed

    Liu, Shuhua; Regulacio, Michelle D; Tee, Si Yin; Khin, Yin Win; Teng, Choon Peng; Koh, Leng Duei; Guan, Guijian; Han, Ming-Yong

    2016-08-01

    With their remarkable properties and wide-ranging applications, nanostructures of noble metals and metal oxides have been receiving significantly increased attention in recent years. The desire to combine the properties of these two functional materials for specific applications has naturally prompted research in the design and synthesis of novel nanocomposites, consisting of both noble metal and metal-oxide components. In this review, particular attention is given to core-shell type metal oxide-coated noble metal nanostructures (i.e., metal@oxide), which display potential utility in applications, including photothermal therapy, catalytic conversions, photocatalysis, molecular sensing, and photovoltaics. Emerging research directions and areas are envisioned at the end to solicit more attention and work in this regard. PMID:27291595

  18. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    NASA Astrophysics Data System (ADS)

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

  19. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts.

    PubMed

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S; Kumta, Prashant N

    2016-01-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations. PMID:27380719

  20. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    PubMed Central

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-01-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations. PMID:27380719

  1. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts.

    PubMed

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S; Kumta, Prashant N

    2016-07-06

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

  2. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    DOE PAGESBeta

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-06

    We report that identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Furthermore, we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM basedmore » systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.« less

  3. Measuring the Noble Metal and Iodine Composition of Extracted Noble Metal Phase from Spent Nuclear Fuel Using Instrumental Neutron Activation Analysis

    SciTech Connect

    Palomares, R. I.; Dayman, Kenneth J.; Landsberger, Sheldon; Biegalski, Steven R.; Soderquist, Chuck Z.; Casella, Amanda J.; Brady Raap, Michaele C.; Schwantes, Jon M.

    2015-04-01

    Mass quantities of noble metal and iodine nuclides in the metallic noble metal phase extracted from spent fuel are measured using instrumental neutron activation analysis (NAA). Nuclide presence is predicted using fission yield analysis, and mass quantification is derived from standard gamma spectroscopy and radionuclide decay analysis. The nuclide compositions of noble metal phase derived from two dissolution methods, UO2 fuel dissolved in nitric acid and UO2 fuel dissolved in ammonium-carbonate and hydrogen-peroxide solution, are compared. Lastly, the implications of the rapid analytic speed of instrumental NAA are discussed in relation to potential nuclear forensics applications.

  4. Synthesis of graphitic nanostructures on noble metals

    NASA Astrophysics Data System (ADS)

    Parmentier, Amelie

    In this research, two subjects are studied: the growth of graphene from various catalysts with RF-CVD and the growth of graphitic nanostructures from gold-decorated graphene with RF-CVD. In the first topic, various catalysts are made with magnesium oxide and metal nanoparticles: iron, silver and gold. Using a radio-frequency generator, these catalysts are heated and placed in contact with three gases (argon, hydrogen and methane). By controlling various parameters, graphene synthesis can happen. The results are analyzed with Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Thermo-gravimetrical analysis (TGA), and X-ray diffraction (XRD). In the second topic, commercial graphene is functionalized and decorated with different sizes of gold nanoparticles (1.8nm, 5nm, 10nm and 50nm). Using the RF-CVD process, these samples are heated at different temperatures (500°C, 650°C and 800°C). Depending on the parameters, different kinds of graphitic nanostructures are synthesized. Results are analyzed with Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy.

  5. Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

    NASA Technical Reports Server (NTRS)

    Srinivasan, P.; McCubbin, F. M.; Rahman, Z.; Keller, L. P.; Agee, C. B.

    2016-01-01

    CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approx.576-867 C. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Metallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120deg triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3+, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

  6. Reversibility of Noble Metal-Catalyzed Aprotic Li-O₂ Batteries.

    PubMed

    Ma, Shunchao; Wu, Yang; Wang, Jiawei; Zhang, Yelong; Zhang, Yantao; Yan, Xinxiu; Wei, Yang; Liu, Peng; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan; Xu, Ye; Peng, Zhangquan

    2015-12-01

    The aprotic Li-O2 battery has attracted a great deal of interest because, theoretically, it can store far more energy than today's batteries. Toward unlocking the energy capabilities of this neotype energy storage system, noble metal-catalyzed high surface area carbon materials have been widely used as the O2 cathodes, and some of them exhibit excellent electrochemical performances in terms of round-trip efficiency and cycle life. However, whether these outstanding electrochemical performances are backed by the reversible formation/decomposition of Li2O2, i.e., the desired Li-O2 electrochemistry, remains unclear due to a lack of quantitative assays for the Li-O2 cells. Here, noble metal (Ru and Pd)-catalyzed carbon nanotube (CNT) fabrics, prepared by magnetron sputtering, have been used as the O2 cathode in aprotic Li-O2 batteries. The catalyzed Li-O2 cells exhibited considerably high round-trip efficiency and prolonged cycle life, which could match or even surpass some of the best literature results. However, a combined analysis using differential electrochemical mass spectrometry and Fourier transform infrared spectroscopy, revealed that these catalyzed Li-O2 cells (particularly those based on Pd-CNT cathodes) did not work according to the desired Li-O2 electrochemistry. Instead the presence of noble metal catalysts impaired the cells' reversibility, as evidenced by the decreased O2 recovery efficiency (the ratio of the amount of O2 evolved during recharge/that consumed in the preceding discharge) coupled with increased CO2 evolution during charging. The results reported here provide new insights into the O2 electrochemistry in the aprotic Li-O2 batteries containing noble metal catalysts and exemplified the importance of the quantitative assays for the Li-O2 reactions in the course of pursuing truly rechargeable Li-O2 batteries.

  7. Noble Metals and Spinel Settling in High Level Waste Glass Melters

    SciTech Connect

    Sundaram, S. K.; Perez, Joseph M.

    2000-09-30

    In the continuing effort to support the Defense Waste Processing Facility (DWPF), the noble metals issue is addressed. There is an additional concern about the amount of noble metals expected to be present in the future batches that will be considered for vitrification in the DWPF. Several laboratory, as well as melter-scale, studies have been completed by various organizations (mainly PNNL, SRTC, and WVDP in the USA). This letter report statuses the noble metals issue and focuses at the settling of noble metals in melters.

  8. Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts.

    PubMed

    Hunt, Sean T; Milina, Maria; Alba-Rubio, Ana C; Hendon, Christopher H; Dumesic, James A; Román-Leshkov, Yuriy

    2016-05-20

    We demonstrated the self-assembly of transition metal carbide nanoparticles coated with atomically thin noble metal monolayers by carburizing mixtures of noble metal salts and transition metal oxides encapsulated in removable silica templates. This approach allows for control of the final core-shell architecture, including particle size, monolayer coverage, and heterometallic composition. Carbon-supported Ti(0.1)W(0.9)C nanoparticles coated with Pt or bimetallic PtRu monolayers exhibited enhanced resistance to sintering and CO poisoning, achieving an order of magnitude increase in specific activity over commercial catalysts for methanol electrooxidation after 10,000 cycles. These core-shell materials provide a new direction to reduce the loading, enhance the activity, and increase the stability of noble metal catalysts.

  9. Photoresponse from noble metal nanoparticles-multi walled carbon nanotube composites

    SciTech Connect

    Scarselli, M.; Camilli, L.; Castrucci, P.; De Crescenzi, M.; Matthes, L.; Pulci, O.; Gatto, E.; Venanzi, M.

    2012-12-10

    In this Letter, we investigated the photo-response of multi wall carbon nanotube-based composites obtained from in situ thermal evaporation of noble metals (Au, Ag, and Cu) on the nanotube films. The metal deposition process produced discrete nanoparticles on the nanotube outer walls. The nanoparticle-carbon nanotube films were characterized by photo-electrochemical measurements in a standard three electrode cell. The photocurrent from the decorated carbon nanotubes remarkably increased with respect to that of bare multiwall tubes. With the aid of first-principle calculations, these results are discussed in terms of metal nanoparticle-nanotube interactions and electronic charge transfer at the interface.

  10. The strong reactions of Lewis-base noble-metals with vanadium and other acidic transition metals

    SciTech Connect

    Ebbinghaus, B.B.

    1991-05-01

    The noble metals often thought of as unreactive solids,react strongly with nearly 40% of the elements in the periodictable: group IIIB-VB transition metals, lanthanides, theactinides, and group IIIA-IVA non-transition metals. These strong reactions arise from increased bonding/electron transfer fromnonbonding electrons d electron pairs on the noble metal tovacant orbitals on V, etc. This effect is a generalized Lewis acid-base interaction. The partial Gibbs energy of V in the noblemetals has been measured as a function of concentration at a temperature near 1000C. Thermodynamics of the intermetallics are determined by ternary oxide equilibria, ternary carbide equilibria, and the high-temperature galvanic cell technique. These experimental methods use equilibrated solid composite mixtures in which grains of V oxides or of V carbides are interspersed with grains of V-NM(noble-metal) alloys. In equilibrium the activity of V in the oxide or the carbide equals the activity in the alloy. Consequently, the thermodynamics available in the literature for the V oxides and V carbides are reviewed. Test runs on the galvanic cell were attempted. The V oxide electrode reacts with CaF[sub 2], ThO[sub 2], YDT(0.85ThO[sub 2]-0.15YO[sub 1.5]), and LDT(0.85ThO[sub 2]- 0.15LaO[sub 1.5]) to interfere with the measured data observed toward the beginning of a galvanic cell experiment are the most accurate. The interaction of vanadium at infinite dilution in the noble-metals was determined.

  11. The strong reactions of Lewis-base noble-metals with vanadium and other acidic transition metals

    SciTech Connect

    Ebbinghaus, B.B.

    1991-05-01

    The noble metals often thought of as unreactive solids,react strongly with nearly 40% of the elements in the periodictable: group IIIB-VB transition metals, lanthanides, theactinides, and group IIIA-IVA non-transition metals. These strong reactions arise from increased bonding/electron transfer fromnonbonding electrons d electron pairs on the noble metal tovacant orbitals on V, etc. This effect is a generalized Lewis acid-base interaction. The partial Gibbs energy of V in the noblemetals has been measured as a function of concentration at a temperature near 1000C. Thermodynamics of the intermetallics are determined by ternary oxide equilibria, ternary carbide equilibria, and the high-temperature galvanic cell technique. These experimental methods use equilibrated solid composite mixtures in which grains of V oxides or of V carbides are interspersed with grains of V-NM(noble-metal) alloys. In equilibrium the activity of V in the oxide or the carbide equals the activity in the alloy. Consequently, the thermodynamics available in the literature for the V oxides and V carbides are reviewed. Test runs on the galvanic cell were attempted. The V oxide electrode reacts with CaF{sub 2}, ThO{sub 2}, YDT(0.85ThO{sub 2}-0.15YO{sub 1.5}), and LDT(0.85ThO{sub 2}- 0.15LaO{sub 1.5}) to interfere with the measured data observed toward the beginning of a galvanic cell experiment are the most accurate. The interaction of vanadium at infinite dilution in the noble-metals was determined.

  12. Functionalized magnetite particles for adsorption of colloidal noble metal nanoparticles.

    PubMed

    Lopes, Joana L; Marques, Karine L; Girão, Ana V; Pereira, Eduarda; Trindade, Tito

    2016-08-01

    Magnetite (inverse spinel type) particles have been surface-modified with siliceous shells enriched in dithiocarbamate groups. The deposition of colloidal noble metal nanoparticles (Au, Ag, Pt, Pd) onto the modified magnetites can be performed by treating the respective hydrosols with the magnetic sorbents, thus allowing their uptake from water under a magnetic gradient. In particular, for Au colloids, these magnetic particles are very efficient sorbents that we ascribe to the strong affinity of sulfur-containing groups at the magnetite surfaces for this metal. Considering the extensive use of Au colloids in laboratorial and industrial contexts, the approach described here might have an impact on the development of nanotechnologies to recover this precious metal. En route to these findings, we varied several operational parameters in order to investigate this strategy as a new bottom-up assembly method for producing plasmonic-magnetic nanoassemblies. PMID:27156089

  13. Functionalized magnetite particles for adsorption of colloidal noble metal nanoparticles.

    PubMed

    Lopes, Joana L; Marques, Karine L; Girão, Ana V; Pereira, Eduarda; Trindade, Tito

    2016-08-01

    Magnetite (inverse spinel type) particles have been surface-modified with siliceous shells enriched in dithiocarbamate groups. The deposition of colloidal noble metal nanoparticles (Au, Ag, Pt, Pd) onto the modified magnetites can be performed by treating the respective hydrosols with the magnetic sorbents, thus allowing their uptake from water under a magnetic gradient. In particular, for Au colloids, these magnetic particles are very efficient sorbents that we ascribe to the strong affinity of sulfur-containing groups at the magnetite surfaces for this metal. Considering the extensive use of Au colloids in laboratorial and industrial contexts, the approach described here might have an impact on the development of nanotechnologies to recover this precious metal. En route to these findings, we varied several operational parameters in order to investigate this strategy as a new bottom-up assembly method for producing plasmonic-magnetic nanoassemblies.

  14. Photocatalytic water reduction with copper-based photosensitizers: a noble-metal-free system.

    PubMed

    Luo, Shu-Ping; Mejía, Esteban; Friedrich, Aleksej; Pazidis, Alexandra; Junge, Henrik; Surkus, Annette-Enrica; Jackstell, Ralf; Denurra, Stefania; Gladiali, Serafino; Lochbrunner, Stefan; Beller, Matthias

    2013-01-01

    Of noble descent: a fully noble-metal-free system for the photocatalytic reduction of water at room temperature has been developed. This system consists of Cu(I) complexes as photosensitizers and [Fe(3)(CO)(12)] as the water-reduction catalyst. The novel Cu-based photosensitizers are relatively inexpensive, readily available from commercial sources, and stable to ambient conditions, thus making them an attractive alternative to the widely used noble-metal based systems. PMID:23047871

  15. Surface entropy of liquid transition and noble metals

    NASA Astrophysics Data System (ADS)

    Gosh, R. C.; Das, Ramprosad; Sen, Sumon C.; Bhuiyan, G. M.

    2015-07-01

    Surface entropy of liquid transition and noble metals has been investigated using an expression obtained from the hard-sphere (HS) theory of liquid. The expression is developed from the Mayer's extended surface tension formula [Journal of Non-Crystalline Solids 380 (2013) 42-47]. For interionic interaction in metals, Brettonet-Silbert (BS) pseudopotentials and embedded atom method (EAM) potentials have been used. The liquid structure is described by the variational modified hypernetted chain (VMHNC) theory. The essential ingredient of the expression is the temperature dependent effective HS diameter (or packing fraction), which is calculated from the aforementioned potentials together with the VMHNC theory. The obtained results for the surface entropy using the effective HS diameter are found to be good in agreement with the available experimental as well as other theoretical values.

  16. Silica coated noble metal nanoparticle hydrosols as supported catalyst precursors.

    PubMed

    Kong, Tung Shing Adam; Yu, Kai Man Kerry; Tsang, Shik Chi

    2006-04-01

    Synthesis of well-defined nanoparticles has been intensively pursued not only for their fundamental scientific interest, but also for many technological applications. One important development of the nanomaterial is in the area of chemical catalysis. We have now developed a new aqueous-based method for the synthesis of silica encapsulated noble metal nanoparticles in controlled dimensions. Thus, colloid stable silica encapsulated approximately 5 nm platinum nanoparticle is synthesized by a multi-step method. The thickness of the silica coating could be controlled using a different amount of silica precursor. These particles supported on a high surface area alumina are also demonstrated to display a superior hydrogenation activity and stability against metal sintering after thermal activation.

  17. Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

    NASA Technical Reports Server (NTRS)

    Srinivasan, P.; McCubbin, F. M.; Rahman, Z.; Keller, L. P.; Agee, C. B.

    2016-01-01

    CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approximately 576-867 degrees Centigrade. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Me-tallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120-degree triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3 plus, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

  18. 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).

  19. Star-like copolymer stabilized noble-metal nanoparticle powders.

    PubMed

    Cao, Peng-Fei; Yan, Yun-Hui; Mangadlao, Joey Dacula; Rong, Li-Han; Advincula, Rigoberto

    2016-04-14

    The amphiphilic star-like copolymer polyethylenimine-block-poly(ε-caprolactone) (PEI-b-PCL) was utilized to transfer the pre-synthesized citrate-capped noble metal nanoparticles (NMNPs) from an aqueous layer to an organic layer without any additional reagents. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were utilized to study the assembly of the polymers coated on the surface of the citrate-capped NMNPs. After removing the organic solvent, the polymer-coated NMNPs in powder form (PCP-NMNPs) were obtained. The excellent solubility of the PEI-b-PCL allows the PCP-NMNPs to be easily dispersed in most of the organic solvents without any significant aggregation. Moreover, the good thermal stability and long-term stability make PCP-NMNPs an excellent NMNP-containing hybrid system for different specific applications, such as surface coating, catalysis and thermoplastic processing of nanocomposite materials.

  20. Synthesis and reactivities of cubane-type sulfido clusters containing noble metals.

    PubMed

    Hidai, M; Kuwata, S; Mizobe, Y

    2000-01-01

    Cubane-type sulfido clusters containing noble metals are newcomers compared with the corresponding clusters of the first transition series metals and molybdenum, which have been extensively studied in relation to metalloenzymes and industrial hydrodesulfurization catalysts. This Account reviews the recent progress in studies on the synthesis and reactivities of these noble metal cubane-type clusters. One of the goals in this new area lies in development of the unique catalysis of the noble metals embedded in the robust and redox-active cubane-type cores. Rational synthetic approaches indispensable to the preparation of such effective cluster catalysts are discussed to a significant extent.

  1. The Interaction of Hydrogen with Simple and Noble Metals Surfaces

    NASA Astrophysics Data System (ADS)

    Sprunger, Phillip T.

    The basic concepts of adsorption are illustrated by the investigation of a simple adsorbate (hydrogen) with the "simplest" metals (simple and noble metals). Theoretically tractable, these systems serve as an excellent test of our basic understanding of chemisorption. The interaction of atomic and molecular hydrogen with the surfaces of Mg(0001), Mg(1120), Li(110), K(110), Ag(110), and Ag(111) have been studied with a variety of experimental probes. In all cases, no evidence for H_2 associative or dissociative adsorption is observed at the substrate temperature investigated (>=q90 K). In the case of the simple metals below 150 K, atomic hydrogen is bound to the surfaces in a strongly chemisorbed state (hydride). For Mg and Li, the hydride is localized to the surface wherein the substrate electron density is lower than the bulk. Because of the low electron density, hydrogen is absorbed into the bulk of K at low temperatures and forms a bulk-hydride phase. However, these low-temperature phases are metastable. In the case of Mg, hydrogen moves into lower energy configuration bonding sites which are closer to or below the surface plane. However, the hydride characteristics are absent; the H atom is effectively screened because of the higher jellium density. In contrast, upon annealing, hydrogen is absorbed into the bulk of Li and K and phase separation occurs forming regions of clean metal and bulk hydride areas. The results are compared to theoretical studies; the propensity for absorption over adsorption is understood in terms of jellium-based models. In the case of silver, at 100 K, atomic hydrogen bonds in trigonal sites on both the (110) and (111) surfaces. As a function of H concentration, a sequence of lattice gas superstructures is observed; these phases are accompanied by small H-induced displacements of the substrate surface atoms. In the case of Ag(110), the low-temperature phase is metastable; upon annealing, hydrogen desorption from low energy states is

  2. RISK REDUCTION VIA GREENER SYNTHESIS OF NOBLE METAL NANOSTRUCTURES AND NANOCOMPOSITES

    EPA Science Inventory

    Aqueous preparation of nanoparticles using vitamins B2 and C which can function both as reducing and capping agents are described. Bulk and shape-controlled synthesis of noble nanostructures via microwave (MW)-assisted spontaneous reduction of noble metal salts using a-D-glucose,...

  3. Noble metal/functionalized cellulose nanofiber composites for catalytic applications.

    PubMed

    Gopiraman, Mayakrishnan; Bang, Hyunsik; Yuan, Guohao; Yin, Chuan; Song, Kyung-Hun; Lee, Jung Soon; Chung, Ill Min; Karvembu, Ramasamy; Kim, Ick Soo

    2015-11-01

    In this study, cellulose acetate nanofibers (CANFs) with a mean diameter of 325 ± 2.0 nm were electrospun followed by deacetylation and functionalization to produce anionic cellulose nanofibers (f-CNFs). The noble metal nanoparticles (RuNPs and AgNPs) were successfully decorated on the f-CNFs by a simple wet reduction method using NaBH4 as a reducing agent. TEM and SEM images of the nanocomposites (RuNPs/CNFs and AgNPs/CNFs) confirmed that the very fine RuNPs or AgNPs were homogeneously dispersed on the surface of f-CNFs. The weight percentage of the Ru and Ag in the nanocomposites was found to be 13.29 wt% and 22.60 wt% respectively; as confirmed by SEM-EDS analysis. The metallic state of the Ru and Ag in the nanocomposites was confirmed by XPS and XRD analyses. The usefulness of these nanocomposites was realized from their superior catalytic activity. In the aerobic oxidation of benzyl alcohol to benzaldehyde, the RuNPs/CNFs system gave a better yield of 89% with 100% selectivity. Similarly, the AgNPs/CNFs produced an excellent yield of 99% (100% selectivity) in the aza-Michael reaction of 1-phenylpiperazine with acrylonitrile. Mechanism has been proposed for the catalytic systems. PMID:26256382

  4. Noble metal/functionalized cellulose nanofiber composites for catalytic applications.

    PubMed

    Gopiraman, Mayakrishnan; Bang, Hyunsik; Yuan, Guohao; Yin, Chuan; Song, Kyung-Hun; Lee, Jung Soon; Chung, Ill Min; Karvembu, Ramasamy; Kim, Ick Soo

    2015-11-01

    In this study, cellulose acetate nanofibers (CANFs) with a mean diameter of 325 ± 2.0 nm were electrospun followed by deacetylation and functionalization to produce anionic cellulose nanofibers (f-CNFs). The noble metal nanoparticles (RuNPs and AgNPs) were successfully decorated on the f-CNFs by a simple wet reduction method using NaBH4 as a reducing agent. TEM and SEM images of the nanocomposites (RuNPs/CNFs and AgNPs/CNFs) confirmed that the very fine RuNPs or AgNPs were homogeneously dispersed on the surface of f-CNFs. The weight percentage of the Ru and Ag in the nanocomposites was found to be 13.29 wt% and 22.60 wt% respectively; as confirmed by SEM-EDS analysis. The metallic state of the Ru and Ag in the nanocomposites was confirmed by XPS and XRD analyses. The usefulness of these nanocomposites was realized from their superior catalytic activity. In the aerobic oxidation of benzyl alcohol to benzaldehyde, the RuNPs/CNFs system gave a better yield of 89% with 100% selectivity. Similarly, the AgNPs/CNFs produced an excellent yield of 99% (100% selectivity) in the aza-Michael reaction of 1-phenylpiperazine with acrylonitrile. Mechanism has been proposed for the catalytic systems.

  5. Synthesis and self-assembly of thio derivatives of calix[4]arene on noble metal surfaces.

    PubMed

    Genorio, Bostjan; He, Tao; Meden, Anton; Polanc, Slovenko; Jamnik, Janko; Tour, James M

    2008-10-21

    Self-assembled monolayers (SAMs) provide a simple route to functionalize electrode surfaces with organic molecules. Herein we use cavity-containing derivatives of calix[4]arenes in SAMs. Bound to noble metal surface, the assembled molecules are candidates to serve as molecular sieves for H 2 molecules and H (+) ions, which could have relevance for fuel cell applications. Tetra- O-alkylated calix[4]arenes with thiolacetate and thiolamide wide-rim anchoring groups in cone and partial-cone conformations were designed, synthesized and self-assembled onto Au, Pt, and Pd surfaces. The resulting SAMs were systematically examined. Single crystal X-ray diffraction of 5,11,17,23-tetrakis(thioacetyl)-25,26,27,28-tetra- i-propoxycalix[4]arene confirmed the cone conformation and revealed the cavity dimensions of the SAMs that were formed by immersing noble metal substrates (Au, Pt and Pd deposited on Si-wafers) in solutions of calix[4]arenes. Surface characterization techniques including ellipsometry, cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS) were used, indicating that the metal surface is terminated with a monomolecular layer. Experimental thicknesses obtained from the ellipsometry are consistent with the calculated values. CV results showed 50 to 80% physical passivation against the Fe(CN) 6 (3-/4-) couple, implying an overall relatively low concentration of defects and pinholes in the films. The binding energies of the S2p core level in the XPS were consistent with the literature values and revealed that up to 3.2 out of four anchoring groups were bonded to the noble metal surface.

  6. Fate of Noble Metals during the Pyroprocessing of Spent Nuclear Fuel

    SciTech Connect

    B.R. Westphal; D. Vaden; S.X. Li; G.L. Fredrickson; R.D. Mariani

    2009-09-01

    During the pyroprocessing of spent nuclear fuel by electrochemical techniques, fission products are separated as the fuel is oxidized at the anode and refined uranium is deposited at the cathode. Those fission products that are oxidized into the molten salt electrolyte are considered active metals while those that do not react are considered noble metals. The primary noble metals encountered during pyroprocessing are molybdenum, zirconium, ruthenium, rhodium, palladium, and technetium. Pyroprocessing of spent fuel to date has involved two distinctly different electrorefiner designs, in particular the anode to cathode configuration. For one electrorefiner, the anode and cathode collector are horizontally displaced such that uranium is transported across the electrolyte medium. As expected, the noble metal removal from the uranium during refining is very high, typically in excess of 99%. For the other electrorefiner, the anode and cathode collector are vertically collocated to maximize uranium throughput. This arrangement results in significantly less noble metals removal from the uranium during refining, typically no better than 20%. In addition to electrorefiner design, operating parameters can also influence the retention of noble metals, albeit at the cost of uranium recovery. Experiments performed to date have shown that as much as 100% of the noble metals can be retained by the cladding hulls while affecting the uranium recovery by only 6%. However, it is likely that commercial pyroprocessing of spent fuel will require the uranium recovery to be much closer to 100%. The above mentioned design and operational issues will likely be driven by the effects of noble metal contamination on fuel fabrication and performance. These effects will be presented in terms of thermal properties (expansion, conductivity, and fusion) and radioactivity considerations. Ultimately, the incorporation of minor amounts of noble metals from pyroprocessing into fast reactor metallic fuel

  7. Fluorescence enhancement in visible light: dielectric or noble metal?

    PubMed

    Sun, S; Wu, L; Bai, P; Png, C E

    2016-07-28

    A high permittivity dielectric gives the impression of outperforming plasmonic noble metal in visible light fluorescence enhancement primarily because of its small loss. Nonetheless, the performances of these two platforms in various situations remain obscure due to the different optical confinement mechanisms as well as the complexity in the fluorescence enhancement process. This study presents a comprehensive comparison between these two platforms based on nanoparticles (NPs) to evaluate their capability and applicability in fluorescence enhancement by taking into account the fluorescence excitation rate, the quantum yield, the fluorophore wavelengths and Stokes shifts as well as the far field intensity. In a low permittivity sensing medium (e.g. air), the dielectric NP can achieve comparable or higher fluorescence enhancement than the metal NP due to its decent NP-enhanced excitation rate and larger quantum yield. In a relatively high permittivity sensing medium (e.g. water), however, there is a significant decrement of the excitation rate of the dielectric NP as the permittivity contrast decreases, leading to a smaller fluorescence enhancement compared to the metallic counterpart. Combining the fluorescence enhancement and the far field intensity studies, we further conclude that for both dielectric and plasmonic NPs, the optimal situation occurs when the fluorescence excitation wavelength, the fluorescence emission wavelength and the electric-dipole-mode of the dielectric NP (or the plasmonic resonance of the metal NP) are the same and all fall in the low conductivity region of the NP material. We also find that the electric-dipole-mode of the dielectric NP performs better than the magnetic-dipole-mode for fluorescence enhancement applications because only the electric-dipole-mode can be strongly excited by the routinely used fluorescent dyes and quantum dots, which behave as electric dipoles by nature.

  8. Fluorescence enhancement in visible light: dielectric or noble metal?

    PubMed

    Sun, S; Wu, L; Bai, P; Png, C E

    2016-07-28

    A high permittivity dielectric gives the impression of outperforming plasmonic noble metal in visible light fluorescence enhancement primarily because of its small loss. Nonetheless, the performances of these two platforms in various situations remain obscure due to the different optical confinement mechanisms as well as the complexity in the fluorescence enhancement process. This study presents a comprehensive comparison between these two platforms based on nanoparticles (NPs) to evaluate their capability and applicability in fluorescence enhancement by taking into account the fluorescence excitation rate, the quantum yield, the fluorophore wavelengths and Stokes shifts as well as the far field intensity. In a low permittivity sensing medium (e.g. air), the dielectric NP can achieve comparable or higher fluorescence enhancement than the metal NP due to its decent NP-enhanced excitation rate and larger quantum yield. In a relatively high permittivity sensing medium (e.g. water), however, there is a significant decrement of the excitation rate of the dielectric NP as the permittivity contrast decreases, leading to a smaller fluorescence enhancement compared to the metallic counterpart. Combining the fluorescence enhancement and the far field intensity studies, we further conclude that for both dielectric and plasmonic NPs, the optimal situation occurs when the fluorescence excitation wavelength, the fluorescence emission wavelength and the electric-dipole-mode of the dielectric NP (or the plasmonic resonance of the metal NP) are the same and all fall in the low conductivity region of the NP material. We also find that the electric-dipole-mode of the dielectric NP performs better than the magnetic-dipole-mode for fluorescence enhancement applications because only the electric-dipole-mode can be strongly excited by the routinely used fluorescent dyes and quantum dots, which behave as electric dipoles by nature. PMID:27374052

  9. Star-like copolymer stabilized noble-metal nanoparticle powders

    NASA Astrophysics Data System (ADS)

    Cao, Peng-Fei; Yan, Yun-Hui; Mangadlao, Joey Dacula; Rong, Li-Han; Advincula, Rigoberto

    2016-03-01

    The amphiphilic star-like copolymer polyethylenimine-block-poly(ε-caprolactone) (PEI-b-PCL) was utilized to transfer the pre-synthesized citrate-capped noble metal nanoparticles (NMNPs) from an aqueous layer to an organic layer without any additional reagents. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were utilized to study the assembly of the polymers coated on the surface of the citrate-capped NMNPs. After removing the organic solvent, the polymer-coated NMNPs in powder form (PCP-NMNPs) were obtained. The excellent solubility of the PEI-b-PCL allows the PCP-NMNPs to be easily dispersed in most of the organic solvents without any significant aggregation. Moreover, the good thermal stability and long-term stability make PCP-NMNPs an excellent NMNP-containing hybrid system for different specific applications, such as surface coating, catalysis and thermoplastic processing of nanocomposite materials.The amphiphilic star-like copolymer polyethylenimine-block-poly(ε-caprolactone) (PEI-b-PCL) was utilized to transfer the pre-synthesized citrate-capped noble metal nanoparticles (NMNPs) from an aqueous layer to an organic layer without any additional reagents. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were utilized to study the assembly of the polymers coated on the surface of the citrate-capped NMNPs. After removing the organic solvent, the polymer-coated NMNPs in powder form (PCP-NMNPs) were obtained. The excellent solubility of the PEI-b-PCL allows the PCP-NMNPs to be easily dispersed in most of the organic solvents without any significant aggregation. Moreover, the good thermal stability and long-term stability make PCP-NMNPs an excellent NMNP-containing hybrid system for different specific applications, such as surface coating, catalysis and thermoplastic processing of nanocomposite materials. Electronic supplementary information (ESI) available: Synthesis scheme and the 1H NMR spectrum of PEI

  10. Physisorption mechanism in graphene/noble metal (111)/Ni(111) heterostructures: An ab-initio study

    NASA Astrophysics Data System (ADS)

    Moaddeli, Mohammad; Salehi, Hamdollah; Amiri, Peiman

    2016-08-01

    The 3D stacking of various 2D systems is an intelligent way of aiming to overcome the limitations usually faced by 2D systems. We study the adsorption of graphene on noble metal monolayers upon Ni (111) substrate, using density functional theory. The bonding mechanism at noble metal-graphene and noble metal-Ni interfaces is found to be physisorption and chemisorption, respectively. The bonding of graphene to Cu, Ag, and Au (111) monolayers is so weak that the conical shape of the Dirac point is preserved. The doping effects of a substrate lead to a small opening gap for gr/Cu/Ni and gr/Ag/Ni systems. These predictions are in agreement with experimental results. The intercalation of a noble metal monolayer between graphene and Ni (111) substrate changes the magnetic response from Ni surface and causes the formation of a ferrimagnetic system.

  11. Electronic, Mechanical, and Dielectric Properties of Two-Dimensional Atomic Layers of Noble Metals

    NASA Astrophysics Data System (ADS)

    Kapoor, Pooja; Kumar, Jagdish; Kumar, Arun; Kumar, Ashok; Ahluwalia, P. K.

    2016-08-01

    We present density functional theory-based electronic, mechanical, and dielectric properties of monolayers and bilayers of noble metals (Au, Ag, Cu, and Pt) taken with graphene-like hexagonal structure. The Au, Ag, and Pt bilayers stabilize in AA-stacked configuration, while the Cu bilayer favors the AB stacking pattern. The quantum ballistic conductance of the noble-metal mono- and bilayers is remarkably increased compared with their bulk counterparts. Among the studied systems, the tensile strength is found to be highest for the Pt monolayer and bilayer. The noble metals in mono- and bilayer form show distinctly different electron energy loss spectra and reflectance spectra due to the quantum confinement effect on going from bulk to the monolayer limit. Such tunability of the electronic and dielectric properties of noble metals by reducing the degrees of freedom of electrons offers promise for their use in nanoelectronics and optoelectronics applications.

  12. CO oxidation studies over supported noble metal catalysts and single crystals: A review

    NASA Technical Reports Server (NTRS)

    Boecker, Dirk; Gonzalez, Richard D.

    1987-01-01

    The catalytic oxidation of CO over noble metal catalysts is reviewed. Results obtained on supported noble metal catalysts and single crystals both at high pressures and under UHV conditions are compared. The underlying causes which result in surface instabilities and multiple steady-state oscillations are considered, in particular, the occurrence of hot spots. CO islands of reactivity, surface oxide formation and phase transformations under oscillatory conditions are discussed.

  13. A new type of noble metal mineralization in the Northern Caucasus

    NASA Astrophysics Data System (ADS)

    Bogush, I. A.; Cherkashin, V. I.; Ryabov, G. V.; Abdullayev, M. Sh.

    2016-01-01

    The weathering crust of the Beden ultrabasite massif (the basin of Big Laba River) is identified and studied. Anomalously high contents of noble metals (Au, Pt, Pd) are revealed in the basal horizon of the Jurassic part of the weathering crust. For this reason we suspect an existence of a belt of noble metal miner-alization in the Paleozoic ultrabasites in the Peredovoi Range of the Northern Caucasus.

  14. Recovery of Noble Metals and Technetium from Nuclear Waste

    SciTech Connect

    Moon, J.K.; Han, Y.J.; Lee, E.H.; Jung, C.H.; Lee, B.C.

    2006-07-01

    An adsorptive separation of Pd, Rh and Tc was tested by using simulated chemical solutions. Pd(NO{sub 3}){sub 2} and Rh(NO{sub 3}){sub 3} were used for the noble metal sources, and Re 203 after dissolving it in 0.5 M nitric acid was used for the technetium substitute, respectively. A felt type ACF (activated carbon fiber) after being pretreated with 1 M NaOH, and an EIR (extractant impregnated resin) which was prepared by impregnating Aliquat 336 onto Amberlite XAD-4 resin were evaluated on their adsorption equilibrium and kinetic performances. As the results, the ACF showed a high selectivity for the palladium ions over the rhodium and rhenium ions. On the other hand, the EIR was shown to be effective for separation of rhenium from the palladium-free two component system of rhenium and rhodium. Column tests were also performed to confirm the separation efficiency of palladium and rhenium using a jacketed glass column (diam. 11 x L 150). The ACF bed showed the complete separation of palladium from rhenium and rhodium. The breakthrough volume, when 1% of breakthrough is considered, was about 140 BV for palladium, while only a small amount of an adsorption of rhenium and rhodium were found in the column. Then the EIR column was applied to separate rhenium from rhodium and showed successful separation performance with about 122 BV of breakthrough volume. The palladium and rhenium with high purity were recovered effectively by eluting the beds with nitric acid. (authors)

  15. Biologically activated noble metal alloys at the nanoscale: for lithium ion battery anodes.

    PubMed

    Lee, Yun Jung; Lee, Youjin; Oh, Dahyun; Chen, Tiffany; Ceder, Gerbrand; Belcher, Angela M

    2010-07-14

    We report the synthesis and electrochemical activity of gold and silver noble metals and their alloy nanowires using multiple virus clones as anode materials for lithium ion batteries. Using two clones, one for specificity (p8#9 virus) and one versatility (E4 virus), noble metal nanowires of high-aspect ratio with diameters below 50 nm were successfully synthesized with control over particle sizes, morphologies, and compositions. The biologically derived noble metal alloy nanowires showed electrochemical activities toward lithium even when the electrodes were prepared from bulk powder forms. The improvement in capacity retention was accomplished by alloy formation and surface stabilization. Although the cost of noble metals renders them a less ideal choice for lithium ion batteries, these noble metal/alloy nanowires serve as great model systems to study electrochemically induced transformation at the nanoscale. Given the demonstration of the electrochemical activity of noble metal alloy nanowires with various compositions, the M13 biological toolkit extended its utility for the study on the basic electrochemical property of materials.

  16. Epsilon Metal Waste Form for Immobilization of Noble Metals from Used Nuclear Fuel

    SciTech Connect

    Crum, Jarrod V.; Strachan, Denis M.; Rohatgi, Aashish; Zumhoff, Mac R.

    2013-10-01

    Epsilon metal (ε-metal), an alloy of Mo, Pd, Rh, Ru, and Tc, is being developed as a waste form to treat and immobilize the undissolved solids and dissolved noble metals from aqueous reprocessing of commercial used nuclear fuel. Epsilon metal is an attractive waste form for several reasons: increased durability relative to borosilicate glass, it can be fabricated without additives (100% waste loading), and in addition it also benefits borosilicate glass waste loading by eliminating noble metals from the glass and thus the processing problems related there insolubility in glass. This work focused on the processing aspects of the epsilon metal waste form development. Epsilon metal is comprised of refractory metals resulting in high reaction temperatures to form the alloy, expected to be 1500 - 2000°C making it a non-trivial phase to fabricate by traditional methods. Three commercially available advanced technologies were identified: spark-plasma sintering, microwave sintering, and hot isostatic pressing, and investigated as potential methods to fabricate this waste form. Results of these investigations are reported and compared in terms of bulk density, phase assemblage (X-ray diffraction and elemental analysis), and microstructure (scanning electron microscopy).

  17. Epsilon metal waste form for immobilization of noble metals from used nuclear fuel

    NASA Astrophysics Data System (ADS)

    Crum, Jarrod V.; Strachan, Denis; Rohatgi, Aashish; Zumhoff, Mac

    2013-10-01

    Epsilon metal (ɛ-metal), an alloy of Mo, Pd, Rh, Ru, and Tc, is being developed as a waste form to treat and immobilize the undissolved solids and dissolved noble metals from aqueous reprocessing of commercial used nuclear fuel. Epsilon metal is an attractive waste form for several reasons: increased durability relative to borosilicate glass, it can be fabricated without additives (100% waste loading), and in addition it also benefits borosilicate glass waste loading by eliminating noble metals from the glass, thus the processing problems related to their insolubility in glass. This work focused on the processing aspects of the epsilon metal waste form development. Epsilon metal is comprised of refractory metals resulting in high alloying temperatures, expected to be 1500-2000 °C, making it a non-trivial phase to fabricate by traditional methods. Three commercially available advanced technologies were identified: spark-plasma sintering, microwave sintering, and hot isostatic pressing, and investigated as potential methods to fabricate this waste form. Results of these investigations are reported and compared in terms of bulk density, phase assemblage (X-ray diffraction and elemental analysis), and microstructure (scanning electron microscopy).

  18. Nanostructured elastomers: From smectic liquid crystals to noble metal nanocomposites

    NASA Astrophysics Data System (ADS)

    Lentz, Daniel M.

    Noble metal/polymer nanocomposites are a desirable and useful class of material due to their combination of the beneficial processibility and mechanical properties of polymers with the optical, electrical, barrier, and other engineering properties of metal nanoparticles. Potential applications of such materials include non-linear optical materials with gold nanoparticles or conductive polymer substrates with percolated silver nanoparticles. A processing approach has been developed whereby metal nanoparticles, especially silver and gold, can be infused into the surface of a thermoplastic elastomer following the melt processing operation. This reaction-diffusion approach (nanoinfusion) allows metal nanoparticles to be introduced at relatively low cost while avoiding the issues of thermal degradation, microphase separation, or agglomeration that can occur at elevated temperatures in the melt state. The nanoinfusion process involves immersion of a molded, cast, or extruded plastic article in an aqueous plasticizer solution (Bayer MaterialScience AURARTM Infusion Technology) containing a metal salt such as HAuCl4 or AgNO 3. Infusion of the metal salt into the plastic surface is achieved well below the melt-processing temperature due to plasticization of a thin surface layer of 10-500 microm. The metal salt is subsequently reduced to produce zero-valent metal nanoparticles by a second infusion of a reducing agent or a thermal or photochemical reduction process. The growth and agglomeration of the nanoparticles is arrested by the high viscosity of the polymer matrix, producing a stable nanocomposite. In order to examine how nanoparticle size distribution and concentration are affected by soak times in the salt and reducing agent solutions, combinatorial, high-throughput screening methods have been applied. Particle size distributions are characterized rapidly by small-angle x-ray scattering (SAXS) using a "dual gradient" nanoinfusion matrix. In addition, an improved

  19. A GREEN CHEMISTRY APPROACH TO PREPARATION OF CORE (FE OR CU)-SHELL (NOBLE METALS) NANOCOMPOSITES USING AQUEOUS ASCORBIC ACID

    EPA Science Inventory

    A greener method to fabricate novel core (Fe or Cu)-shell (noble metals) nanocomposites of transition metals such as Fe and Cu and noble metals such as Au, Pt, Pd, and Ag using aqueous ascorbic acid is described. Transition metal salts such as Cu and Fe were reduced using ascor...

  20. Noble metal and graphite formation in metamorphic rocks of the Khanka terrane, Far East Russia

    NASA Astrophysics Data System (ADS)

    Khanchuk, A. I.; Plyusnina, L. P.; Berdnikov, N. V.

    2015-03-01

    Noble metal-graphite mineralization has been identified in the Riphean-Cambrian metamorphic complexes of the northern Khanka terrane, Russia. The graphite mineralization is hosted in magmatic and sedimentary rocks metamorphosed under greenschist to granulite facies conditions. This paper provides the results of our study of the Turgenevo-Tamga graphite deposits. This study analyzes the geochemistry of the noble metals with the aim of determining the spatial relationships between noble metals and graphite. The graphitized rocks, analyzed by various geochemical methods, show a wide range of noble metal concentrations (ppm): Pt (0.02-62.13), Au (0.02-26), Ag (0.56-4.41), Pd (0.003-5.67), Ru (0.007-0.2), Rh (0.001-0.74), Ir (0.002-0.55), and Os (0.011-0.09). Crystallization from gas-condensates is indicated by the relationships between the noble metal mineralization and the graphite, and in particular the inhomogeneous distribution of graphite in the rocks, the inhomogeneous distribution of metals in the graphite, the microglobular graphite structures, and the carbon isotopic compositions. Thermal analysis and Raman spectroscopy indicate that some of the graphite formed from the metamorphism of sedimentary biogenic carbonaceous matter. The uneven distribution of noble metals in the rocks, and the compositional variability of the mineralization, implies that the origin of the metals was largely related to endogenic processes involving reduced fluids derived from depth. Our conclusion is that the noble metals and graphite mainly originated from magmatic fluids, but that some material was derived from exogenic and metamorphic sources.

  1. Bio-related noble metal nanoparticle structure property relationships

    NASA Astrophysics Data System (ADS)

    Leonard, Donovan Nicholas

    Structure property relationships of noble metal nanoparticles (NPs) can be drastically different than bulk properties of the same metals. This research study used state-of-the-art analytical electron microscopy and scanned probe microscopy to determine material properties on the nanoscale of bio-related Au and Pd NPs. Recently, it has been demonstrated the self-assembly of Au NPs on functionalized silica surfaces creates a conductive surface. Determination of the aggregate morphology responsible for electron conduction was studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM). In addition, changes in the electrical properties of the substrates after low temperature (<350°C) annealing was also studied. It was found that coalescence and densification of the Au NP aggregates disrupted the interconnected network which subsequently created a loss of conductivity. Investigation of bio-related Au/SiO2 core-shell NPs determined why published experimental results showed the sol-gel silica shell improved, by almost an order of magnitude, the detection efficiency of a DNA detection assay. Novel 360° rotation scanning TEM (STEM) imaging allowed study of individual NP surface morphology and internal structure. Electron energy loss spectroscopy (EELS) spectrum imaging determined optoelectronic properties and chemical composition of the silica shell used to encapsulate Au NPs. Results indicated the sol-gel deposited SiO2 had a band gap energy of ˜8.9eV, bulk plasmon-peak energy of ˜25.5eV and chemical composition of stoichiometric SiO2. Lastly, an attempt to elicit structure property relationships of novel RNA mediated Pd hexagon NPs was performed. Selected area electron diffraction (SAD), low voltage scanning transmission electron microscopy (LV-STEM), electron energy loss spectroscopy (EELS) and energy dispersive spectroscopy (EDS) were chosen for characterization of atomic ordering, chemical composition and optoelectronic properties of the novel

  2. Solar Noble Gases from ACFER 111 Metal Etched in Vacuo

    NASA Astrophysics Data System (ADS)

    Pedroni, A.; Begemann, F.

    1992-07-01

    Regolith grains dissolved by stepwise etching release a mixture of near-surface implanted Solar Wind gases (SW) and a deeper- sited, isotopically heavier component attributed to Solar Energetic Particles (SEP) (1,2,3). In all regolith materials examined so far the elemental abundance ratios in both components are distinctly different from the canonical solar values (4). The differences are generally explained to be owing to diffusive elemental fractionation although there is no strong evidence that upon their implantation the composition of the gases was indeed solar. In contrast, the solar noble gases present in the H3-H6 chondritic regolith breccia Acfer 111 appear to be nearly unfractionated and thus offer a unique chance for more accurate analyses. A magnetic fraction of Acfer 111 matrix, consisting of approx. 80% metal and 20% silicates, was etched with a 60 g/mol aqueous solution of HNO3 in a high-vacuum extraction line similar to that in (1). The gases released were drawn off in steps and analyzed; the experiment was stopped when ~97% of the metal and ~50% of the silicates were dissolved. As etching proceeds, the isotopic composition of the released gases changes in a pattern similar to that observed previously in other regolithic materials. The isotopic composition of solar neon decreases from ^20Ne/^22Ne=13.1 in the first step to ^20Ne/^22Ne=11.6, which can be interpreted as a change of the mixing ratio of SW (^20Ne/^22Ne=13.7) and SEP (^20Ne/^22Ne=11.3) neon. The isotopic compositions of solar He, Ar, and Kr are consistent with their also being mixtures of SW and SEP having compositions reported previously (2,3), although our data are compromised to some extent by the presence of planetary gases extracted from the silicates and, in the first steps, by atmospheric contamination probably present in terrestrial weathering products (mostly rust). The elemental composition of noble gases released from Acfer 111 was distinct from previous experiments: The (^4He

  3. Ab initio investigation of the oxygen reduction reaction activity on noble metal (Pt, Au, Pd), Pt3M (M = Fe, Co, Ni, Cu) and Pd3M (M = Fe, Co, Ni, Cu) alloy surfaces, for Lisbnd O2 cells

    NASA Astrophysics Data System (ADS)

    Sankarasubramanian, Shrihari; Singh, Nikhilendra; Mizuno, Fuminori; Prakash, Jai

    2016-07-01

    First principles, density functional theory (DFT) modelling of the oxygen reduction reaction (ORR) on noble metal (Pt, Au, Pd), Pt3M (M = Fe, Co, Ni, Cu) and Pd3M (M = Fe, Co, Ni, Cu) alloy surfaces, was carried out. Periodic models of close-packed (111) surfaces were constructed, their geometry was optimized and the most stable geometric surface configuration was identified. The correlation between the intermediate species binding energy and the favored reaction pathway from amongst 1e-, 2e-, and 4e- mechanisms were studied by calculating the binding energies of a 1/4 monolayer of O, O2, LiO, LiO2, Li2O2, and Li2O on various sites and orientations. The reaction free energies (ΔGrxn) were calculated and used to compute the catalytic activity of the surfaces using molecular kinetics theory. Plots of the catalytic activity vs. Oxygen binding energy (EBinding (O)) showed a typical "volcano" profile. The insights gained from this study can be used to guide the choice of cathode catalysts in Lisbnd O2 cells.

  4. The in vitro effect of commercially available noble metal nanocolloids on the splenocyte proliferative response and cytokine production in mice.

    PubMed

    Małaczewska, J

    2014-01-01

    Noble metal nanoparticles, currently among the most popular types of nanomaterials, are capable of penetrating through biological barriers once they enter a living organism. There, they can permeate into organs possessing the reticuloendothelial system, such as the spleen. The objective of this study was to determine the effect of commercial nanocolloids of noble metals (silver, gold and copper), recommended by the manufacturer as dietary supplements, on the in vitro viability, proliferative activity and production of cytokines (IL-1beta, IL-2, IL-6, IL-10 and TNF-alpha) by mouse splenocytes. All of the analyzed colloids had some effect on the activity of mouse splenocytes. Silver colloid was characterized by high toxicity - concentrations of 1.25 ppm and above substantially depressed the viability of cells as well as their proliferative activity and ability to synthesize cytokines. The other two colloids were far less toxic than nanosilver, although their non-toxic concentrations had a significant effect on the production of cytokines by mitogen activated splenocytes. The colloid of gold decreased the level of IL-2, and the colloid of copper caused an increase in IL-2, IL6 and IL-10. At the same time, copper colloid alone induced the synthesis of IL-1beta in mitogen unstimulated cells. The results indicate that colloids of noble metals are capable of affecting the activity of immunocompetent cells in important peripheral organs of the immune system.

  5. Distribution and formation conditions of noble metal mineralization in coal-bearing basins

    NASA Astrophysics Data System (ADS)

    Seredin, V. V.

    2007-02-01

    Original data and a survey of the literature indicate that Au and Au-PGE mineralization are abundant in coal measures. Anomalous contents of noble metals have been established in basins with various types of basement, composed of granite, volcanic rocks, schist, and limestone. These basins are located in Au-and PGE-bearing ore districts, as well as at a considerable distance from known ore deposits and occurrences. Ore formation in coal-bearing basins may occur during sedimentation, peat accumulation, and diagenesis of organic matter or may be epigenetic. Noble metals are supplied to sedimentary basins as minerals that are transported by water and air and as ion species migrating along with surface and subsurface in-and exfiltration solutions of various chemical and genetic types. Ore mineralization concentrates in coal seams and host sedimentary beds of various grain size, including conglomerate, sand, and clay, as well as in zones of hydrothermal alteration superimposed on basement rocks and the sedimentary cover. The mode of occurrence of noble metals in coal basins is diverse as well (noble metal minerals, isomorphic admixtures in sulfides, and organic compounds). The data presented allow coal-bearing basins to be regarded as promising for economic noble metal mineralization fit for recovery as by-products in the course of coal mining.

  6. Activation of Peroxymonosulfate by Surface-Loaded Noble Metal Nanoparticles for Oxidative Degradation of Organic Compounds.

    PubMed

    Ahn, Yong-Yoon; Yun, Eun-Tae; Seo, Ji-Won; Lee, Changha; Kim, Sang Hoon; Kim, Jae-Hong; Lee, Jaesang

    2016-09-20

    This study demonstrates the capability of noble metal nanoparticles immobilized on Al2O3 or TiO2 support to effectively activate peroxymonosulfate (PMS) and degrade select organic compounds in water. The noble metals outperformed a benchmark PMS activator such as Co(2+) (water-soluble) for PMS activation and organic compound degradation at acidic pH and showed the comparable activation capacity at neutral pH. The efficiency was found to depend on the type of noble metal (following the order of Pd > Pt ≈ Au ≫ Ag), the amount of noble metal deposited onto the support, solution pH, and the type of target organic substrate. In contrast to common PMS-activated oxidation processes that involve sulfate radical as a main oxidant, the organic compound degradation kinetics were not affected by sulfate radical scavengers and exhibited substrate dependency that resembled the PMS activated by carbon nanotubes. The results presented herein suggest that noble metals can mediate electron transfer from organic compounds to PMS to achieve persulfate-driven oxidation, rather than through reductive conversion of PMS to reactive sulfate radical. PMID:27564590

  7. Activation of Peroxymonosulfate by Surface-Loaded Noble Metal Nanoparticles for Oxidative Degradation of Organic Compounds.

    PubMed

    Ahn, Yong-Yoon; Yun, Eun-Tae; Seo, Ji-Won; Lee, Changha; Kim, Sang Hoon; Kim, Jae-Hong; Lee, Jaesang

    2016-09-20

    This study demonstrates the capability of noble metal nanoparticles immobilized on Al2O3 or TiO2 support to effectively activate peroxymonosulfate (PMS) and degrade select organic compounds in water. The noble metals outperformed a benchmark PMS activator such as Co(2+) (water-soluble) for PMS activation and organic compound degradation at acidic pH and showed the comparable activation capacity at neutral pH. The efficiency was found to depend on the type of noble metal (following the order of Pd > Pt ≈ Au ≫ Ag), the amount of noble metal deposited onto the support, solution pH, and the type of target organic substrate. In contrast to common PMS-activated oxidation processes that involve sulfate radical as a main oxidant, the organic compound degradation kinetics were not affected by sulfate radical scavengers and exhibited substrate dependency that resembled the PMS activated by carbon nanotubes. The results presented herein suggest that noble metals can mediate electron transfer from organic compounds to PMS to achieve persulfate-driven oxidation, rather than through reductive conversion of PMS to reactive sulfate radical.

  8. Metal-Free and Noble Metal-Free Heteroatom-Doped Nanostructured Carbons as Prospective Sustainable Electrocatalysts.

    PubMed

    Asefa, Tewodros

    2016-09-20

    The large-scale deployment of many types of fuel cells and electrolyzers is currently constrained by the lack of sustainable and efficient catalysts that can replace the less earth-abundant, noble metal-based catalysts, which are commonly used in these renewable energy systems. This burgeoning issue has led to explosive research efforts worldwide to find alternative, metal-free and noble metal-free catalysts that are composed of inexpensive and earth-abundant elements. Hence, the recent discoveries that doping carbon nanomaterials with heteroatoms (such as N, S, B, etc.) can give sustainable materials with good electrocatalytic activity for reactions carried out in fuel cells and electrolyzers have been not only quite exciting but also very promising to address these challenging issues. Interestingly, even though they contain no metals or involve only the inexpensive, more earth-abundant ones, the catalytic activity of some of these materials fares well with those of the commercially used noble metal-based electrocatalysts, such as Pt/C. However, research efforts to improve the catalytic activity, selectivity, and stability of some of these materials for various reactions are still necessary and thus continuing. While some of these efforts have focused on finding synthetic methods that can tune the structures and compositions of already known materials and thereby improve their catalytic properties (activity, selectivity, stability, etc.), others have focused on developing entirely new materials that can exhibit better or superior catalytic properties. In these efforts, additional considerations are also being paid to find facile synthetic routes or renewable and inexpensive precursors that can lead to such types of catalysts in order to make the entire process highly sustainable and widely applicable. In this Account, notable heteroatom-doped carbon catalysts that have been developed for reactions in fuel cells and water electrolyzers, the various synthetic

  9. Metal-Free and Noble Metal-Free Heteroatom-Doped Nanostructured Carbons as Prospective Sustainable Electrocatalysts.

    PubMed

    Asefa, Tewodros

    2016-09-20

    The large-scale deployment of many types of fuel cells and electrolyzers is currently constrained by the lack of sustainable and efficient catalysts that can replace the less earth-abundant, noble metal-based catalysts, which are commonly used in these renewable energy systems. This burgeoning issue has led to explosive research efforts worldwide to find alternative, metal-free and noble metal-free catalysts that are composed of inexpensive and earth-abundant elements. Hence, the recent discoveries that doping carbon nanomaterials with heteroatoms (such as N, S, B, etc.) can give sustainable materials with good electrocatalytic activity for reactions carried out in fuel cells and electrolyzers have been not only quite exciting but also very promising to address these challenging issues. Interestingly, even though they contain no metals or involve only the inexpensive, more earth-abundant ones, the catalytic activity of some of these materials fares well with those of the commercially used noble metal-based electrocatalysts, such as Pt/C. However, research efforts to improve the catalytic activity, selectivity, and stability of some of these materials for various reactions are still necessary and thus continuing. While some of these efforts have focused on finding synthetic methods that can tune the structures and compositions of already known materials and thereby improve their catalytic properties (activity, selectivity, stability, etc.), others have focused on developing entirely new materials that can exhibit better or superior catalytic properties. In these efforts, additional considerations are also being paid to find facile synthetic routes or renewable and inexpensive precursors that can lead to such types of catalysts in order to make the entire process highly sustainable and widely applicable. In this Account, notable heteroatom-doped carbon catalysts that have been developed for reactions in fuel cells and water electrolyzers, the various synthetic

  10. Formation of noble metal nanocrystals in the presence of biomolecules

    NASA Astrophysics Data System (ADS)

    Burt, Justin Lockheart

    One of the most promising, yet least studied routes for producing biocompatible nanostructures involves synthesis in the presence of biomolecules. I hypothesized that globular proteins could provide a suitable framework to regulate the formation of noble metal nanocrystals. As proof of concept, I designed two novel synthesis protocols utilizing bovine serum albumin (BSA) protein to regulate the formation of gold nanocrystals. In the first case, the standard protocol for polyol reduction was modified by replacing ethylene glycol with glycerin, replacing synthetic polymers with BSA as protecting agent, and decreasing the reaction temperature. In the second case, the Brust-Schiffrin two-phase reduction was modified by replacing alkylthiols with BSA as protecting agent, which facilitated a strictly aqueous phase synthesis. Due to superior product yield and rapid reduction at room temperature, the aqueous protocol became the foundation for subsequent studies. I extended this approach to produce well-dispersed ˜2nm silver, gold, and platinum nanocrystals. Having demonstrated the feasibility of BSA-functionalized nanocrystals, some potential uses were explored. BSA-functionalized silver nanocrystals were employed in a broader study on the interaction of silver nanocrystals with HIV. BSA-functionalized gold nanocrystals were utilized for in vivo dosage of a contrast enhancing agent to bacteria. BSA-functionalized platinum nanocrystals were studied as hydrogenation catalysts. Since many intriguing uses for protein-functionalized nanocrystals involve incorporation into biosystems, I sought to enhance biocompatibility by using ascorbic acid as reducing agent. Initial experiments revealed elongated and branched nanocrystals. Such structures were not observed in previous synthesis protocols with BSA, so I hypothesized ascorbic acid was driving their formation. To test my assertion, I reduced ionic gold in an aqueous solution of ascorbic acid, thereby discovering a new method

  11. A 1-dodecanethiol-based phase transfer protocol for the highly efficient extraction of noble metal ions from aqueous phase.

    PubMed

    Chen, Dong; Cui, Penglei; Cao, Hongbin; Yang, Jun

    2015-03-01

    A 1-dodecanethiol-based phase-transfer protocol is developed for the extraction of noble metal ions from aqueous solution to a hydrocarbon phase, which calls for first mixing the aqueous metal ion solution with an ethanolic solution of 1-dodecanethiol, and then extracting the coordination compounds formed between noble metal ions and 1-dodecanethiol into a non-polar organic solvent. A number of characterization techniques, including inductively coupled plasma atomic emission spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis demonstrate that this protocol could be applied to extract a wide variety of noble metal ions from water to dichloromethane with an efficiency of >96%, and has high selectivity for the separation of the noble metal ions from other transition metals. It is therefore an attractive alternative for the extraction of noble metals from water, soil, or waste printed circuit boards.

  12. Colorimetric sensor array with unmodified noble metal nanoparticles for naked-eye detection of proteins and bacteria.

    PubMed

    Li, Dongyang; Dong, Yanhua; Li, Bingyu; Wu, Yayan; Wang, Kai; Zhang, Sichun

    2015-11-21

    Herein we report a novel strategy for the detection and identification of proteins using unmodified noble metal nanoparticles. Five gold nanoparticles (AuNPs) and two silver nanoparticles (AgNPs) with different sizes were utilized as sensing elements to create a colorimetric sensor array. In the presence of proteins, the UV-vis absorbance of the noble metal nanoparticles changed due to the interactions between the protein and nanoparticles, producing distinct absorbance response patterns which can be visually detected by the naked eye. The color pattern of the array is a unique "fingerprints" for each protein sample, which can be differentiated by linear discriminant analysis (LDA). Ten different proteins at concentrations of 0.5, 5 and 50 μM have be successfully discriminated. Moreover, the array was also able to discriminate different bacteria at a concentration of 0.05 OD in 200 μL, as well as cancer cells at the level of 5000 cells in 200 μL. This work demonstrates that an unmodified noble metal nanoparticle-based protein detection array has potential for applications in medical diagnostics.

  13. Theory and computation of hot carriers generated by surface plasmon polaritons in noble metals

    NASA Astrophysics Data System (ADS)

    Bernardi, Marco; Mustafa, Jamal; Neaton, Jeffrey B.; Louie, Steven G.

    2015-06-01

    Hot carriers (HC) generated by surface plasmon polaritons (SPPs) in noble metals are promising for application in optoelectronics, plasmonics and renewable energy. However, existing models fail to explain key quantitative details of SPP-to-HC conversion experiments. Here we develop a quantum mechanical framework and apply first-principles calculations to study the energy distribution and scattering processes of HCs generated by SPPs in Au and Ag. We find that the relative positions of the s and d bands of noble metals regulate the energy distribution and mean free path of the HCs, and that the electron-phonon interaction controls HC energy loss and transport. Our results prescribe optimal conditions for HC generation and extraction, and invalidate previously employed free-electron-like models. Our work combines density functional theory, GW and electron-phonon calculations to provide microscopic insight into HC generation and ultrafast dynamics in noble metals.

  14. Theory and computation of hot carriers generated by surface plasmon polaritons in noble metals.

    PubMed

    Bernardi, Marco; Mustafa, Jamal; Neaton, Jeffrey B; Louie, Steven G

    2015-01-01

    Hot carriers (HC) generated by surface plasmon polaritons (SPPs) in noble metals are promising for application in optoelectronics, plasmonics and renewable energy. However, existing models fail to explain key quantitative details of SPP-to-HC conversion experiments. Here we develop a quantum mechanical framework and apply first-principles calculations to study the energy distribution and scattering processes of HCs generated by SPPs in Au and Ag. We find that the relative positions of the s and d bands of noble metals regulate the energy distribution and mean free path of the HCs, and that the electron-phonon interaction controls HC energy loss and transport. Our results prescribe optimal conditions for HC generation and extraction, and invalidate previously employed free-electron-like models. Our work combines density functional theory, GW and electron-phonon calculations to provide microscopic insight into HC generation and ultrafast dynamics in noble metals. PMID:26033445

  15. Functional Application of Noble Metal Nanoparticles In Situ Synthesized on Ramie Fibers.

    PubMed

    Tang, Bin; Yao, Ya; Li, Jingliang; Qin, Si; Zhu, Haijin; Kaur, Jasjeet; Chen, Wu; Sun, Lu; Wang, Xungai

    2015-12-01

    Different functions were imparted to ramie fibers through treatment with noble metal nanoparticles including silver and gold nanoparticles. The in situ synthesis of silver and gold nanoparticles was achieved by heating in the presence of ramie fibers in the corresponding solutions of precursors. The unique optical property of synthesized noble metal nanoparticles, i.e., localized surface plasmon resonance, endowed ramie fibers with bright colors. Color strength (K/S) of fibers increased with heating temperature. Silver nanoparticles were obtained in alkaline solution, while acidic condition was conducive to gold nanoparticles. The optical properties of treated ramie fibers were investigated using UV-vis absorption spectroscopy. Scanning electron microscopy (SEM) was employed to observe the morphologies of silver and gold nanoparticles in situ synthesized on fibers. The ramie fibers treated with noble metal nanoparticles showed remarkable catalytic activity for reduction of 4-nitrophenol (4-NP) by sodium borohydride. Moreover, the silver nanoparticle treatment showed significant antibacterial property on ramie fibers. PMID:26383541

  16. Theory and computation of hot carriers generated by surface plasmon polaritons in noble metals

    PubMed Central

    Bernardi, Marco; Mustafa, Jamal; Neaton, Jeffrey B.; Louie, Steven G.

    2015-01-01

    Hot carriers (HC) generated by surface plasmon polaritons (SPPs) in noble metals are promising for application in optoelectronics, plasmonics and renewable energy. However, existing models fail to explain key quantitative details of SPP-to-HC conversion experiments. Here we develop a quantum mechanical framework and apply first-principles calculations to study the energy distribution and scattering processes of HCs generated by SPPs in Au and Ag. We find that the relative positions of the s and d bands of noble metals regulate the energy distribution and mean free path of the HCs, and that the electron–phonon interaction controls HC energy loss and transport. Our results prescribe optimal conditions for HC generation and extraction, and invalidate previously employed free-electron-like models. Our work combines density functional theory, GW and electron–phonon calculations to provide microscopic insight into HC generation and ultrafast dynamics in noble metals. PMID:26033445

  17. Nano-structured noble metal catalysts based on hexametallate architecture for the reforming of hydrocarbon fuels

    DOEpatents

    Gardner, Todd H.

    2015-09-15

    Nano-structured noble metal catalysts based on hexametallate lattices, of a spinel block type, and which are resistant to carbon deposition and metal sulfide formation are provided. The catalysts are designed for the reforming of hydrocarbon fuels to synthesis gas. The hexametallate lattices are doped with noble metals (Au, Pt, Rh, Ru) which are atomically dispersed as isolated sites throughout the lattice and take the place of hexametallate metal ions such as Cr, Ga, In, and/or Nb. Mirror cations in the crystal lattice are selected from alkali metals, alkaline earth metals, and the lanthanide metals, so as to reduce the acidity of the catalyst crystal lattice and enhance the desorption of carbon deposit forming moieties such as aromatics. The catalysts can be used at temperatures as high as 1000.degree. C. and pressures up to 30 atmospheres. A method for producing these catalysts and applications of their use also is provided.

  18. Vitrification of noble metals containing NCAW simulant with an engineering scale melter (ESM): Campaign report

    SciTech Connect

    Grunewald, W.; Roth, G.; Tobie, W.; Weisenburger, S.; Weiss, K.; Elliott, M.; Eyler, L.L.

    1996-03-01

    ESM has been designed as a 10th-scale model of the DWPF-type melter, currently the reference melter for nitrification of Hanford double shell tankwaste. ESM and related equipment have been integrated to the existing mockup vitrification plant VA-WAK at KfK. On June 2-July 10, 1992, a shakedown test using 2.61 m{sup 3} of NCAW (neutralized current acid waste) simulant without noble metals was performed. On July 11-Aug. 30, 1992, 14.23 m{sup 3} of the same simulant with nominal concentrations of Ru, Rh, and Pd were vitrified. Objective was to investigate the behavior of such a melter with respect to discharge of noble metals with routine glass pouring via glass overflow. Results indicate an accumulation of noble metals in the bottom area of the flat-bottomed ESM. About 65 wt% of the noble metals fed to the melter could be drained out, whereas 35 wt% accumulated in the melter, based on analysis of glass samples from glass pouring stream in to the canisters. After the melter was drained at the end of the campaign through a bottom drain valve, glass samples were taken from the residual bottom layer. The samples had significantly increased noble metals content (factor of 20-45 to target loading). They showed also a significant decrease of the specific electric resistance compared to bulk glass (factor of 10). A decrease of 10- 15% of the resistance between he power electrodes could be seen at the run end, but the total amount of noble metals accumulated was not yet sufficient enough to disturb the Joule heating of the glass tank severely.

  19. Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

    DOEpatents

    Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

    2015-02-24

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

  20. Noble metal-comparable SERS enhancement from semiconducting metal oxides by making oxygen vacancies

    NASA Astrophysics Data System (ADS)

    Cong, Shan; Yuan, Yinyin; Chen, Zhigang; Hou, Junyu; Yang, Mei; Su, Yanli; Zhang, Yongyi; Li, Liang; Li, Qingwen; Geng, Fengxia; Zhao, Zhigang

    2015-07-01

    Surface-enhanced Raman spectroscopy (SERS) represents a very powerful tool for the identification of molecular species, but unfortunately it has been essentially restricted to noble metal supports (Au, Ag and Cu). While the application of semiconductor materials as SERS substrate would enormously widen the range of uses for this technique, the detection sensitivity has been much inferior and the achievable SERS enhancement was rather limited, thereby greatly limiting the practical applications. Here we report the employment of non-stoichiometric tungsten oxide nanostructure, sea urchin-like W18O49 nanowire, as the substrate material, to magnify the substrate-analyte molecule interaction, leading to significant magnifications in Raman spectroscopic signature. The enrichment of surface oxygen vacancy could bring additional enhancements. The detection limit concentration was as low as 10-7 M and the maximum enhancement factor was 3.4 × 105, in the rank of the highest sensitivity, to our best knowledge, among semiconducting materials, even comparable to noble metals without `hot spots'.

  1. A new model describing the metal-support interaction in noble metal catalysts

    SciTech Connect

    Mojet, B.L.; Koningsberger, D.C.; Miller, J.T.; Ramaker, D.E.

    1999-09-10

    The catalytic activity and spectroscopic properties of supported noble metal catalysts are strongly influenced by the acidity/alkalinity of the support but are relatively independent of the metal (Pd or Pt) or the type of support (zeolite LTL or SiO{sub 2}). As the alkalinity of the support increases, the TOF of the metal particles for neopentane hydrogenolysis decreases. At the same time, there is a decrease in the XPS binding energy and a shift from linear to bridge bonded CO in the IR spectra. Analysis of the shape resonance in XANES spectra indicates that in the presence of chemisorbed hydrogen the difference in energy between the Pt-H antibonding orbital and the Fermi level decreases as the alkalinity of the support increases. Based on the results from the IR, XPS, and shape resonance data a new model is proposed in which the interaction between the metal and support leads to a shift in the energy of the metal valence orbitals. The EXAFS structural analysis indicates that the small metal particles are in contact only with the oxide ions of the support. Finally, a new spectroscopic characterization, Atomic XAFS, is presented which provides new insights into the origin of the electronic changes in the metal. As the alkalinity of the support increases, there is decrease in the metal ionization potential. The primary interaction is a Coulomb attraction between metal particle and support oxygen ions, which affects the metal interatomic potential. This model for the metal-support interaction explicitly excludes the need for electron transfer, and it can account for all observed changes in the catalytic, electronic, and structural properties of the supported metal particles induced by support acidity ranging from acidic to neutral to alkaline.

  2. Noble metal nanoparticle@metal oxide core/yolk-shell nanostructures as catalysts: recent progress and perspective

    NASA Astrophysics Data System (ADS)

    Li, Guodong; Tang, Zhiyong

    2014-03-01

    Controllable integration of noble metals (e.g., Au, Ag, Pt, and Pd) and metal oxides (e.g., TiO2, CeO2, and ZrO2) into single nanostructures has attracted immense research interest in heterogeneous catalysis, because they not only combine the properties of both noble metals and metal oxides, but also bring unique collective and synergetic functions in comparison with single-component materials. Among many strategies recently developed, one of the most efficient ways is to encapsulate and protect individual noble metal nanoparticles by a metal oxide shell of a certain thickness to generate the core-shell or yolk-shell structure, which exhibits enhanced catalytic performance compared with conventional supported catalysts. In this review article, we summarize the state-of-the art progress in synthesis and catalytic application of noble metal nanoparticle@metal oxide core/yolk-shell nanostructures. We hope that this review will help the readers to obtain better insight into the design and application of well-defined nanocomposites in both the energy and environmental fields.

  3. 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

  4. 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. 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.

  5. Noble Metal Decoration and Alignment of Carbon Nanotubes in Carboxymethyl Cellulose

    EPA Science Inventory

    A facile microwave (MW) method is described that accomplishes alignment and decoration of noble metals on carbon nanotubes wrapped with carboxymethyl cellulose (CMC). Carbon nanotubes (CNTs) such as single-wall (SWNT), multi-wall (MWNT) and Buckminsterfullerene (C-60) were well ...

  6. Acid Strength and Bifunctional Catalytic Behavior of Alloys Comprised of Noble Metals and Oxophilic Metal Promoters

    SciTech Connect

    Hibbitts, David D.; Tan, Qiaohua; Neurock, Matthew

    2014-06-01

    The promotion of metal catalysts with partially oxidized oxophilic MOx species, such as ReOx-promoted Rh, has been demonstrated to produce Brønsted acid sites that can promote hydrogenolysis of oxygenate intermediates such as those found in biomass-derived species. A wide variety of alloy compositions and structures are examined in this work to investigate strongly acidic promoters by using DFT-calculated deprotonation energies (DPE) as a measure of acid strength. Sites with the highest acid strength had DPE less than 1100 kJ mol-1, similar to DPE values of heteropolyacids or acid-containing zeolites, and were found on alloys composed of an oxophilic metal (such as Re or W) with a noble metal (such as Rh or Pt). NH3 adsorbs more strongly to sites with increasing acid strength and the activation barriers for acid-catalyzed ring opening of a furan ring decrease with increasing acid strength, which was also shown to be stronger for OH acid sites bound to multiple oxophilic metal atoms in a three-fold configuration rather than OH sites adsorbed in an atop configuration on one oxophilic metal, indicating that small MOx clusters may yield sites with the highest acid strength.

  7. Evaluation of {gamma}-MnO{sub 2} as a VOC removal catalyst: Comparison with a noble metal catalyst

    SciTech Connect

    Lahousse, C.; Bernier, A.; Grange, P.; Delmon, B.; Papaefthimiou, P.; Ioannides, T.; Verykios, X.

    1998-08-15

    The performances of two very active catalysts for VOC removal (one metal oxide and one noble metal catalyst, namely {gamma}-MnO{sub 2} and Pt/TiO{sub 2}) are compared. The comparison takes into account not only the activity but also the sensitivity to competition effects between compounds, the influence of water vapor and the stability. The metal oxide catalyst proves to be more active than the supported noble metal one. Moreover, its performance is less affected by interferences between VOC`s than those of the noble metal catalyst. Conversely, the activity of the noble metal appears slightly more stable. Both are affected by water vapor which slightly decreases their efficiency. On the metal oxide catalyst, water shortens the time needed to get a stable catalytic activity.

  8. Noble metal nanodisks epitaxially formed on ZnO nanorods and their effect on photoluminescence

    NASA Astrophysics Data System (ADS)

    Chu, Sheng; Ren, Jingjian; Yan, Dong; Huang, Jian; Liu, Jianlin

    2012-07-01

    Triangular and hexagonal shaped noble metal (Au, Ag, Pt, Pd) nanodisks were synthesized on the top facets of ZnO nanorods via simple deposition-annealing method. Other metals (Ni, Cu, Cr, Pb, Al) only formed irregular shaped nanostructures on ZnO nanorods. The morphology, elemental composition, as well as growth mechanism of the metal nanodisks/ZnO nanorod composite materials were studied. The localized surface plasmon resonant effects from different metal nanodisks on the photoluminescence of ZnO nanorods were investigated. It was demonstrated that the carriers transfer between the metal nanodisks and ZnO can efficiently manipulate the photoluminescence intensities from the nanorods.

  9. Techniques for the quantitative analysis of fission-product noble metals

    SciTech Connect

    Lautensleger, A.W.; Hara, F.T.

    1982-08-01

    Analytical procedures for the determination of ruthenium, rhodium, and palladium in precursor waste, solvent metal, and final glass waste forms have been developed. Two procedures for the analysis of noble metals in the calcine and glass waste forms are described in this report. The first is a fast and simple technique that combines inductively coupled argon plasma atomic emission spectrometry (ICP) and x-ray fluorescence techniques and can only be used on nonradioactive materials. The second procedure is based on a noble metal separation step, followed by an analysis using ICP. This second method is more complicated than the first, but it will work on radioactive materials. Also described is a procedure for the ICP analysis of noble metals in the solvent metal matrix. The only solvent metal addressed in this procedure is lead, but with minor changes the procedure could be applied to any of the solvent metals being considered in the Pacific Northwest Laboratory (PNL) extraction process. A brief explanation of atomic spectroscopy and the ICP analytical process, as well as of certain aspects of ICP performance (interelement spectral line interferences and certain matrix effects) is given.

  10. Core shell hybrids based on noble metal nanoparticles and conjugated polymers: synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Fratoddi, Ilaria; Venditti, Iole; Battocchio, Chiara; Polzonetti, Giovanni; Cametti, Cesare; Russo, Maria Vittoria

    2011-12-01

    Noble metal nanoparticles of different sizes and shapes combined with conjugated functional polymers give rise to advanced core shell hybrids with interesting physical characteristics and potential applications in sensors or cancer therapy. In this paper, a versatile and facile synthesis of core shell systems based on noble metal nanoparticles (AuNPs, AgNPs, PtNPs), coated by copolymers belonging to the class of substituted polyacetylenes has been developed. The polymeric shells containing functionalities such as phenyl, ammonium, or thiol pending groups have been chosen in order to tune hydrophilic and hydrophobic properties and solubility of the target core shell hybrids. The Au, Ag, or Pt nanoparticles coated by poly(dimethylpropargylamonium chloride), or poly(phenylacetylene-co-allylmercaptan). The chemical structure of polymeric shell, size and size distribution and optical properties of hybrids have been assessed. The mean diameter of the metal core has been measured (about 10-30 nm) with polymeric shell of about 2 nm.

  11. Preliminary investigation of a technique to separate fission noble metals from fission product mixtures

    SciTech Connect

    Mellinger, G.B.; Jensen, G.A.

    1982-08-01

    A variation of the gold-ore fire assay technique was examined as a method for recovering Pd, Rh and Ru from fission products. The mixture of fission product oxides is combined with glass-forming chemicals, a metal oxide such as PbO (scavenging agent), and a reducing agent such as charcoal. When this mixture is melted, a metal button is formed which extracts the noble metals. The remainder cools to form a glass for nuclear waste storage. Recovery depended only on reduction of the scavenger oxide to metal. When such reduction was achieved, no difference in noble metal recovery efficiency was found among the scavengers studied (PbO, SnO, CuO, Bi/sub 2/O/sub 3/, Sb/sub 2/O/sub 3/). Not all reducing agents studied, however, were able to reduce all scavenger oxides to metal. Only graphite would reduce SnO and CuO and allow noble metal recovery. The scavenger oxides Sb/sub 2/O/sub 3/, Bi/sub 2/O/sub 3/, and PbO, however, were reduced by all of the reducing agents tested. Similar noble metal recovery was found with each. Lead oxide was found to be the most promising of the potential scavengers. It was reduced by all of the reducing agents tested, and its higher density may facilitate the separation. Use of lead oxide also appeared to have no deterimental effect on the glass quality. Charcoal was identified as the preferred reducing agent. As long as a separable metal phase was formed in the melt, noble metal recovery was not dependent on the amount of reducing agent and scavenger oxide. High glass viscosities inhibited separation of the molten scavenger, while low viscosities allowed volatile loss of RuO/sub 4/. A viscosity of approx. 20 poise at the processing temperature offered a good compromise between scavenger separation and Ru recovery. Glasses in which PbO was used as the scavenging agent were homogeneous in appearance. Resistance to leaching was close to that of certain waste glasses reported in the literature. 12 figures. 7 tables.

  12. Highly selective electrodeposition of sub-10 nm crystalline noble metallic nanorods inside vertically aligned multiwall carbon nanotubes.

    PubMed

    Wang, Xuyang; Wang, Ranran; Wu, Qiang; Zhang, Xiaohua; Yang, Zhaohui; Guo, Jun; Chen, Muzi; Tang, Minghua; Cheng, Yajun; Chu, Haibin

    2016-07-01

    In this paper crystalline noble metallic nanorods including Au and Ag with sub-10 nm diameter, are encapsulated within prealigned and open-ended multiwall carbon nanotubes (MWCNTs) through an electrodeposition method. As the external surface of CNTs has been insulated by the epoxy the CNT channel becomes the only path for the mass transport as well as the nanoreactor for the metal deposition. Highly crystallized Au and Ag2O nanorods parallel to the radial direction of CNTs are confirmed by high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy and x-ray powder diffraction spectroscopy. The Ag2O nanorods are formed by air oxidation on the Ag metals and show a single crystalline structure with (111) planes. The Au nanorods exhibit a complex crystalline structure including twin-crystal and lattice dislocation with (111) and (200) planes. These crystalline noble metallic nanostructures may have important applications for nanocatalysts for fuel cells as well as nanoelectronic and nanophotonic devices. This method is deemed to benefit the precise deposition of other crystalline nanostructures inside CNTs with a small diameter.

  13. Highly selective electrodeposition of sub-10 nm crystalline noble metallic nanorods inside vertically aligned multiwall carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Wang, Xuyang; Wang, Ranran; Wu, Qiang; Zhang, Xiaohua; Yang, Zhaohui; Guo, Jun; Chen, Muzi; Tang, Minghua; Cheng, Yajun; Chu, Haibin

    2016-07-01

    In this paper crystalline noble metallic nanorods including Au and Ag with sub-10 nm diameter, are encapsulated within prealigned and open-ended multiwall carbon nanotubes (MWCNTs) through an electrodeposition method. As the external surface of CNTs has been insulated by the epoxy the CNT channel becomes the only path for the mass transport as well as the nanoreactor for the metal deposition. Highly crystallized Au and Ag2O nanorods parallel to the radial direction of CNTs are confirmed by high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy and x-ray powder diffraction spectroscopy. The Ag2O nanorods are formed by air oxidation on the Ag metals and show a single crystalline structure with (111) planes. The Au nanorods exhibit a complex crystalline structure including twin-crystal and lattice dislocation with (111) and (200) planes. These crystalline noble metallic nanostructures may have important applications for nanocatalysts for fuel cells as well as nanoelectronic and nanophotonic devices. This method is deemed to benefit the precise deposition of other crystalline nanostructures inside CNTs with a small diameter.

  14. Cálculo del esfuerzo ideal de metales nobles mediante primeros principios en la dirección <100>

    NASA Astrophysics Data System (ADS)

    Bautista-Hernández, A.; López-Fuentes, M.; Pacheco-Espejel, V.; Rivas-Silva, J. F.

    2005-04-01

    We present calculations of the ideal strength on the < 100 > direction for noble metals (Cu, Ag and Au), by means of first principles calculations. First, we obtain the structural parameters (cell parameters, bulk modulus) for each studied metal. We deform on the < 100 > direction calculating the total energy and the stress tensor through the Hellman-Feynman theorem, by the relaxation of the unit cell in the perpendicular directions to the deformation one. The calculated cell constants differ 1.3 % from experimental data. The maximum ideal strength are 29.6, 17 and 19 GPa for Cu, Ag and Au respectively. Meanwhile, the calculated elastic modulus are 106 (Cu), 71 (Ag), and 45 GPa (Au) and are in agreement with the experimental values for polycrystalline samples. The values of maximum strength are explained by the optimum volume values due to the atomic radius size for each element.

  15. Process for making a noble metal on tin oxide catalyst

    NASA Technical Reports Server (NTRS)

    Upchurch, Billy T. (Inventor); Davis, Patricia (Inventor); Miller, Irvin M. (Inventor)

    1989-01-01

    A quantity of reagent grade tin metal or compound, chloride-free, and high-surface-area silica spheres are placed in deionized water, followed by deaerating the mixture by boiling and adding an oxidizing agent, such as nitric acid. The nitric acid oxidizes the tin to metastannic acid which coats the spheres because the acid is absorbed on the substrate. The metastannic acid becomes tin oxide upon drying and calcining. The tin-oxide coated silica spheres are then placed in water and boiled. A chloride-free precious metal compound in aqueous solution is then added to the mixture containing the spheres, and the precious metal compound is reduced to a precious metal by use of a suitable reducing agent such as formic acid. Very beneficial results were obtained using the precious metal compound tetraammine platinum(II) hydroxide.

  16. H2-SCR at low temperatures on noble metal supported catalysts

    NASA Astrophysics Data System (ADS)

    Mihet, Maria; Lazar, Mihaela Diana; Almasan, V.; Mirel, V.

    2012-02-01

    The selective catalytic reduction of NO using hydrogen as reducing agent (H2-SCR) is investigated on alumina supported noble metal catalysts at low temperatures (<350°C). Three noble metal supported catalysts (Pt/Al2O3, Pd/Al2O3, and Rh/Al2O3 with 1 wt.% metal loading), prepared by the incipient wetness impregnation method, were characterized by N2 adsorption-desorption at -196°C, NO-TPD, and H2-TPD. Catalytic activity tests of the investigated noble metal catalysts were performed under plug flow conditions, using a feed stream of 0.5% NO, 0.60% H2 and Ar as balance gas, at temperatures below 350°C, and a GHSV of 4500 h-1. Pt/Al2O3 and Pd/Al2O3 proved to be the most active catalysts for H2-SCR in terms of NO conversion, while the Pd catalyst showed the best N2 selectivity and N2 yield. NO conversion > 95% and N2 selectivity above 80% were obtained for each catalyst at 200°C.

  17. Noble-Metal-Free Materials for Surface-Enhanced Raman Spectroscopy Detection.

    PubMed

    Tan, Xianjun; Melkersson, Jenny; Wu, Shiqun; Wang, Lingzhi; Zhang, Jinlong

    2016-09-01

    Surface-enhanced Raman spectroscopy (SERS) is an attractive tool for the sensing of molecules in the fields of chemical and biochemical analysis as it enables the sensitive detection of molecular fingerprint information even at the single-molecule level. In addition to traditional coinage metals in SERS analysis, recent research on noble-metal-free materials has also yielded highly sensitive SERS activity. This Minireview presents the recent development of noble-metal-free materials as SERS substrates and their potential applications, especially semiconductors and emerging graphene-based nanostructures. Rather than providing an exhaustive review of this field, possible contributions from semiconductor substrates, characteristics of graphene enhanced Raman scattering, as well as effect factors such as surface plasmon resonance, structure and defects of the nanostructures that are considered essential for SERS activity are emphasized. The intention is to illustrate, through these examples, that the promise of noble-metal-free materials for enhancing detection sensitivity can further fuel the development of SERS-related applications. PMID:27191682

  18. Electrochemical synthesis of elongated noble metal nanoparticles, such as nanowires and nanorods, on high-surface area carbon supports

    DOEpatents

    Adzic, Radoslav; Blyznakov, Stoyan; Vukmirovic, Miomir

    2015-08-04

    Elongated noble-metal nanoparticles and methods for their manufacture are disclosed. The method involves the formation of a plurality of elongated noble-metal nanoparticles by electrochemical deposition of the noble metal on a high surface area carbon support, such as carbon nanoparticles. Prior to electrochemical deposition, the carbon support may be functionalized by oxidation, thus making the manufacturing process simple and cost-effective. The generated elongated nanoparticles are covalently bound to the carbon support and can be used directly in electrocatalysis. The process provides elongated noble-metal nanoparticles with high catalytic activities and improved durability in combination with high catalyst utilization since the nanoparticles are deposited and covalently bound to the carbon support in their final position and will not change in forming an electrode assembly.

  19. The sol-gel entrapment of noble metals in hybrid silicas: a molecular insight

    PubMed Central

    2013-01-01

    Background Why are metal nanoparticles sol-gel entrapped in ORMOSIL so active and stable? In other words, why ORMOSIL-entrapped metal nanoparticles are more active and selective than many heterogenized counterparts, including silica-entrapped noble metals? Results Unveiling specific interactions between MNPs and the molecular structure of ORMOSIL, this work investigates subtle structural aspects through DRIFT spectroscopy. Conclusions The results point to interactions between entrapped Pd and Pt nanocrystallites with the organosilica sol-gel cages similar to those taking place in enzymes. PMID:24079552

  20. Biphasic catalysis using amphiphilic polyphenols-chelated noble metals as highly active and selective catalysts

    PubMed Central

    Mao, Hui; Yu, Hong; Chen, Jing; Liao, Xuepin

    2013-01-01

    In the field of catalysis, it is highly desired to develop novel catalysts that combine the advantages of both homogeneous and heterogeneous catalysts. Here we disclose that the use of plant pholyphenol as amphiphilic large molecule ligand/stabilizer allows for the preparation of noble metal complex and noble metal nanoparticle catalysts. These catalysts are found to be highly selective and active in aqueous-organic biphasic catalysis of cinnamaldehyde and quinoline, and can be reused at least 3 times without significant loss of activity. Moreover, the catalytic activity and reusability of the catalysts can be rationally controlled by simply adjusting the content of polyphenols in the catalysts. Our strategy may be extended to design a wide range of aqueous-organic biphasic catalysis system. PMID:23863916

  1. Protein-protected luminescent noble metal quantum clusters: an emerging trend in atomic cluster nanoscience

    PubMed Central

    Xavier, Paulrajpillai Lourdu; Chaudhari, Kamalesh; Baksi, Ananya; Pradeep, Thalappil

    2012-01-01

    Noble metal quantum clusters (NMQCs) are the missing link between isolated noble metal atoms and nanoparticles. NMQCs are sub-nanometer core sized clusters composed of a group of atoms, most often luminescent in the visible region, and possess intriguing photo-physical and chemical properties. A trend is observed in the use of ligands, ranging from phosphines to functional proteins, for the synthesis of NMQCs in the liquid phase. In this review, we briefly overview recent advancements in the synthesis of protein protected NMQCs with special emphasis on their structural and photo-physical properties. In view of the protein protection, coupled with direct synthesis and easy functionalization, this hybrid QC-protein system is expected to have numerous optical and bioimaging applications in the future, pointers in this direction are visible in the literature. PMID:22312454

  2. Photosensitized Reduction of Carbon Dioxide in Solution Using Noble-Metal Clusters for Electron Transfer

    NASA Astrophysics Data System (ADS)

    Toshima, Naoki; Yamaji, Yumi; Teranishi, Toshiharu; Yonezawa, Tetsu

    1995-03-01

    Carbon dioxide was reduced to methane by visible-light irradiation of a solution composed of tris(bipyridine)ruthenium(III) as photosensitizer, ethylenediaminetetraacetic acid disodium salt as sacrificial reagent, methyl viologen as electron relay, and a colloidal dispersion of polymer-protected noble-metal clusters, prepared by alcohol-reduction, as catalyst. Among the noble-metal clusters examined, Pt clusters showed the highest activity for the formation of methane as well as hydrogen. In order to improve the activity, oxidized clusters and bimetallic clusters were also applied. For example, the CH4 yield in 3-h irradiation increased from 51 x 10-3 μmol with unoxidized Pt clusters to 72 x 10-3 μmol with partially oxidized ones. In the case of Pt/Ru bimetalic systems, the improvement of the catalytic activity by air treatment was much greater than in case of monometallic clusters.

  3. Two types of noble metal mineralization in the Kaalamo massif (Karelia)

    NASA Astrophysics Data System (ADS)

    Ivashchenko, V. I.; Ruchyev, A. M.; Golubev, A. I.

    2016-05-01

    Noble metal mineralization of the syngenetic (Southern Kaalamo) and epigenetic (Surisuo) types are defined in the Kaalamo massif. The ƩPt, Pd, Au content is as high as 0.9-1.1 g/t. Syngenetic mineralization started at the late magmatic stage (at around 800°C) gradually evolving to cease during the hydrothermal-metasomatic stage (<271°C). Epigenetic mineralization was formed at temperatures ranging from 500 to <230°C in zones of intense shear deformations and low-temperature metasomatosis during the collisional stage of the Svecofennian tectono-magmatic cycle (approximately 1.85 Ga ago). Taking into consideration the geological position of the Kaalamo massif in the Raakhe-Ladoga metallogenic zone with widely developed intense shear dislocations, the epigenetic mineralization type seems to be more promising with respect to noble metals.

  4. Reactive Gas Environment Induced Structural Modification of Noble-Transition Metal Alloy Nanoparticles

    NASA Astrophysics Data System (ADS)

    Petkov, V.; Yang, L.; Yin, J.; Loukrakpam, R.; Shan, S.; Wanjala, B.; Luo, J.; Chapman, K. W.; Zhong, C. J.

    2012-09-01

    Noble-transition metal (noble=Pt,Au; transition=Co,Ni,Cu) alloy particles with sizes of about 5 nm have been studied by in situ high-energy x-ray diffraction while subjected to oxidizing (O2) and reducing (H2) gas atmospheres at elevated temperatures. The different gas atmospheres do not affect substantially the random alloy, face-centered-cubic structure type of the particles but do affect the way the metal atoms pack together. In an O2 atmosphere, atoms get extra separated from each other, whereas, in an H2 atmosphere, they come closer together. The effect is substantial, amounting to 0.1 Å difference in the first neighbor atomic distances, and concurs with a dramatic change of the particle catalytic properties. It is argued that such reactive gas induced “expansion shrinking” is a common phenomenon that may be employed for the engineering of “smart” nanoparticles responding advantageously to envisaged gas environments.

  5. Decoration of diatom biosilica with noble metal and semiconductor nanoparticles (<10 nm): assembly, characterization, and applications.

    PubMed

    Jantschke, Anne; Herrmann, Anne-Kristin; Lesnyak, Vladimir; Eychmüller, Alexander; Brunner, Eike

    2012-01-01

    Diatom-templated noble metal (Ag, Pt, Au) and semiconductor (CdTe) nanoparticle arrays were synthesized by the attachment of prefabricated nanoparticles of defined size. Two different attachment techniques-layer-by-layer deposition and covalent linking-could successfully be applied. The synthesized arrays were shown to be useful for surface-enhanced Raman spectroscopy (SERS) of components, for catalysis, and for improved image quality in scanning electron microscopy (SEM).

  6. Stability of noble metal catalysts for the hydrogen-oxygen reaction.

    NASA Technical Reports Server (NTRS)

    Armstrong, W. E.; Jennings, T. J.; Voge, H. H.

    1972-01-01

    Stability of various supported noble metal catalysts for initiation of the hydrogen-oxygen reaction was tested by means of steam-hydrogen treatment at 1000-1200 C followed by a simple activity test. Many catalysts were stable to 1100 C, but all lost some activity at 1200 C. The most active with very good stability was an iridium/alumina catalyst of high iridium content.

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

    SciTech Connect

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

    2008-07-01

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

  8. Measuring and Predicting Fission Product Noble Metals in SRS HLW Sludges

    SciTech Connect

    Bibler, N

    2005-04-05

    The noble metals Ru, Rh, Pd, and Ag were produced in the Savannah River Site (SRS) reactors as products of the fission of U-235. Consequently they are in the High Level Waste (HLW) sludges that are currently being immobilized into a borosilicate glass in the Defense Waste Processing Facility (DWPF). The noble metals are a concern in the DWPF because they catalyze the decomposition of formic acid used in the process to produce the flammable gas hydrogen. As the concentration of these noble metals in the sludge increases, more hydrogen will be produced when this sludge is processed. In the SRS Tank Farm it takes approximately two years to prepare a sludge batch for processing in the DWPF. This length of time is necessary to mix the appropriate sludges, blend them to form a sludge batch and then wash it to enable processing in the DWPF. This means that the exact composition of a sludge batch is not known for {approx}two years. During this time, studies with simulated nonradioactive sludges must be performed to determine the desired DWPF processing parameters for the new sludge batch. Consequently, prediction of the noble metal concentrations is desirable to prepare appropriate simulated sludges for studies of the DWPF process for that sludge batch. These studies give a measure of the amount of hydrogen that will be produced when that sludge batch is processed. This report describes in detail the measurement of these noble metal concentrations in sludges and a way to predict their concentrations from an estimate of the lanthanum concentration in the sludge. Results for two sludges are presented in this report. These are Sludge Batch 3 (SB3) currently being processed by the DWPF and a sample of unwashed sludge from Tank 11 that will be part of Sludge Batch 4. The concentrations of the noble metals in HLW sludges are measured by using mass spectroscopy to determine concentrations of the isotopes that comprise each noble metal. For example, the noble metal Ru is comprised

  9. Rice straw modified by click reaction for selective extraction of noble metal ions.

    PubMed

    Wang, Jingjing; Wei, Jun; Li, Juan

    2015-02-01

    Rice straw was modified by azide-alkyne click reaction in order to realize selective extraction of noble metal ions. The ability of the modified straw to adsorb Pd(2+) and Pt(4+) was assessed using a batch adsorption technique. It was found that the sorption equilibrium could be reached within 1h and the adsorption capacity increased with temperature for both Pd(2+) and Pt(4+). The maximum sorption capacities for Pd(2+) and Pt(4+) were respectively attained in 1.0 and 0.1 mol/L HCl. The modified straw showed excellent selectivity for noble metal ions in comparison to the pristine straw. In addition, the modified straw was examined as a column packing material for extraction of noble metal ions. It was indicated that 1.0 mL/min was the best flow rate for Pd(2+) and Pt(4+). The modified straw could be repeatedly used for 10 times without any significant loss in the initial binding affinity.

  10. The role of van der Waals interactions in the adsorption of noble gases on metal surfaces

    SciTech Connect

    Chen, De-Li; Al-Saidi, W A; Johnson, J Karl

    2012-10-03

    Adsorption of noble gases on metal surfaces is determined by weak interactions. We applied two versions of the nonlocal van der Waals density functional (vdW-DF) to compute adsorption energies of Ar, Kr, and Xe on Pt(111), Pd(111), Cu(111), and Cu(110) metal surfaces. We have compared our results with data obtained using other density functional approaches, including the semiempirical vdW corrected DFT-D2. The vdW-DF results show considerable improvements in the description of adsorption energies and equilibrium distances over other DFTbased methods, giving good agreement with experiments. We have also calculated perpendicular vibrational energies for noble gases on the metal surfaces using vdWDF data and found excellent agreement with available experimental results. Our vdW-DF calculations show that adsorption of noble gases on low-coordination sites is energetically favored over high-coordination sites, but only by a few meV. Analysis of the 2-dimensional potential energy surface shows that the high-coordination sites are local maxima on the 2-dimensional potential energy surface and therefore unlikely to be observed in experiments, which provides an explanation of the experimental observations. The DFT-D2 approach with the standard parameterization was found to overestimate the dispersion interactions, and to give the wrong adsorption site preference for four of the nine systems we studied.

  11. Noninvasive noble metal nanoparticle arrays for surface-enhanced Raman spectroscopy of proteins

    NASA Astrophysics Data System (ADS)

    Inya-Agha, Obianuju; Forster, Robert J.; Keyes, Tia E.

    2007-02-01

    Noble metal nanoparticles arrays are well established substrates for surface enhanced Raman spectroscopy (SERS). Their ability to enhance optical fields is based on the interaction of their surface valence electrons with incident electromagnetic radiation. In the array configuration, noble metal nanoparticles have been used to produce SER spectral enhancements of up to 10 8 orders of magnitude, making them useful for the trace analysis of physiologically relevant analytes such as proteins and peptides. Electrostatic interactions between proteins and metal surfaces result in the preferential adsorption of positively charged protein domains onto metal surfaces. This preferential interaction has the effect of disrupting the native conformation of the protein fold, with a concomitant loss of protein function. A major historic advantage of Raman microspectroscopy has been is its non-invasive nature; protein denaturation on the metal surfaces required for SER spectroscopy renders it a much more invasive technique. Further, part of the analytical power of Raman spectroscopy lies in its use as a secondary conformation probe. The protein structural loss which occurs on the metal surface results in secondary conformation readings which are not true to the actual native state of the analyte. This work presents a method for chemical fabrication of noble metal SERS arrays with surface immobilized layers which can protect protein native conformation without excessively mitigating the electromagnetic enhancements of spectra. Peptide analytes are used as model systems for proteins. Raman spectra of alpha lactalbumin on surfaces and when immobilized on these novel arrays are compared. We discuss the ability of the surface layer to protect protein structure whilst improving signal intensity.

  12. Noble metal (Pd, Ru, Rh, Pt, Au, Ag) doped graphene hybrids for electrocatalysis

    NASA Astrophysics Data System (ADS)

    Giovanni, Marcella; Poh, Hwee Ling; Ambrosi, Adriano; Zhao, Guanjia; Sofer, Zdeněk; Šaněk, Filip; Khezri, Bahareh; Webster, Richard D.; Pumera, Martin

    2012-07-01

    Metal decorated graphene materials are highly important for catalysis. In this work, noble metal doped-graphene hybrids were prepared by a simple and scalable method. The thermal reductions of metal doped-graphite oxide precursors were carried out in nitrogen and hydrogen atmospheres and the effects of these atmospheres as well as the metal components on the characteristics and catalytic capabilities of the hybrid materials were studied. The hybrids exfoliated in nitrogen atmosphere contained a higher amount of oxygen-containing groups and lower density of defects on their surfaces than hybrids exfoliated in hydrogen atmosphere. The metals significantly affected the electrochemical behavior and catalysis of compounds that are important in energy production and storage and in electrochemical sensing. Research in the field of energy storage and production, electrochemical sensing and biosensing as well as biomedical devices can take advantage of the properties and catalytic capabilities of the metal doped graphene hybrids.

  13. Noble Metal Immersion Spectroscopy of Silica Alcogels and Aerogels

    NASA Technical Reports Server (NTRS)

    Smith, David D.; Sibille, Laurent; Cronise, Raymond J.; Noever, David A.

    1998-01-01

    We have fabricated aerogels containing gold and silver nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

  14. 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

  15. Self-assembled biomimetic nanoreactors II: Noble metal active centers

    NASA Astrophysics Data System (ADS)

    McTaggart, Matt; Malardier-Jugroot, Cecile; Jugroot, Manish

    2015-09-01

    The structure and stability of polymer-metal nanoreactors is detailed, including a complete characterization of the first successful synthesis of stable, dispersible, atomically thin gold nanosheets. Further developments in the synthesis of monodisperse, ∼2.5 nm platinum nanoclusters in aqueous solution and ambient conditions are described and pH stability of the composite material is established. The facile nanoreactor synthesis, environmentally friendly reaction conditions, and structural stability makes these biomimetic systems attractive for applications ranging from chemical detoxification to nanoelectronics.

  16. Unveiling nickelocene bonding to a noble metal surface

    NASA Astrophysics Data System (ADS)

    Bachellier, N.; Ormaza, M.; Faraggi, M.; Verlhac, B.; Vérot, M.; Le Bahers, T.; Bocquet, M.-L.; Limot, L.

    2016-05-01

    The manipulation of a molecular spin state in low-dimensional materials is central to molecular spintronics. The designs of hybrid devices incorporating magnetic metallocenes are very promising in this regard, but are hampered by the lack of data regarding their interaction with a metal. Here, we combine low-temperature scanning tunneling microscopy and density functional theory calculations to investigate a magnetic metallocene at the single-molecule level—nickelocene. We demonstrate that the chemical and electronic structures of nickelocene are preserved upon adsorption on a copper surface. Several bonding configurations to the surface are identified, ranging from the isolated molecule to molecular layers governed by van der Waals interactions.

  17. Air- and water-resistant noble metal coated ferromagnetic cobalt nanorods.

    PubMed

    Lentijo-Mozo, Sergio; Tan, Reasmey P; Garcia-Marcelot, Cécile; Altantzis, Thomas; Fazzini, Pier-Francesco; Hungria, Teresa; Cormary, Benoit; Gallagher, James R; Miller, Jeffrey T; Martinez, Herve; Schrittwieser, Stefan; Schotter, Joerg; Respaud, Marc; Bals, Sara; Van Tendeloo, Gustaaf; Gatel, Christophe; Soulantica, Katerina

    2015-03-24

    Cobalt nanorods possess ideal magnetic properties for applications requiring magnetically hard nanoparticles. However, their exploitation is undermined by their sensitivity toward oxygen and water, which deteriorates their magnetic properties. The development of a continuous metal shell inert to oxidation could render them stable, opening perspectives not only for already identified applications but also for uses in which contact with air and/or aqueous media is inevitable. However, the direct growth of a conformal noble metal shell on magnetic metals is a challenge. Here, we show that prior treatment of Co nanorods with a tin coordination compound is the crucial step that enables the subsequent growth of a continuous noble metal shell on their surface, rendering them air- and water-resistant, while conserving the monocrystallity, metallicity and the magnetic properties of the Co core. Thus, the as-synthesized core-shell ferromagnetic nanorods combine high magnetization and strong uniaxial magnetic anisotropy, even after exposure to air and water, and hold promise for successful implementation in in vitro biodiagnostics requiring probes of high magnetization and anisotropic shape.

  18. Bioactivity of noble metal nanoparticles decorated with biopolymers and their application in drug delivery.

    PubMed

    Rai, Mahendra; Ingle, Avinash P; Gupta, Indarchand; Brandelli, Adriano

    2015-12-30

    The unique properties of nanomaterials can be applied to solve different problems including new ways of drug delivery. Noble metal nanoparticles are most promising because they have been used for medicinal purposes since ancient time. It is evident from the past studies that the metallic nanoparticles are much more effective against various microorganisms when compared to their conventional counterparts. However, decoration of such nanoparticles with biomaterials add more advantages to their antimicrobial activity. Decoration of metal nanoparticles with biopolymers is a quite new area of research. Studies performed hitherto shown that nanoparticles of noble metals like silver, gold and platinum demonstrated better antibacterial, antifungal and antiviral activities when conjugated with biopolymers. The development of such technology has potential to develop materials that are more effective in the field of health science. Considering the importance and uniqueness of this concept, the present review aims to discuss the use of biopolymer-decorated metal nanoparticles for combating various diseases caused by microbial pathogens. Moreover, the nanotoxicity aspect has also been discussed. PMID:26520406

  19. Bioactivity of noble metal nanoparticles decorated with biopolymers and their application in drug delivery.

    PubMed

    Rai, Mahendra; Ingle, Avinash P; Gupta, Indarchand; Brandelli, Adriano

    2015-12-30

    The unique properties of nanomaterials can be applied to solve different problems including new ways of drug delivery. Noble metal nanoparticles are most promising because they have been used for medicinal purposes since ancient time. It is evident from the past studies that the metallic nanoparticles are much more effective against various microorganisms when compared to their conventional counterparts. However, decoration of such nanoparticles with biomaterials add more advantages to their antimicrobial activity. Decoration of metal nanoparticles with biopolymers is a quite new area of research. Studies performed hitherto shown that nanoparticles of noble metals like silver, gold and platinum demonstrated better antibacterial, antifungal and antiviral activities when conjugated with biopolymers. The development of such technology has potential to develop materials that are more effective in the field of health science. Considering the importance and uniqueness of this concept, the present review aims to discuss the use of biopolymer-decorated metal nanoparticles for combating various diseases caused by microbial pathogens. Moreover, the nanotoxicity aspect has also been discussed.

  20. Egg derived nitrogen-self-doped carbon/carbon nanotube hybrids as noble-metal-free catalysts for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Zhang, Jian; Wu, Siyu; Chen, Xu; Pan, Mu; Mu, Shichun

    2014-12-01

    Currently, the development of nitrogen (N) doped carbon based non-precious metal ORR catalysts has become one of the most attractive topics in low temperature fuel cells. Here, we demonstrate a green synthesis route of N-self-doped carbon materials by using eggs as N sources combining with iron sources and multi-walled carbon nanotubes (CE-Fe-MWNT). After carbonized, such hybrid materials possess an outstanding electrocatalytic activity towards ORR comparable to the commercial Pt/C catalyst in alkaline media, and both superior stability and fuel (methanol and CO) tolerance than the commercial Pt/C catalyst, which provide a promising alternative to noble metal catalysts by using abundant natural biological resources.

  1. Baseline milestone HWVP-87-V110202F: Preliminary evaluation of noble metal behavior in the Hanford waste vitrification plant reference glass HW-39

    SciTech Connect

    Geldart, R.W.; Bates, S.O.; Jette, S.J.

    1996-03-01

    The precipitation and aggregation of ruthenium (Ru), rhodium (RLh) and palladium (Pd) in the Hanford Waste Vitrification Plant (HWVP) low chromium reference glass HLW-39 were investigated to determine if there is a potential for formation of a noble metal sludge in the HWVP ceramic melter. Significant noble metal accumulations on the floor of the melter will result in the electrical shorting of the electrodes and premature failure of the melter. The purpose of this study was to obtain preliminary information on the characteristics of noble metals in a simulated HWVP glass. Following a preliminary literature view to obtain information concerning the noble metals behavior, a number of variability studies were initiated. The effects of glass redox conditions, melt temperature, melting time and noble metal concentration on the phase characteristics of these noble metals were examined.

  2. Thermodynamic aspects of dehydrogenation reactions on noble metal surfaces.

    PubMed

    Svane, K L; Hammer, B

    2014-11-01

    The reaction free energy for dehydrogenation of phenol, aniline, thiophenol, benzoic acid, and 1,4-benzenediol on the close packed copper, silver, and gold surfaces has been studied by density functional theory calculations. Dehydrogenation of thiophenol is found to be favourable on all three surfaces while aniline does not dehydrogenate on any of them. For phenol, benzenediol and benzoic acid dehydrogenation is favourable on copper and silver only, following the general trend of an increasing reaction free energy when going form gold to silver to copper. This trend can be correlated with the changes in bond lengths within the molecule upon dehydrogenation. While copper is able to replace hydrogen, leaving small changes in the bond lengths of the aromatic ring, the metal-molecule bond is weaker for silver and gold, resulting in a partial loss of aromaticity. This difference in bond strength leads to pronounced differences in adsorption geometries upon multiple dehydrogenations.

  3. Thermodynamic aspects of dehydrogenation reactions on noble metal surfaces.

    PubMed

    Svane, K L; Hammer, B

    2014-11-01

    The reaction free energy for dehydrogenation of phenol, aniline, thiophenol, benzoic acid, and 1,4-benzenediol on the close packed copper, silver, and gold surfaces has been studied by density functional theory calculations. Dehydrogenation of thiophenol is found to be favourable on all three surfaces while aniline does not dehydrogenate on any of them. For phenol, benzenediol and benzoic acid dehydrogenation is favourable on copper and silver only, following the general trend of an increasing reaction free energy when going form gold to silver to copper. This trend can be correlated with the changes in bond lengths within the molecule upon dehydrogenation. While copper is able to replace hydrogen, leaving small changes in the bond lengths of the aromatic ring, the metal-molecule bond is weaker for silver and gold, resulting in a partial loss of aromaticity. This difference in bond strength leads to pronounced differences in adsorption geometries upon multiple dehydrogenations. PMID:25381535

  4. Ab Initio Electronic Relaxation Times and Transport in Noble Metals

    NASA Astrophysics Data System (ADS)

    Mustafa, Jamal I.; Bernardi, Marco; Neaton, Jeffrey B.; Louie, Steven G.

    Relaxation times employed to study electron transport in metals are typically assumed to be constants and obtained empirically using the Drude model. Here, we employ ab initio calculations to compute the electron-phonon relaxation times of Cu, Ag, and Au, and find that they vary significantly on the Fermi surface, spanning ~15 -45 fs. We compute room temperature resistivities in excellent agreement with experiment by combining GW bandstructures, Wannier-interpolated band velocities, and ab initio relaxation times. Our calculations are compared to other approximations used for the relaxation times. Additionally, an importance sampling scheme is introduced to speed up the convergence of resistivity and transport calculations by sampling directly points on the Fermi surface. This work was supported by NSF Grant No. DMR15-1508412 and U.S. DOE under Contract No. DE-AC02-05CH11231. Computational resources have been provided by DOE at LBNL's NERSC facility.

  5. Thermodynamic aspects of dehydrogenation reactions on noble metal surfaces

    SciTech Connect

    Svane, K. L. Hammer, B.

    2014-11-07

    The reaction free energy for dehydrogenation of phenol, aniline, thiophenol, benzoic acid, and 1,4-benzenediol on the close packed copper, silver, and gold surfaces has been studied by density functional theory calculations. Dehydrogenation of thiophenol is found to be favourable on all three surfaces while aniline does not dehydrogenate on any of them. For phenol, benzenediol and benzoic acid dehydrogenation is favourable on copper and silver only, following the general trend of an increasing reaction free energy when going form gold to silver to copper. This trend can be correlated with the changes in bond lengths within the molecule upon dehydrogenation. While copper is able to replace hydrogen, leaving small changes in the bond lengths of the aromatic ring, the metal-molecule bond is weaker for silver and gold, resulting in a partial loss of aromaticity. This difference in bond strength leads to pronounced differences in adsorption geometries upon multiple dehydrogenations.

  6. Noble metals on the nanoscale: optical and photothermal properties and some applications in imaging, sensing, biology, and medicine.

    PubMed

    Jain, Prashant K; Huang, Xiaohua; El-Sayed, Ivan H; El-Sayed, Mostafa A

    2008-12-01

    result of field coupling. A universal scaling model, relating the plasmon resonance frequency to the interparticle distance in terms of the particle size, becomes potentially useful for measuring nanoscale distances (and their changes) in biological systems. The strong plasmon absorption and photothermal conversion of gold nanoparticles has been exploited in cancer therapy through the selective localized photothermal heating of cancer cells. For nanorods or nanoshells, the LSPR can be tuned to the near-infrared region, making it possible to perform in vivo imaging and therapy. The examples of the applications of noble metal nanostructures provided herein can be readily generalized to other areas of biology and medicine because plasmonic nanomaterials exhibit great range, versatility, and systematic tunability of their optical attributes. PMID:18447366

  7. Noble metals on the nanoscale: optical and photothermal properties and some applications in imaging, sensing, biology, and medicine.

    PubMed

    Jain, Prashant K; Huang, Xiaohua; El-Sayed, Ivan H; El-Sayed, Mostafa A

    2008-12-01

    result of field coupling. A universal scaling model, relating the plasmon resonance frequency to the interparticle distance in terms of the particle size, becomes potentially useful for measuring nanoscale distances (and their changes) in biological systems. The strong plasmon absorption and photothermal conversion of gold nanoparticles has been exploited in cancer therapy through the selective localized photothermal heating of cancer cells. For nanorods or nanoshells, the LSPR can be tuned to the near-infrared region, making it possible to perform in vivo imaging and therapy. The examples of the applications of noble metal nanostructures provided herein can be readily generalized to other areas of biology and medicine because plasmonic nanomaterials exhibit great range, versatility, and systematic tunability of their optical attributes.

  8. A general phase transfer protocol for synthesizing alkylamine-stabilized nanoparticles of noble metals.

    PubMed

    Yang, J; Lee, Jim Yang; Too, Heng-Phon

    2007-04-01

    The ethanol-mediated phase transfer protocol was extended herein to prepare alkylamine-stabilized nanoparticles of several noble metals by transferring them from aqueous environment into toluene. This method relies on the use of ethanol as a mediator to provide and maintain adequate contact between dodecylamine and metal nanoparticles during the transfer process and involves first mixing the metal hydrosols and an ethanol solution of dodecylamine and then extracting the dodecylamine-stabilized metal nanoparticles into toluene. Alkylamine-stabilized Ag, Pd, Rh, Ir and Os nanoparticles with 7.09, 3.45, 6.89, 2.42 and 4.52 nm in diameter, respectively, could be prepared this way. The self-assembly of dodecylamine-stabilized Ag and Rh nanoparticles was also detected by transmission electron microscopy (TEM).

  9. Solar noble gases revealed by closed system stepped etching of a metal separate from Fayetteville

    NASA Technical Reports Server (NTRS)

    Murer, CH.; Baur, H.; Signer, P.; Wieler, R.

    1993-01-01

    Solar He, Ne, and Ar in a Fe-Ni separate from the chondrite Fayetteville are analyzed by closed system stepped oxidation. We report here data of the first 15 steps comprising 55 percent of the total solar gases. He-4/Ar-36 and Ne-20/Ar-36 are quite constant at values about 20 percent below those of present day solar wind (SWC). In this, Fe-Ni differs from lunar ilmenites where He-4/Ar-36 and Ne-20/Ar-36 in the first steps are several times below SWC. Thus, metal retains SW-noble gases even better than ilmenite, almost without element fractionation. Nevertheless, the isotopic composition of SW-He, -Ne, and -Ar in the first steps of the metal sample are identical to those found in a recently irradiated lunar ilmenite, indicating that ilmenites and chondritic metal both contain isotopically unfractionated SW noble gases. A preliminary analysis of a smaller Fayetteville metal separate shows Ne from solar energetic particles (SEP-Ne) with Ne-20/Ne-22 less than or equal to 11.5.

  10. Defense by-products production and utilization program: noble metal recovery screening experiments

    SciTech Connect

    Hazelton, R.F.; Jensen, G.A.; Raney, P.J.

    1986-03-01

    Isotopes of the platinum metals (rutheium, rhodium, and palladium) are produced during uranium fuel fission in nuclear reactors. The strategic values of these noble metals warrant considering their recovery from spent fuel should the spent fuel be processed after reactor discharge. A program to evaluate methods for ruthenium, rhodium, and palladium recovery from spent fuel reprocessing liquids was conducted at Pacific Northwest Laboratory (PNL). The purpose of the work reported in this docuent was to evaluate several recovery processes revealed in the patent and technical literature. Beaker-scale screening tests were initiated for three potential recovery processes: precipitation during sugar denitration of nitric acid reprocessing solutions after plutonium-uranium solvent extraction, adsorption using nobe metal selective chelates on active carbon, and reduction forming solid noble metal deposits on an amine-borane reductive resin. Simulated reprocessing plant solutions representing typical nitric acid liquids from defense (PUREX) or commercial fuel reprocessing facilities were formulated and used for evaluation of the three processes. 9 refs., 3 figs., 9 tabs.

  11. Synthesis of Supported Ultrafine Non-noble Subnanometer-Scale Metal Particles Derived from Metal-Organic Frameworks as Highly Efficient Heterogeneous Catalysts.

    PubMed

    Kang, Xinchen; Liu, Huizhen; Hou, Minqiang; Sun, Xiaofu; Han, Hongling; Jiang, Tao; Zhang, Zhaofu; Han, Buxing

    2016-01-18

    The properties of supported non-noble metal particles with a size of less than 1 nm are unknown because their synthesis is a challenge. A strategy has now been created to immobilize ultrafine non-noble metal particles on supports using metal-organic frameworks (MOFs) as metal precursors. Ni/SiO2 and Co/SiO2 catalysts were synthesized with an average metal particle size of 0.9 nm. The metal nanoparticles were immobilized uniformly on the support with a metal loading of about 20 wt%. Interestingly, the ultrafine non-noble metal particles exhibited very high activity for liquid-phase hydrogenation of benzene to cyclohexane even at 80 °C, while Ni/SiO2 with larger Ni particles fabricated by a conventional method was not active under the same conditions.

  12. Exploring methods for compositional and particle size analysis of noble metal nanoparticles in Daphnia magna.

    PubMed

    Krystek, Petra; Brandsma, Sicco; Leonards, Pim; de Boer, Jacob

    2016-01-15

    The identification and quantification of the bioaccumulation of noble metal engineered nanoparticles (ENPs) by aquatic organisms is of great relevance to understand the exposure and potential toxicity mechanisms of nanoscale materials. Four analytical scenarios were investigated in relation to various sized and composed noble metal (gold (Au), platinum (Pt) and silver (Ag)) ENPs during acute, short-term exposure of Daphnia (D.) magna. Next to the total elemental quantification of absorbed ENPs by D. magna, especially information on the size and particle distribution of ENPs in D. magna is of relevance. Dissolution of the exposed biological material prior to measurement by asymmetric flow field flow fractionation coupled to inductively coupled plasma mass spectrometry (AF4-ICPMS) is challenging because the ENPs must stay stable regarding to particle size and composition. Next to dissolution of exposed D. magna by tetra methyl ammonium hydroxide (TMAH), a new enzymatic dissolution approach was explored by using trypsin. The presence of various sized and composed ENPs has been confirmed by AF4-ICPMS but the chosen dissolution medium was crucial for the results. TMAH and trypsin led to comparable results for medium-sized (50nm) noble metals ENPs in exposed D. magna. But it was also shown that the dissolution of biological materials with smaller (<5nm) ENPs led to different results in particle size and elemental concentration depending on the selected dissolution medium. A significant uptake of Au and Pt ENPs by D. magna or adsorption to particles occurred because only 1-5% of the exposed ENPs remained in the exposure medium.

  13. Method for localized deposition of noble metal catalysts with control of morphology

    DOEpatents

    Ricco, Antonio J.; Manginell, Ronald P.; Huber, Robert J.

    1998-01-01

    A combustible gas sensor that uses a resistively heated, noble metal-coated, micromachined polycrystalline Si filament to calorimetrically detect the presence and concentration of combustible gases. A thin catalytic Pt film was deposited by CVD from the precursor Pt(acac).sub.2 onto microfilaments resistively heated to approximately 500 .degree. C.; Pt deposits only on the hot filament. The filaments tested to date are 2 .mu.m thick .times.10 .mu.m wide .times.100, 250, 500, or 1000 .mu.m-long polycrystalline Si; some are overcoated with a 0.25 .mu.m-thick protective CVD Si.sub.3 N.sub.4 layer.

  14. Zeolitic BIF Crystal Directly Producing Noble-Metal Nanoparticles in Its Pores for Catalysis

    PubMed Central

    Zhang, Hai-Xia; Liu, Meng; Bu, Xianhui; Zhang, Jian

    2014-01-01

    As an integral part of a porous framework and uniformly distributed throughout the internal pore space, the high density of the exposed B–H bond in zeolite-like porous BIF-20 (BIF = Boron Imidazolate Framework) is shown here to effectively produce nanoparticles within its confined pore space. Small noble-metal nanoparticles (Ag or Au) are directly synthesized into its pores without the need for any external reducing agent or photochemical reactions, and the resulting Ag@BIF-20 (or Au@BIF-20) samples show high catalytic activities for the reduction of 4-nitrophenol. PMID:24473155

  15. Recent advances in noble metal based composite nanocatalysts: colloidal synthesis, properties, and catalytic applications.

    PubMed

    Xu, Yong; Chen, Lei; Wang, Xuchun; Yao, Weitang; Zhang, Qiao

    2015-06-28

    This Review article provides a report on progress in the synthesis, properties and catalytic applications of noble metal based composite nanomaterials. We begin with a brief discussion on the categories of various composite materials. We then present some important colloidal synthetic approaches to the composite nanostructures; here, major attention has been paid to bimetallic nanoparticles. We also introduce some important physiochemical properties that are beneficial from composite nanomaterials. Finally, we highlight the catalytic applications of such composite nanoparticles and conclude with remarks on prospective future directions. PMID:26036784

  16. Recent advances in noble metal based composite nanocatalysts: colloidal synthesis, properties, and catalytic applications

    NASA Astrophysics Data System (ADS)

    Xu, Yong; Chen, Lei; Wang, Xuchun; Yao, Weitang; Zhang, Qiao

    2015-06-01

    This Review article provides a report on progress in the synthesis, properties and catalytic applications of noble metal based composite nanomaterials. We begin with a brief discussion on the categories of various composite materials. We then present some important colloidal synthetic approaches to the composite nanostructures; here, major attention has been paid to bimetallic nanoparticles. We also introduce some important physiochemical properties that are beneficial from composite nanomaterials. Finally, we highlight the catalytic applications of such composite nanoparticles and conclude with remarks on prospective future directions.

  17. Noble-Metal-Free Molybdenum Disulfide Cocatalyst for Photocatalytic Hydrogen Production.

    PubMed

    Yuan, Yong-Jun; Lu, Hong-Wei; Yu, Zhen-Tao; Zou, Zhi-Gang

    2015-12-21

    Photocatalytic water splitting using powered semiconductors as photocatalysts represents a promising strategy for clean, low-cost, and environmentally friendly production of H2 utilizing solar energy. The loading of noble-metal cocatalysts on semiconductors can significantly enhance the solar-to-H2 conversion efficiency. However, the high cost and scarcity of noble metals counter their extensive utilization. Therefore, the use of alternative cocatalysts based on non-precious metal materials is pursued. Nanosized MoS2 cocatalysts have attracted considerable attention in the last decade as a viable alternative to improve solar-to-H2 conversion efficiency because of its superb catalytic activity, excellent stability, low cost, availability, environmental friendliness, and chemical inertness. In this perspective, the design, structures, synthesis, and application of MoS2 -based composite photocatalysts for solar H2 generation are summarized, compared, and discussed. Finally, this Review concludes with a summary and remarks on some challenges and opportunities for the future development of MoS2 -based photocatalysts.

  18. Noble-Metal-Free Molybdenum Disulfide Cocatalyst for Photocatalytic Hydrogen Production.

    PubMed

    Yuan, Yong-Jun; Lu, Hong-Wei; Yu, Zhen-Tao; Zou, Zhi-Gang

    2015-12-21

    Photocatalytic water splitting using powered semiconductors as photocatalysts represents a promising strategy for clean, low-cost, and environmentally friendly production of H2 utilizing solar energy. The loading of noble-metal cocatalysts on semiconductors can significantly enhance the solar-to-H2 conversion efficiency. However, the high cost and scarcity of noble metals counter their extensive utilization. Therefore, the use of alternative cocatalysts based on non-precious metal materials is pursued. Nanosized MoS2 cocatalysts have attracted considerable attention in the last decade as a viable alternative to improve solar-to-H2 conversion efficiency because of its superb catalytic activity, excellent stability, low cost, availability, environmental friendliness, and chemical inertness. In this perspective, the design, structures, synthesis, and application of MoS2 -based composite photocatalysts for solar H2 generation are summarized, compared, and discussed. Finally, this Review concludes with a summary and remarks on some challenges and opportunities for the future development of MoS2 -based photocatalysts. PMID:26586523

  19. Polyacrylonitrile/noble metal/SiO₂ nanofibers as substrates for the amplified detection of picomolar amounts of metal ions through plasmon-enhanced fluorescence.

    PubMed

    Zhang, Han; Cao, Minhua; Wu, Wei; Xu, Haibo; Cheng, Si; Fan, Li-Juan

    2015-01-28

    Electrospun polymer/noble metal hybrid nanofibers have developed rapidly as surface-enhanced Raman scattering (SERS)-active substrates over the last few years. However, polymer/noble metal nanofibers with plasmon-enhanced fluorescence (PEF) activity have received no attention to date. Herein, we show a general and facile approach for the preparation of polyacrylonitrile (PAN)/noble metal/SiO2 nanofibrous mats with PEF activity for the first time by combining electrospinning and controlled silica coatings. These PEF-active nanofibrous mats can selectively improve the fluorescence intensity of conjugated polyelectrolytes (CPEs). Importantly, the CPE solution in the presence of a PAN/noble metal/SiO2 nanofibrous mat showed dramatic fluorescence quenching towards picomolar (pM) amounts of heavy metal ions, while the fluorescence of the CPE solution without the nanofibrous mat had no apparent quenching towards micromolar (μM) amounts of metal ions. The combination of the distance-dependent fluorescence enhancement performance of metal NPs and the ionic characteristics of the CPE solution makes the polymer/noble metal nanofibers promising substrates for greatly improving the detection sensitivity towards metal ions. We believe that this work provides a general strategy for preparing plasmon band-tuned PEF-active substrates with advantages including good selectivity, remarkable sensitivity and recyclability, which make them a preferable choice for practical sensing applications. PMID:25494487

  20. Noble metal nanoparticles embedding into polymeric materials: From fundamentals to applications.

    PubMed

    Prakash, Jai; Pivin, J C; Swart, H C

    2015-12-01

    This review covers some key concepts related to embedding of the noble metal nanoparticles in polymer surfaces. The metal nanoparticles embedded into the polymer matrix can provide high-performance novel materials that find applications in modern nanotechnology. In particular, the origin of various processes that drive the embedding phenomenon, growth of the nanostructure at the surface, factors affecting the embedding including role of surface, interface energies and thermodynamic driving forces with emphasis on the fundamental and technological applications, under different conditions (annealing and ion beams) have been discussed. In addition to the conventional thermal process for embedding which includes the measure of fundamental polymer surface properties with relevant probing techniques, this review discusses the recent advances carried out in the understanding of embedding phenomenon starting from thin metal films to growth of the nanoparticles and embedded nanostructures using novel ion beam techniques. PMID:26584861

  1. Protected Noble-Metal Clusters at the Transition from Molecules to Materials

    NASA Astrophysics Data System (ADS)

    Whetten, Robert L.

    2015-03-01

    Protected noble-metal clusters are found at a molecular level of definite composition and structure up to a size of 145-165 metal atoms. Curiously, this size-range is also where several key signatures of metallic character begin to converge. These substances have been of great interest for many application-areas in the past couple decades, but the understanding of their structure and bonding, remarkable self-selection, electronic structure and optical properties has only recently started to reach a fundamental or molecular level of definition. This presentation emphasizes this recent progress and also outlines the prospects for extending the molecular domain of metallurgy well beyond the 200- atom range, thanks to advances in experimental & theoretical methods.

  2. Noble-metal Ag nanoparticle chains: annealing Ag/Bi superlattice nanowires in vacuum

    NASA Astrophysics Data System (ADS)

    Xu, Shao Hui; Fei, Guang Tao; You, Qiao; Gao, Xu Dong; Huo, Peng Cheng; De Zhang, Li

    2016-09-01

    One-dimensional noble-metal Ag nanoparticle chains have been prepared by electrodepositing Ag/Bi superlattice nanowires in a porous anodic alumina oxide (AAO) template and following an annealing process in vacuum. It is found that Bi, as a sacrificial metal, can be removed completely after annealing at 450 °C with a vacuum degree of 10-5 Torr. The regulation of particle size, shape and interparticle spacing of Ag NP chains has been realized by adjusting the segment length of the Ag/Bi superlattice nanowires and the annealing condition. With an extension of the annealing time, it is observed that Ag particles display the transform trend from ellipsoid to sphere. Our findings could inspire further investigation on the design and fabrication of metal nanoparticle chains.

  3. Noble-metal Ag nanoparticle chains: annealing Ag/Bi superlattice nanowires in vacuum

    NASA Astrophysics Data System (ADS)

    Xu, Shao Hui; Fei, Guang Tao; You, Qiao; Gao, Xu Dong; Huo, Peng Cheng; De Zhang, Li

    2016-09-01

    One-dimensional noble-metal Ag nanoparticle chains have been prepared by electrodepositing Ag/Bi superlattice nanowires in a porous anodic alumina oxide (AAO) template and following an annealing process in vacuum. It is found that Bi, as a sacrificial metal, can be removed completely after annealing at 450 °C with a vacuum degree of 10‑5 Torr. The regulation of particle size, shape and interparticle spacing of Ag NP chains has been realized by adjusting the segment length of the Ag/Bi superlattice nanowires and the annealing condition. With an extension of the annealing time, it is observed that Ag particles display the transform trend from ellipsoid to sphere. Our findings could inspire further investigation on the design and fabrication of metal nanoparticle chains.

  4. Noble-metal Ag nanoparticle chains: annealing Ag/Bi superlattice nanowires in vacuum.

    PubMed

    Xu, Shao Hui; Fei, Guang Tao; You, Qiao; Gao, Xu Dong; Huo, Peng Cheng; De Zhang, Li

    2016-09-16

    One-dimensional noble-metal Ag nanoparticle chains have been prepared by electrodepositing Ag/Bi superlattice nanowires in a porous anodic alumina oxide (AAO) template and following an annealing process in vacuum. It is found that Bi, as a sacrificial metal, can be removed completely after annealing at 450 °C with a vacuum degree of 10(-5) Torr. The regulation of particle size, shape and interparticle spacing of Ag NP chains has been realized by adjusting the segment length of the Ag/Bi superlattice nanowires and the annealing condition. With an extension of the annealing time, it is observed that Ag particles display the transform trend from ellipsoid to sphere. Our findings could inspire further investigation on the design and fabrication of metal nanoparticle chains.

  5. Dithiocarbamate Self-Assembled Monolayers as Efficient Surface Modifiers for Low Work Function Noble Metals.

    PubMed

    Meyer, Dominik; Schäfer, Tobias; Schulz, Philip; Jung, Sebastian; Rittich, Julia; Mokros, Daniel; Segger, Ingolf; Maercks, Franziska; Effertz, Christian; Mazzarello, Riccardo; Wuttig, Matthias

    2016-09-01

    Tuning the work function of the electrode is one of the crucial steps to improve charge extraction in organic electronic devices. Here, we show that N,N-dialkyl dithiocarbamates (DTC) can be effectively employed to produce low work function noble metal electrodes. Work functions between 3.1 and 3.5 eV are observed for all metals investigated (Cu, Ag, and Au). Ultraviolet photoemission spectroscopy (UPS) reveals a maximum decrease in work function by 2.1 eV as compared to the bare metal surface. Electronic structure calculations elucidate how the complex interplay between intrinsic dipoles and dipoles induced by bond formation generates such large work function shifts. Subsequently, we quantify the improvement in contact resistance of organic thin film transistor devices with DTC coated source and drain electrodes. These findings demonstrate that DTC molecules can be employed as universal surface modifiers to produce stable electrodes for electron injection in high performance hybrid organic optoelectronics. PMID:27504721

  6. Noble-metal Ag nanoparticle chains: annealing Ag/Bi superlattice nanowires in vacuum.

    PubMed

    Xu, Shao Hui; Fei, Guang Tao; You, Qiao; Gao, Xu Dong; Huo, Peng Cheng; De Zhang, Li

    2016-09-16

    One-dimensional noble-metal Ag nanoparticle chains have been prepared by electrodepositing Ag/Bi superlattice nanowires in a porous anodic alumina oxide (AAO) template and following an annealing process in vacuum. It is found that Bi, as a sacrificial metal, can be removed completely after annealing at 450 °C with a vacuum degree of 10(-5) Torr. The regulation of particle size, shape and interparticle spacing of Ag NP chains has been realized by adjusting the segment length of the Ag/Bi superlattice nanowires and the annealing condition. With an extension of the annealing time, it is observed that Ag particles display the transform trend from ellipsoid to sphere. Our findings could inspire further investigation on the design and fabrication of metal nanoparticle chains. PMID:27487089

  7. Abiological catalysis by artificial haem proteins containing noble metals in place of iron.

    PubMed

    Key, Hanna M; Dydio, Paweł; Clark, Douglas S; Hartwig, John F

    2016-06-13

    Enzymes that contain metal ions--that is, metalloenzymes--possess the reactivity of a transition metal centre and the potential of molecular evolution to modulate the reactivity and substrate-selectivity of the system. By exploiting substrate promiscuity and protein engineering, the scope of reactions catalysed by native metalloenzymes has been expanded recently to include abiological transformations. However, this strategy is limited by the inherent reactivity of metal centres in native metalloenzymes. To overcome this limitation, artificial metalloproteins have been created by incorporating complete, noble-metal complexes within proteins lacking native metal sites. The interactions of the substrate with the protein in these systems are, however, distinct from those with the native protein because the metal complex occupies the substrate binding site. At the intersection of these approaches lies a third strategy, in which the native metal of a metalloenzyme is replaced with an abiological metal with reactivity different from that of the metal in a native protein. This strategy could create artificial enzymes for abiological catalysis within the natural substrate binding site of an enzyme that can be subjected to directed evolution. Here we report the formal replacement of iron in Fe-porphyrin IX (Fe-PIX) proteins with abiological, noble metals to create enzymes that catalyse reactions not catalysed by native Fe-enzymes or other metalloenzymes. In particular, we prepared modified myoglobins containing an Ir(Me) site that catalyse the functionalization of C-H bonds to form C-C bonds by carbene insertion and add carbenes to both β-substituted vinylarenes and unactivated aliphatic α-olefins. We conducted directed evolution of the Ir(Me)-myoglobin and generated mutants that form either enantiomer of the products of C-H insertion and catalyse the enantio- and diastereoselective cyclopropanation of unactivated olefins. The presented method of preparing artificial haem

  8. Rational design of binder-free noble metal/metal oxide arrays with nanocauliflower structure for wide linear range nonenzymatic glucose detection.

    PubMed

    Li, Zhenzhen; Xin, Yanmei; Zhang, Zhonghai; Wu, Hongjun; Wang, Peng

    2015-01-01

    One-dimensional nanocomposites of metal-oxide and noble metal were expected to present superior performance for nonenzymatic glucose detection due to its good conductivity and high catalytic activity inherited from noble metal and metal oxide respectively. As a proof of concept, we synthesized gold and copper oxide (Au/CuO) composite with unique one-dimensional nanocauliflowers structure. Due to the nature of the synthesis method, no any foreign binder was needed in keeping either Au or CuO in place. To the best of our knowledge, this is the first attempt in combining metal oxide and noble metal in a binder-free style for fabricating nonenzymatic glucose sensor. The Au/CuO nanocauliflowers with large electrochemical active surface and high electrolyte contact area would promise a wide linear range and high sensitive detection of glucose with good stability and reproducibility due to its good electrical conductivity of Au and high electrocatalytic activity of CuO.

  9. CO-oxidation catalysts: Low-temperature CO oxidation over Noble-Metal Reducible Oxide (NMRO) catalysts

    NASA Technical Reports Server (NTRS)

    Herz, Richard K.

    1990-01-01

    Oxidation of CO to CO2 is an important reaction technologically and environmentally and a complex and interesting reaction scientifically. In most cases, the reaction is carried out in order to remove CO as an environmental hazard. A major application of heterogeneous catalysts is catalytic oxidation of CO in the exhaust of combustion devices. The reaction over catalysts in exhaust gas is fast and often mass-transfer-limited since exhaust gases are hot and O2/CO ratios are high. The main challenges to catalyst designers are to control thermal sintering and chemical poisoning of the active materials. The effect of the noble metal on the oxide is discussed, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form unique catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

  10. Measuring the spin polarization of alkali-metal atoms using nuclear magnetic resonance frequency shifts of noble gases

    SciTech Connect

    Liu, X. H.; Luo, H.; Qu, T. L. Yang, K. Y.; Ding, Z. C.

    2015-10-15

    We report a novel method of measuring the spin polarization of alkali-metal atoms by detecting the NMR frequency shifts of noble gases. We calculated the profile of {sup 87}Rb D1 line absorption cross sections. We then measured the absorption profile of the sample cell, from which we calculated the {sup 87}Rb number densities at different temperatures. Then we measured the frequency shifts resulted from the spin polarization of the {sup 87}Rb atoms and calculated its polarization degrees at different temperatures. The behavior of frequency shifts versus temperature in experiment was consistent with theoretical calculation, which may be used as compensative signal for the NMRG closed-loop control system.

  11. Anchoring noble metal nanoparticles on CeO2 modified reduced graphene oxide nanosheets and their enhanced catalytic properties.

    PubMed

    Ji, Zhenyuan; Shen, Xiaoping; Xu, Yuling; Zhu, Guoxing; Chen, Kangmin

    2014-10-15

    The strategy of structurally integrating noble metal, metal oxide, and graphene is expected to offer prodigious opportunities toward emerging functions of graphene-based nanocomposites. In this study, we develop a facile two-step approach to disperse noble metal (Pt and Au) nanoparticles on the surface of CeO2 functionalized reduced graphene oxide (RGO) nanosheets. It is shown that Pt and Au with particle sizes of about 5 and 2nm are well dispersed on the surface of RGO/CeO2. The reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH4 was used as a model reaction to quantitatively evaluate the catalytic properties of the as-synthesized RGO/Pt/CeO2 and RGO/Au/CeO2 ternary nanocomposites. In such triple-component catalysts, CeO2 nanocrystals provide unique and critical roles for optimizing the catalytic performance of noble metallic Pt and Au, allowing them to express enhanced catalytic activities in comparison with RGO/Pt and RGO/Au catalysts. In addition, a possible mechanism for the enhanced catalytic activities of the RGO/Pt/CeO2 and RGO/Au/CeO2 ternary catalysts in the reduction of 4-NP is proposed. It is expected that our prepared graphene-based triple-component composites, which inherit peculiar properties of graphene, metal oxide, and noble metal, are attractive candidates for catalysis and other applications.

  12. 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

  13. Noble metal nanoclusters and nanoparticles precede mineral formation in magmatic sulphide melts

    PubMed Central

    Helmy, Hassan M.; Ballhaus, Chris; Fonseca, Raúl O.C.; Wirth, Richard; Nagel, Thorsten; Tredoux, Marian

    2013-01-01

    In low temperature aqueous solutions, it has long been recognized by in situ experiments that many minerals are preceded by crystalline nanometre-sized particles and non-crystalline nanophases. For magmatic systems, nanometre-sized precursors have not yet been demonstrated to exist, although the suggestion has been around for some time. Here we demonstrate by high temperature quench experiments that platinum and arsenic self-organize to nanoparticles, well before the melt has reached a Pt–As concentration at which discrete Pt arsenide minerals become stable phases. If all highly siderophile elements associate to nanophases in undersaturated melts, the distribution of the noble metals between silicate, sulphide and metal melts will be controlled by the surface properties of nano-associations, more so than by the chemical properties of the elements. PMID:24008992

  14. The Effect of Novel Mercapto Silane Systems on Resin Bond Strength to Dental Noble Metal Alloys.

    PubMed

    Lee, Yangho; Kim, Kyo-Han; Kim, Young Kyung; Son, Jun Sik; Lee, Eunkyung; Kwon, Tae-Yub

    2015-07-01

    Self-assembled monolayers of thiols (RSH), which are key elements in nanoscience and nanotechnology, have been used to link a range of materials to planar gold surfaces or gold nanoparticles. In this study, the adhesive performance of mercapto silane systems to dental noble metal alloys was evaluated in vitro and compared with that of commercial dental primers. Dental gold-palladium-platinum (Au-Pd-Pt), gold-palladium-silver (Au-Pd-Ag), and palladium-silver (Pd-Ag) alloys were used as the bonding substrates after air-abrasion (sandblasting). One of the following primers was applied to each alloy: (1) no primer treatment (control), (2) three commer- cial primers: V-Primer, Metal Primer II, and M.L. Primer, and (3) two experimental silane primer systems: 2-step application with 3-mercaptopropyltrimethoxysilane (SPS) (1.0 wt%) and then 3-methacryloxypropyltrimethoxysilane (MPS) (1.0 wt%), and a silane blend consisting of SPS and MPS (both 1.0 wt%). Composite resin cylinders with a diameter of 2.38 mm were bonded to the surfaces and irradiated for 40 sec using a curing light. After storage in water at 37 °C for 24 h, all the bonded specimens were thermocycled 5000 times before the shear bond strength test. Regardless of the alloy type, the mercapto silane systems (both the 2-step and blend systems) consistently showed superior bonding performance than the commercial primers. Contact angle analysis of the primed surfaces indicated that higher resin bond strengths were produced on more hydrophilic alloy surfaces. These novel mercapto silane systems are a promising alternative for improving resin bonding to dental noble metal alloys.

  15. Noble metal nanowires: from plasmon waveguides to passive and active devices.

    PubMed

    Lal, Surbhi; Hafner, Jason H; Halas, Naomi J; Link, Stephan; Nordlander, Peter

    2012-11-20

    Using chemical synthesis, researchers can produce noble metal nanowires with highly regular, crystalline properties unachievable by alternative, top-down nanofabrication methods. Sitting at the intersection of nanochemistry and nanooptics, noble metal nanowires have generated intense and growing research interest. These nanostructures combine subwavelength transverse dimensions (50-100 nm) and longitudinal dimensions that can reach tens of micrometers or more, which makes them an ideal platform to launch surface plasmon waves by direct illumination of one end of the structure. Because of this property, researchers are using noble metal nanowires as a tool for fundamental studies of subwavelength plasmon-based optics and the properties of surface plasmon guided wave propagation in highly confined geometries below the classical optical diffraction limit. In this Account, we review some of the recent developments in plasmonic nanowire fabrication, nanowire plasmon imaging, and nanowire optical components and devices. The addition of an adjacent nanowire, substrate, or other symmetry-breaking defect can enable the direct coupling of light to and from free space to the guided waves on a nanowire structure. Such structures lead to more complex nanowire-based geometries with multiple optical inputs and outputs. Additional nanowire imaging methods are also possible: plasmon propagation on nanowires produces intense near-field diffraction, which can induce fluorescence in nearby quantum dots or photobleach adjacent molecules. When the nanowire is deposited on a dielectric substrate, the plasmon propagation along chemically synthesized nanowires exceeds 10 μm, which makes these structures useful in nonlocal applications such as remote surface-enhanced Raman spectroscopy (SERS) sensing. Nanowires can be used as passive optical devices, which include, for example, polarization manipulators, linear polarization rotators, or even broadband linear-to-circular polarization

  16. Noble metal nanowires: from plasmon waveguides to passive and active devices.

    PubMed

    Lal, Surbhi; Hafner, Jason H; Halas, Naomi J; Link, Stephan; Nordlander, Peter

    2012-11-20

    Using chemical synthesis, researchers can produce noble metal nanowires with highly regular, crystalline properties unachievable by alternative, top-down nanofabrication methods. Sitting at the intersection of nanochemistry and nanooptics, noble metal nanowires have generated intense and growing research interest. These nanostructures combine subwavelength transverse dimensions (50-100 nm) and longitudinal dimensions that can reach tens of micrometers or more, which makes them an ideal platform to launch surface plasmon waves by direct illumination of one end of the structure. Because of this property, researchers are using noble metal nanowires as a tool for fundamental studies of subwavelength plasmon-based optics and the properties of surface plasmon guided wave propagation in highly confined geometries below the classical optical diffraction limit. In this Account, we review some of the recent developments in plasmonic nanowire fabrication, nanowire plasmon imaging, and nanowire optical components and devices. The addition of an adjacent nanowire, substrate, or other symmetry-breaking defect can enable the direct coupling of light to and from free space to the guided waves on a nanowire structure. Such structures lead to more complex nanowire-based geometries with multiple optical inputs and outputs. Additional nanowire imaging methods are also possible: plasmon propagation on nanowires produces intense near-field diffraction, which can induce fluorescence in nearby quantum dots or photobleach adjacent molecules. When the nanowire is deposited on a dielectric substrate, the plasmon propagation along chemically synthesized nanowires exceeds 10 μm, which makes these structures useful in nonlocal applications such as remote surface-enhanced Raman spectroscopy (SERS) sensing. Nanowires can be used as passive optical devices, which include, for example, polarization manipulators, linear polarization rotators, or even broadband linear-to-circular polarization

  17. Effect of Mercury-Noble Metal Interactions on SRAT Processing of SB3 Simulants (U)

    SciTech Connect

    Koopman, D. C.; Baich, M. A.

    2004-12-31

    Controlling hydrogen generation below the Defense Waste Processing Facility (DWPF) safety basis constrains the range of allowable acid additions in the DWPF Chemical Processing Cell. This range is evaluated in simulant tests at the Savannah River National Laboratory (SRNL). A minimum range of allowable acid additions is needed to provide operational flexibility and to handle typical uncertainties in process and analytical measurements used to set acid additions during processing. The range of allowable acid additions is a function of the composition of the feed to DWPF. Feed changes that lead to a smaller range of allowable acid additions have the potential to impact decisions related to wash endpoint control of DWPF feed composition and to the introduction of secondary waste streams into DWPF. A limited program was initiated in SRNL in 2001 to study the issue of hydrogen generation. The program was reinitiated at the end of fiscal year 2004. The primary motivation for the study is that a real potential exists to reduce the conservatism in the range of allowable acid additions in DWPF. Increasing the allowable range of acid additions can allow decisions on the sludge wash endpoint or the introduction of secondary waste streams to DWPF to be based on other constraints such as glass properties, organic carbon in the melter off-gas, etc. The initial phase of the study consisted of a review of site reports and off-site literature related to catalytic hydrogen generation from formic acid and/or formate salts by noble metals. Many things are already known about hydrogen generation during waste processing. This phase also included the development of an experimental program to improve the understanding of hydrogen generation. This phase is being documented in WSRC-TR-2002-00034. A number of areas were identified where an improved understanding would be beneficial. A phased approach was developed for new experimental studies related to hydrogen generation. The first phase

  18. Deposition behavior of UO2 and noble-metal elements in oxide-electrowinning reprocessing

    NASA Astrophysics Data System (ADS)

    Kosugi, K.; Fukushima, M.; Myochin, M.; Mizuguchi, K.; Oomori, T.

    2005-02-01

    As a candidate process for future reprocessing technology of nuclear spent fuel, oxide-electrowinning method has been studied. In this method, the uranium is collected on the cathode in the form of UO2 by electrolysis in the molten chloride. Thereby, the noble metal (NM) elements accompany the uranium deposition, because of very close redox potential between NM elements and UO2. To clarify the electrolysis behavior of the uranium and NM elements in the low-current-density electrolysis, the laboratory scale experiments were performed under various conditions of cathode current density and solutes concentration in the chloride melt, and the separation efficiency and the morphology of the deposition were investigated. It was found that the separation of Pd from uranium was more difficult than that of Rh. The presence of U4+ greatly influenced current efficiency of the electrolysis process.

  19. Determination of seven noble metals in standard rock samples by means of thermal neutron activation analysis.

    PubMed

    Ayabe, M; Hirao, Y; Kimura, K

    1980-10-01

    Ruthenium, silver, rhenium, osmium, iridium, platinum and gold in standard rock samples from Geological Survey of Japan (JB-1, JB-2, JG-1 and JA-1) were determined by thermal neutron activation method with a systematic chemical separation. U.S. Geological Survey standard rocks (BCR-1 and G-2) were also analyzed to obtain an information about the accuracy and precision on the method. Generally agreement of our results with previous values for BCR-1 and G-2 was excellent. The noble metal contents in the igneous rocks from Japanese region were approximately comparable to those in the corresponding rocks from the continental region, and showed a tendency to decrease with increasing silica contents, with weak interrelations to other major elements.

  20. Local heating in noble metal nanocontacts under high biases at 77 K

    NASA Astrophysics Data System (ADS)

    Tsutsui, Makusu; Teramae, Yumi; Kurokawa, Shu; Sakai, Akira

    2006-10-01

    Effects of local heating of noble metal nanocontacts under high biases at 77 K are investigated by measuring the bias dependence of the two-level fluctuation (TLF) frequency of the contact conductance. The TLF frequency increases exponentially in a bias range from 0.2 to 0.6 V for Au and Cu nanocontacts. This result indicates that the effective contact temperature of these contacts remains unchanged up to 0.6 V, in accordance with the theoretical prediction by Todorov et al. [T.N. Todorov, J. Hoekstra, A.P. Sutton, Phys. Rev. Lett. 86 (2001) 3606]. In contrast, the TLF frequency of Ag nanocontacts starts to increase more rapidly above 0.45 V than that of Au and Cu nanocontacts. The steep rise in the TLF frequency is possibly attributed to a poor heat transfer to the bulk part of the contact and a resulting rapid increase in the effective temperature.

  1. Elucidation of noble metal/formic acid chemistry during DWPF feed preparation. Revision 1

    SciTech Connect

    Landon, L.F.

    1991-12-31

    Eleven reports are included: evaluation of noble metal compounds as catalysts for aerobic decomposition of formic acid; reaction of NaNO{sub 3} and NaNO{sub 2} with formic acid under argon; effects of Ru, Rh, Pd chlorides on formic acid decomposition in presence of IDMS (pH=11.0) sludge; effects of additives on catalysts on decomposition of formic acid to hydrogen; Rh-catalyzed decomposition of formic acid; the question of whether this decomposition can be heterogeneous catalysis; inhibition of this reaction by additives; nitrilotriacetic acid inhibitor; uses of gelatin and other water soluble polymers to control flocculation rate; comparison of catalytic activities of Rh, Ru, Pd in Purex and HM sludges; experiments on homogeneous vs heterogeneous nature of Rh catalyst. Figs, refs, tabs.

  2. Elucidation of noble metal/formic acid chemistry during DWPF feed preparation

    SciTech Connect

    Landon, L.F.

    1991-01-01

    Eleven reports are included: evaluation of noble metal compounds as catalysts for aerobic decomposition of formic acid; reaction of NaNO[sub 3] and NaNO[sub 2] with formic acid under argon; effects of Ru, Rh, Pd chlorides on formic acid decomposition in presence of IDMS (pH=11.0) sludge; effects of additives on catalysts on decomposition of formic acid to hydrogen; Rh-catalyzed decomposition of formic acid; the question of whether this decomposition can be heterogeneous catalysis; inhibition of this reaction by additives; nitrilotriacetic acid inhibitor; uses of gelatin and other water soluble polymers to control flocculation rate; comparison of catalytic activities of Rh, Ru, Pd in Purex and HM sludges; experiments on homogeneous vs heterogeneous nature of Rh catalyst. Figs, refs, tabs.

  3. Highly Sensitive and Reproducible SERS Performance from Uniform Film Assembled by Magnetic Noble Metal Composite Microspheres.

    PubMed

    Niu, Chunyu; Zou, Bingfang; Wang, Yongqiang; Cheng, Lin; Zheng, Haihong; Zhou, Shaomin

    2016-01-26

    To realize highly sensitive and reproducible SERS performance, a new route was put forward to construct uniform SERS film by using magnetic composite microspheres. In the experiment, monodisperse Fe3O4@SiO2@Ag microspheres with hierarchical surface were developed and used as building block of SERS substrate, which not only realized fast capturing analyte through dispersion and collection under external magnet but also could be built into uniform film through magnetically induced self-assembly. By using R6G as probe molecule, the as-obtained uniform film exhibited great improvement on SERS performance in both sensitivity and reproducibility when compared with nonuniform film, demonstrating the perfect integration of high sensitivity of hierarchal noble metal microspheres and high reproducibility of ordered microspheres array. Furthermore, the as-obtained product was used to detect pesticide thiram and also exhibited excellent SERS performance for trace detection.

  4. High density decoration of noble metal nanoparticles on polydopamine-functionalized molybdenum disulphide.

    PubMed

    Hussain, Muhammad Asif; Yang, MinHo; Lee, Tae Jae; Kim, Jung Won; Choi, Bong Gill

    2015-08-01

    Here, we report a highly stable colloidal suspension of nanoparticles (i.e., Pt and Au)-deposited MoS2 sheets, in which polydopamine (PD) serves as surface functional groups. The adoption of polydopamine coating onto the MoS2 surface enables homogeneous deposition of nanoparticles in an aqueous solution. As-synthesized nanohybrids are thoroughly characterized by transmission electron microscopy (TEM), Raman spectroscopy, and X-ray diffraction (XRD) measurement. These intensive investigations reveal that noble metal nanocrystals are uniformly distributed on the surface of ultrathin MoS2 sheets (∼4 layers). Moreover, as-prepared Au/PD/MoS2 nanohybrids can be applied as a heterogeneous catalyst for reduction of 4-nitrophenol to 4-aminophenol, and they exhibit an excellent catalytic activity.

  5. Structure and optical properties of noble metal and oxide nanoparticles dispersed in various polysaccharide biopolymers

    NASA Astrophysics Data System (ADS)

    Djoković, V.; Božanic, D. K.; Vodnik, V. V.; Krsmanović, R. M.; Trandafilovic, L. V.; Dimitrijević-Branković, S.

    2011-10-01

    We present the results on the structure and the optical properties of noble metal (Ag, Au) and oxide (ZnO) nanoparticles synthesized by various methods in different polysaccharide matrices such as chitosan, glycogen, alginate and starch. The structure of the obtained nanoparticles was studied in detail with microscopic techniques (TEM, SEM), while the XPS spectroscopy was used to investigate the effects at the nanoparticle-biomolecule interfaces. The antimicrobial activity of the nanocomposite films with Ag nanoparticles was tested against the Staphylococcus aureus, Escherichia coli and Candida albicans pathogens. In addition, we will present the results on the structure and optical properties of the tryptophan amino acid functionalized silver nanoparticles dispersed in water soluble polymer matrices.

  6. A simple route to diverse noble metal-decorated iron oxide nanoparticles for catalysis

    NASA Astrophysics Data System (ADS)

    Walker, Joan M.; Zaleski, Jeffrey M.

    2016-01-01

    Developing facile synthetic routes to multifunctional nanoparticles combining the magnetic properties of iron oxides with the optical and catalytic utility of noble metal particles remains an important goal in realizing the potential of hybrid nanomaterials. To this end, we have developed a single route to noble metal-decorated magnetic nanoparticles (Fe3O4@SiO2-M M = Au, Pd, Ag, and PtAg) and characterized them by HRTEM and STEM/EDX imaging to reveal their nanometer size (16 nm Fe3O4 and 1-5 nm M seeds) and uniformity. This represents one of the few examples of genuine multifunctional particles on the nanoscale. We show that these hybrid structures have excellent catalytic activity for the reduction of 4-nitrophenol (knorm = 2 × 107 s-1 mol(Pd)-1 5 × 106 s-1 mol(Au)-1 5 × 105 s-1 mol(PtAg)-1 7 × 105 s-1 mol(Ag)-1). These rates are the highest reported for nano-sized comparables, and are competitive with mesoparticles of similar composition. Due to their magnetic response, the particles are also suitable for magnetic recovery and maintain >99% conversion for at least four cycles. Using this synthetic route, Fe3O4@SiO2-M particles show great promise for further development as a precursor to complicated anisotropic materials or for applications ranging from nanocatalysis to biomedical sensing.Developing facile synthetic routes to multifunctional nanoparticles combining the magnetic properties of iron oxides with the optical and catalytic utility of noble metal particles remains an important goal in realizing the potential of hybrid nanomaterials. To this end, we have developed a single route to noble metal-decorated magnetic nanoparticles (Fe3O4@SiO2-M M = Au, Pd, Ag, and PtAg) and characterized them by HRTEM and STEM/EDX imaging to reveal their nanometer size (16 nm Fe3O4 and 1-5 nm M seeds) and uniformity. This represents one of the few examples of genuine multifunctional particles on the nanoscale. We show that these hybrid structures have excellent catalytic

  7. Visible-light-driven hydrogen production in a dye sensitized polyoxometalate system without noble metals

    NASA Astrophysics Data System (ADS)

    Liu, Xing; Li, Yuexiang; Peng, Shaoqin; Lai, Hua; Yi, Zhengji

    2016-05-01

    In this work, a noble-metal-free homogeneous system was constructed in one step with Keggin-type polyoxometalate (POM) SiW12O404- as a catalyst, Eosin Y as a photosensitizer, and triethanolamine (TEOA) as a sacrificial electron donor for water splitting to produce hydrogen under visible-light irradiation. A two-electron reduced heteropoly blue SiW12O406- is produced by photosensitization under visible-light irradiation. The effect of various component concentrations and POMs with different central atoms (PW12O403-, GeW12O404-, etc.) on hydrogen production was discussed. This simple system made of earth-abundant elements is expected to contribute toward the development of functional and efficient artificial photosynthetic system.

  8. Effects of metal primers on bonding of adhesive resin cement to noble alloys for porcelain fusing.

    PubMed

    Okuya, Nobuhiro; Minami, Hiroyuki; Kurashige, Hisanori; Murahara, Sadaaki; Suzuki, Shiro; Tanaka, Takuo

    2010-03-01

    This study evaluated the effects of metal primers on the bonding of adhesive resin to four pure metals (Au, Pd, Ag, Cu) and two noble alloys for porcelain fusing (high-gold and high-palladium content alloys). Bonding surface was polished with 600-grit silicon carbide paper and primed with one of the three metal primers (V-Primer, Metaltite, and M.L. Primer). Bonded specimens were fabricated by applying adhesive resin (Super-Bond C&B) on the primed surface. Shear bond strength (SBS) was determined both before and after thermocycling (4-60 degrees C for 2,000 cycles). The highest SBS values to each pure metal after thermocycling were 33.5 MPa for Au by M.L. Primer, 35.0 MPa for Ag by V-Primer, and 34.4 MPa for Cu by Metaltite. SBS to high-gold content alloy after thermocycling was 33.3 MPa by M.L. Primer. None of the primers was effective for pure Pd and high-palladium content alloy after thermocycling.

  9. Synthesis and characterization of ZnO nanostructures on noble-metal coated substrates

    NASA Astrophysics Data System (ADS)

    Dikovska, A. Og.; Atanasova, G. B.; Avdeev, G. V.; Nedyalkov, N. N.

    2016-06-01

    In this work, ZnO nanostructures were fabricated on noble-metal (Au, Ag and Au-Ag alloys) coated silicon substrates by applying pulsed laser deposition. The samples were prepared at a substrate temperature of 550 °C, an oxygen pressure of 5 Pa, and a laser fluence of 2 J cm-2 - process parameters usually used for deposition of smooth and dense thin films. The metal layer's role is substantial for the preparation of nanostructures. Heating of the substrate changed the morphology of the metal layer and, subsequently, nanoparticles were formed. The use of different metal particles resulted in different morphologies and properties of the ZnO nanostructures synthesized. The morphology of the ZnO nanostructures was related to the Au-Ag alloy's content of the catalyst layer. It was found that the morphology of the ZnO nanostructures evolved from nanorods to nanobelts as the ratio of Au/Ag in the alloy catalyst was varied. The use of a small quantity of Ag in the Au-Ag catalyst (Au3Ag) layer resulted predominantly in the deposition of ZnO nanorods. A higher Ag content in the catalyst alloy (AuAg2) layer resulted in the growth of a dense structure of ZnO nanobelts.

  10. Measurement of the Inhomogeneity in Type B and Land-Jewell Noble-Metal Thermocouples

    NASA Astrophysics Data System (ADS)

    Webster, E. S.; Greenen, A.; Pearce, J.

    2016-07-01

    Inhomogeneity is the largest contributor to uncertainty in temperature measurements made with thermocouples, and the knowledge of inhomogeneity is essential if low-uncertainty measurements are required. Inhomogeneity is a particular problem for long-term applications at temperatures near or above 1500 ^{circ }hbox {C}, where pairs of alloyed noble-metal thermocouples must be used and the alloy components and potential contaminants become very mobile and cause large deviations in the Seebeck coefficient. While changes in inhomogeneity are a known and well-studied problem in noble-metal alloys at temperatures below 1100 ^{circ }hbox {C}, the effects are not well quantified at higher temperatures. This paper reports the first detailed measurements of inhomogeneity in a number of Type B and Land-Jewell thermocouples exposed to either short-term calibration up to 1600 ^{circ }hbox {C} or long-term in situ measurements for a period of approximately 3000 h at 1600 ^{circ }hbox {C}. The inhomogeneity is measured in a high-resolution scanner operating over the range from 600 ^{circ }hbox {C} to 900 ^{circ }hbox {C}. The results show that drifts of between 0.2 % and 0.6 % can be expected for reversible crystallographic and oxidation effects, whereas drift caused by irreversible contamination effects can be expected to be between 0.6 % and 1.1 %. It is also shown that the deviations in emfs caused by irreversible homogeneities in these thermocouples scale approximately linearly with temperature. This scalability allows uncertainties assessed at one temperature, to be extrapolated to other temperatures. Additionally it is shown that a preconditioning anneal at 1100 ^{circ }hbox {C} should be applied both before and after calibration to remove undesirable crystallographic and rhodium-oxidation effects.

  11. Metastability and structural polymorphism in noble metals: the role of composition and metal atom coordination in mono- and bimetallic nanoclusters.

    PubMed

    Sanchez, Sergio I; Small, Matthew W; Bozin, Emil S; Wen, Jian-Guo; Zuo, Jian-Min; Nuzzo, Ralph G

    2013-02-26

    This study examines structural variations found in the atomic ordering of different transition metal nanoparticles synthesized via a common, kinetically controlled protocol: reduction of an aqueous solution of metal precursor salt(s) with NaBH₄ at 273 K in the presence of a capping polymer ligand. These noble metal nanoparticles were characterized at the atomic scale using spherical aberration-corrected scanning transmission electron microscopy (C(s)-STEM). It was found for monometallic samples that the third row, face-centered-cubic (fcc), transition metal [(3M)-Ir, Pt, and Au] particles exhibited more coherently ordered geometries than their second row, fcc, transition metal [(2M)-Rh, Pd, and Ag] analogues. The former exhibit growth habits favoring crystalline phases with specific facet structures while the latter samples are dominated by more disordered atomic arrangements that include complex systems of facets and twinning. Atomic pair distribution function (PDF) measurements further confirmed these observations, establishing that the 3M clusters exhibit longer ranged ordering than their 2M counterparts. The assembly of intracolumn bimetallic nanoparticles (Au-Ag, Pt-Pd, and Ir-Rh) using the same experimental conditions showed a strong tendency for the 3M atoms to template long-ranged, crystalline growth of 2M metal atoms extending up to over 8 nm beyond the 3M core.

  12. Polyacrylonitrile/noble metal/SiO2 nanofibers as substrates for the amplified detection of picomolar amounts of metal ions through plasmon-enhanced fluorescence

    NASA Astrophysics Data System (ADS)

    Zhang, Han; Cao, Minhua; Wu, Wei; Xu, Haibo; Cheng, Si; Fan, Li-Juan

    2015-01-01

    Electrospun polymer/noble metal hybrid nanofibers have developed rapidly as surface-enhanced Raman scattering (SERS)-active substrates over the last few years. However, polymer/noble metal nanofibers with plasmon-enhanced fluorescence (PEF) activity have received no attention to date. Herein, we show a general and facile approach for the preparation of polyacrylonitrile (PAN)/noble metal/SiO2 nanofibrous mats with PEF activity for the first time by combining electrospinning and controlled silica coatings. These PEF-active nanofibrous mats can selectively improve the fluorescence intensity of conjugated polyelectrolytes (CPEs). Importantly, the CPE solution in the presence of a PAN/noble metal/SiO2 nanofibrous mat showed dramatic fluorescence quenching towards picomolar (pM) amounts of heavy metal ions, while the fluorescence of the CPE solution without the nanofibrous mat had no apparent quenching towards micromolar (μM) amounts of metal ions. The combination of the distance-dependent fluorescence enhancement performance of metal NPs and the ionic characteristics of the CPE solution makes the polymer/noble metal nanofibers promising substrates for greatly improving the detection sensitivity towards metal ions. We believe that this work provides a general strategy for preparing plasmon band-tuned PEF-active substrates with advantages including good selectivity, remarkable sensitivity and recyclability, which make them a preferable choice for practical sensing applications.Electrospun polymer/noble metal hybrid nanofibers have developed rapidly as surface-enhanced Raman scattering (SERS)-active substrates over the last few years. However, polymer/noble metal nanofibers with plasmon-enhanced fluorescence (PEF) activity have received no attention to date. Herein, we show a general and facile approach for the preparation of polyacrylonitrile (PAN)/noble metal/SiO2 nanofibrous mats with PEF activity for the first time by combining electrospinning and controlled silica

  13. Magnetic properties of ZnS doped with noble metals (X = Ru, Rh, Pd, and Ag)

    NASA Astrophysics Data System (ADS)

    Tan, Zhiyun; Xiao, Wenzhi; Wang, Lingling; Yang, Youchang

    2012-12-01

    Density functional theory calculations are carried out to study the electronic structures and magnetic properties in zinc-blende structure ZnS doped with nonmagnetic noble metals (X = Ru, Rh, Pd, and Ag). Results show robust magnetic ground states for X-doped ZnS. The total magnetic moments are about 2.0, 3.0, and 2.0 μB per supercell for the Ru-, Rh-, and Pd-doped ZnS, respectively. As the atomic number of X element increases, the local magnetic moment tends toward delocalize and the hybridization between X-4d and S-3p states become stronger. This trend is strongly related to the difference in electronegativity between the substitutional X and the cation in the ZnS host. For Ag-doped ZnS, both non-spin- and spin-polarized calculations yield nearly equal total energy. The substitution of Zn in ZnS parent material by the nonmagnetic 4d transition-metals may lead to half-metallic ferromagnetism which stems from the hybridization between X-4d and S-3p states and could be attributed to a double-exchange mechanism. Curie temperature values are estimated using mean-field approximation.

  14. Evidence for two pinning mechanisms with noble metals on InP(110)

    SciTech Connect

    Cao, R.; Miyano, K.; Lindau, I.; Spicer, W.E.

    1989-05-01

    Interfacial chemistry and Fermi-level movement for interfaces of noble metals on InP(110) prepared at room temperature (RT) and 80 K low temperature (LT) have been examined using photoelectron spectroscopy. An interfacial reaction is detected for all the RT interfaces as well as the LT Cu/InP interface, and the Fermi levels are pinned at 0.95 eV above the valence-band maximum (VBM). However, for LT Au/InP and Ag/InP, no reaction is seen, and the Fermi level is pinned around 0.7 eV above the VBM. The 0.7-eV pinning position at the near ideal LT Au/InP and Ag/InP interface is associated with metal induced gap states (MIGS), whereas, that at 0.95 eV is associated with defects formed during the interfacial reaction. These results indicate that both MIGS and defects can be important in the Fermi-level pinning and that the former is dominant only when the defect density is sufficiently low.

  15. Noble-transition metal nanoparticle breathing in a reactive gas atmosphere.

    PubMed

    Petkov, Valeri; Shan, Shiyao; Chupas, Peter; Yin, Jun; Yang, Lefu; Luo, Jin; Zhong, Chuan-Jian

    2013-08-21

    In situ high-energy X-ray diffraction coupled to atomic pair distribution function analysis is used to obtain fundamental insight into the effect of the reactive gas environment on the atomic-scale structure of metallic particles less than 10 nm in size. To substantiate our recent discovery we investigate a wide range of noble-transition metal nanoparticles and confirm that they expand and contract radially when treated in oxidizing (O2) and reducing (H2) atmospheres, respectively. The results are confirmed by supplementary XAFS experiments. Using computer simulations guided by the experimental diffraction data we quantify the effect in terms of both relative lattice strain and absolute atomic displacements. In particular, we show that the effect leads to a small percent of extra surface strain corresponding to several tenths of Ångström displacements of the atoms at the outmost layer of the particles. The effect then gradually decays to zero within 4 atomic layers inside the particles. We also show that, reminiscent of a breathing type structural transformation, the effect is reproducible and reversible. We argue that because of its significance and widespread occurrence the effect should be taken into account in nanoparticle research.

  16. Understanding the degradation pathway of the pesticide, chlorpyrifos by noble metal nanoparticles.

    PubMed

    Bootharaju, M S; Pradeep, T

    2012-02-01

    Application of nanoparticles (NPs) in environmental remediation such as water purification requires a detailed understanding of the mechanistic aspects of the interaction between the species involved. Here, an attempt was made to understand the chemistry of noble metal nanoparticle-pesticide interaction, as these nanosystems are being used extensively for water purification. Our model pesticide, chlorpyrifos (CP), belonging to the organophosphorothioate group, is shown to decompose to 3,5,6-trichloro-2-pyridinol (TCP) and diethyl thiophosphate at room temperature over Ag and Au NPs, in supported and unsupported forms. The degradation products were characterized by absorption spectroscopy and electrospray ionization mass spectrometry (ESI MS). These were further confirmed by ESI tandem mass spectrometry. The interaction of CP with NP surfaces was investigated using transmission electron microscopy, energy dispersive analysis of X-rays, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS reveals no change in the oxidation state of silver after the degradation of CP. It is proposed that the degradation of CP proceeds through the formation of AgNP-S surface complex, which is confirmed by Raman spectroscopy. In this complex, the P-O bond cleaves to yield a stable aromatic species, TCP. The rate of degradation of CP increases with increase of temperature and pH. Complete degradation of 10 mL of 2 ppm CP solution is achieved in 3 h using 100 mg of supported Ag@citrate NPs on neutral alumina at room temperature at a loading of ∼0.5 wt %. The effect of alumina and monolayer protection of NPs on the degradation of CP is also investigated. The rate of degradation of CP by Ag NPs is greater than that of Au NPs. The results have implications to the application of noble metal NPs for drinking water purification, as pesticide contamination is prevalent in many parts of the world. Study shows that supported Ag and Au NPs may be employed in sustainable

  17. Solar wind noble gases and nitrogen in metal from lunar soil 68501

    NASA Technical Reports Server (NTRS)

    Becker, Richard H.; Pepin, Robert O.

    1994-01-01

    Noble gases and N were analyzed in handpicked metal separates from lunar soil 68501 by a combination of step-wise combustions and pyrolyses. Helium and Ne were found to be unfractionated with respect to one another when normalized to solar abundances, for both the bulk sample and for all but the highest temperature steps. However, they are depleted relative to Ar, Kr and Xe by at least a factor of 5. The heavier gases exhibit mass-dependent fractionation relative to solar system abundance ratios but appear unfractionated, both in the bulk metal and in early temperature steps, when compared to relative abundances derived from lunar ilmenite 71501 by chemical etching, recently put forward as representing the abundance ratios in solar wind. Estimates of the contribution of solar energetic particles (SEP) to the originally implanted solar gases, derived from a basic interpretation of He and Ne isotopes, yield values of about 10%. Analysis of the Ar isotopes requires a minimum of 20% SEP, and Kr isotopes, using our preferred composition for solar wind Kr, yield a result that overlaps both these values. It is possible to reconcile the data from these gases if significant loss of solar wind Ar, Kr and presumably Xe has occurred relative to the SEP component, most likely by erosive processes that are mass independent, although mass-dependent losses (Ar greater than Kr greater than Xe) cannot be excluded. If such losses did occur, the SEP contribution to the solar implanted gases must have been no more than a few percent. Nitrogen is a mixture of indigenous meteoritic N, whose isotopic composition is inferred to be relatively light, and implanted solar N, which has probably undergone diffusive redistribution and fractionation. If the heavy noble gases have not undergone diffusive loss, then N/Ar in the solar wind can be inferred to be at least several times the accepted solar ratio. The solar wind N appears, even after correction for fractionation effects, to have a minimum

  18. Noble metal based plasmonic nanomaterials and their application for bio-imaging and photothermal therapy

    NASA Astrophysics Data System (ADS)

    Zhu, Dewei

    During the past two decades, researchers have gained more and more insight into the manipulation of nanomaterials to create useful technologies. Numerous classes of nanomaterials have been produced and studied based upon their intriguing chemical and physical properties and their potential applications in diverse fields, ranging from electronics to renewable energy and biomedicine. In this dissertation, we describe the synthesis and potential biomedical applications of several types of noble metal-based nanomaterials in which we control size, shape, and coupling to other materials to tune their localized surface plasmon resonance (LSPR) interaction with light. We demonstrate the application of these novel nanostructures as contrast agents for photoacoustic imaging and as photosensitizers for photothermal therapy. Chapter one first presents protocols for producing monodisperse spherical nanoparticles of gold and silver. The diameter of the nanospheres can be adjusted from less than 2 nm to greater than 10 nm by controlling the reaction conditions, including ligands that cap the nanosphere surfaces, reaction time, and reaction temperature. Next, we describe the synthesis of multi-branched Au nanocrystals with predominantly tripodal, tetrapodal and star-shaped morphologies. We demonstrate tuning of the LSPR energy in these materials by changing the branch length. In the third part of this chapter, we present a novel method for coupling heavily-doped p-type copper selenide (Cu2-xSe) NPs with Au NPs by seeded nanocrystal growth to form a new type of semiconductor-metal heterogeneous nanostructure. This new class of plasmonic nanomaterials can simultaneously exhibit two types of LSPR in a single system, producing a broad optical absorbance that is nearly flat across the near infrared (NIR) spectral region (750-1150nm), along with a small shoulder at 566 nm that originates from the Au NP. We conclude this first chapter by demonstrating the use of self-doped copper sulfide

  19. Contrasting behavior of noble-metal elements during magmatic differentiation in basalts from the Cook Islands, Polynesia

    NASA Astrophysics Data System (ADS)

    Tatsumi, Yoshiyuki; Oguri, Kiwamu; Shimoda, Gen; Kogiso, Tetsu; Barsczus, Hans G.

    2000-02-01

    Concentrations of noble metals (Ir, Ru, Rh, Pt, Pd, and Au) in ocean-island basalts from the Cook Islands, Polynesia, were determined by improved fire-assay and tellurium coprecipitation techniques with an inductively-coupled-plasma mass spectrometer. Isotope, major element, and trace element compositions of these basalts indicate that the present samples include distinctive HIMU (high μ = high 238U/204Pb) and normal non-HIMU basalts. Examination based on Ni-Mg-Fe partitioning between olivine and liquid suggests an only minor effect of accumulation of phenocrysts in governing the compositional variations of the present samples. The fractionation trends obtained show monotonic decrease and increase in noble-metal elements with decreasing MgO content in HIMU and non-HIMU basalts, respectively. These characteristic trends indicate that HIMU magmas are differentiated by fractional crystallization and have higher sulfide/silicate ratios than non-HIMU basalts.

  20. Turning aluminium into a noble-metal-like catalyst for low-temperature activation of molecular hydrogen.

    PubMed

    Chopra, Irinder S; Chaudhuri, Santanu; Veyan, Jean François; Chabal, Yves J

    2011-11-01

    Activation of molecular hydrogen is the first step in producing many important industrial chemicals that have so far required expensive noble-metal catalysts and thermal activation. We demonstrate here that aluminium doped with very small amounts of titanium can activate molecular hydrogen at temperatures as low as 90 K. Using an approach that uses CO as a probe molecule, we identify the atomistic arrangement of the catalytically active sites containing Ti on Al(111) surfaces, combining infrared reflection-absorption spectroscopy and first-principles modelling. CO molecules, selectively adsorbed on catalytically active sites, form a complex with activated hydrogen that is removed at remarkably low temperatures (115 K; possibly as a molecule). These results provide the first direct evidence that Ti-doped Al can carry out the essential first step of molecular hydrogen activation under nearly barrierless conditions, thereby challenging the monopoly of noble metals in hydrogen activation. PMID:21946610

  1. Reorganization of a topological surface state: Theory for Bi2Te3(111) covered by noble metals

    NASA Astrophysics Data System (ADS)

    Muñoz, Francisco; Flieger, Markus; Henk, Jürgen; Mertig, Ingrid

    2014-09-01

    The electronic structure of Bi2Te3 covered by noble metals is investigated by first-principles calculations. The Dirac surface state of the topological insulator Bi2Te3 hybridizes with the sp states of the noble metal, which gives rise to strong reorganization of the surface electronic structure. Striking features of the modified Dirac surface state are (i) the introduction of new Dirac points within the fundamental band gap of Bi2Te3, (ii) a very weak dispersion, and (iii) a multisheeted Fermi surface which results in an orientation-dependent number of conducting channels in the fundamental band gap of Bi2Te3. Our findings have impact for spin-dependent surface transport.

  2. Bond Strength of Resin Cements to Noble and Base Metal Alloys with Different Surface Treatments

    PubMed Central

    Raeisosadat, Farkhondeh; Ghavam, Maryam; Hasani Tabatabaei, Masoomeh; Arami, Sakineh; Sedaghati, Maedeh

    2014-01-01

    Objectives: The bond strength of resin cements to metal alloys depends on the type of the metal, conditioning methods and the adhesive resins used. The purpose of this study was to evaluate the bond strength of resin cements to base and noble metal alloys after sand blasting or application of silano-pen. Materials and Method: Cylinders of light cured Z 250 composite were cemented to “Degubond 4” (Au Pd) and “Verabond” (Ni Cr) alloys by either RelyX Unicem or Panavia F2, after sandblasting or treating the alloys with Silano-Pen. The shear bond strengths were evaluated. Data were analyzed by three-way ANOVA and t tests at a significance level of P<0.05. Results: When the alloys were treated by Silano-Pen, RelyX Unicem showed a higher bond strength for Degubond 4 (P=0.021) and Verabond (P< 0.001). No significant difference was observed in the bond strength of Panavia F2 to the alloys after either of surface treatments, Degubond 4 (P=0.291) and Verabond (P=0.899). Panavia F2 showed a higher bond strength to sandblasted Verabond compared to RelyX Unicem (P=0.003). The bond strength of RelyX Unicem was significantly higher to Silano-Pen treated Verabond (P=0.011). The bond strength of the cements to sandblasted Degubond 4 showed no significant difference (P=0.59). RelyX Unicem had a higher bond strength to Silano-Pen treated Degubond 4 (P=0.035). Conclusion: The bond strength of resin cements to Verabond alloy was significantly higher than Degubond 4. RelyX Unicem had a higher bond strength to Silano-Pen treated alloys. Surface treatments of the alloys did not affect the bond strength of Panavia F2. PMID:25628687

  3. Optical properties of ZnO thin films dispersed with noble metal nanoparticles synthesized by sol-gel method

    NASA Astrophysics Data System (ADS)

    Wakaki, M.; Noguchi, T.; Yokoyama, E.

    2014-03-01

    Zinc Oxide (ZnO) is an inexpensive n-type semiconductor having a direct band gap of 3.3eV with a large exciton binding energy of 60meV. Noble metal nanoparticles show a surface plasmon resonance in the visible region due to collective oscillations of electrons at the surface of metal nanoparticles. The unique features in the composite system of dielectrics-metal nanoparticles have potential applications in optoelectronic devices such as transparent conductive films, solar cells, photocatalysts and so on. In this study, ZnO thin films dispersed with Ag or Au nanoparticles were synthesized using a sol-gel technique. X-ray diffraction peaks of ZnO films exhibited a pattern corresponding to the hexagonal wultzite structure. In the TEM analysis of ZnO-Au composite films, spherical Au nanoparticles were observed within the ZnO crystalline matrix. The distribution of the diameter of Au nanoparticles was centered at around 20nm and broadened with the half width of about 20nm. In the ZnO-Ag composite films, Ag nanoparticles grow larger as the annealing temperature becomes higher and various shape of Ag precipitations like triangular and square plates were observed in ZnO-Ag (50:50) composite films. The optical absorption peaks were observed at 580nm and 410nm due to the surface plasmon resonance of gold and silver nanoparticles, respectively. The absorption spectra were analyzed using a typical effective medium approximation of Maxwell-Garnett model and good fitting was obtained for a ZnO-Au composite film assuming spherical Au nanoparticle. The spectra were discussed relating with the size and shape of the nanoparticles, and the refractive index of the matrix.

  4. Noble metal based plasmonic nanomaterials and their application for bio-imaging and photothermal therapy

    NASA Astrophysics Data System (ADS)

    Zhu, Dewei

    During the past two decades, researchers have gained more and more insight into the manipulation of nanomaterials to create useful technologies. Numerous classes of nanomaterials have been produced and studied based upon their intriguing chemical and physical properties and their potential applications in diverse fields, ranging from electronics to renewable energy and biomedicine. In this dissertation, we describe the synthesis and potential biomedical applications of several types of noble metal-based nanomaterials in which we control size, shape, and coupling to other materials to tune their localized surface plasmon resonance (LSPR) interaction with light. We demonstrate the application of these novel nanostructures as contrast agents for photoacoustic imaging and as photosensitizers for photothermal therapy. Chapter one first presents protocols for producing monodisperse spherical nanoparticles of gold and silver. The diameter of the nanospheres can be adjusted from less than 2 nm to greater than 10 nm by controlling the reaction conditions, including ligands that cap the nanosphere surfaces, reaction time, and reaction temperature. Next, we describe the synthesis of multi-branched Au nanocrystals with predominantly tripodal, tetrapodal and star-shaped morphologies. We demonstrate tuning of the LSPR energy in these materials by changing the branch length. In the third part of this chapter, we present a novel method for coupling heavily-doped p-type copper selenide (Cu2-xSe) NPs with Au NPs by seeded nanocrystal growth to form a new type of semiconductor-metal heterogeneous nanostructure. This new class of plasmonic nanomaterials can simultaneously exhibit two types of LSPR in a single system, producing a broad optical absorbance that is nearly flat across the near infrared (NIR) spectral region (750-1150nm), along with a small shoulder at 566 nm that originates from the Au NP. We conclude this first chapter by demonstrating the use of self-doped copper sulfide

  5. Quasi-noble-metal graphene quantum dots deposited stannic oxide with oxygen vacancies: Synthesis and enhanced photocatalytic properties.

    PubMed

    Quan, Bin; Liu, Wei; Liu, Yousong; Zheng, Ying; Yang, Guangcheng; Ji, Guangbin

    2016-11-01

    Quasi-noble-metal graphene quantum dots (GQDs) deposited stannic oxide (SnO2) with oxygen vacancies (VOs) were prepared by simply sintering SnO2 and citric acid (CA) together. The redox process between SnO2 and GQDs shows the formation of oxygen vacancy states below the conduction band of stannic oxide. The produced VOs obviously extend the optical absorption region of SnO2 to the visible-light region. Meanwhile, GQDs can effectively improve the charge-separation efficiency via a quasi function like noble metal and promote the visible-light response to some degree. In addition, the samples calcinated at 450°C reveals the best performance because of its relatively high concentrations of VOs. What is more, the possible degradation mechanism has been inferred as extended visible-light response as well as raised charge-separation efficiency has also been put forward. Our work may offer a simple strategy to combine the defect modulation and noble metal deposition simultaneously for efficient photocatalysis. PMID:27450887

  6. Ab initio study of the trapping of polonium on noble metals

    NASA Astrophysics Data System (ADS)

    Rijpstra, Kim; Van Yperen-De Deyne, Andy; Maugeri, Emilio Andrea; Neuhausen, Jörg; Waroquier, Michel; Van Speybroeck, Veronique; Cottenier, Stefaan

    2016-04-01

    In the future MYRRHA reactor, lead bismuth eutectic (LBE) will be used both as coolant and as spallation target. Due to the high neutron flux a small fraction of the bismuth will transmute to radiotoxic 210Po. Part of this radiotoxic element will evaporate into the gas above the coolant. Extracting it from the gas phase is necessary to ensure a safe handling of the reactor. An issue in the development of suitable filters is the lack of accurate knowledge on the chemical interaction between a candidate filter material and either elemental polonium or polonium containing molecules. Experimental work on this topic is complicated by the high radiotoxicity of polonium. Therefore, we present in this paper a first-principles study on the adsorption of polonium on noble metals as filter materials. The adsorption of monoatomic Po is considered on the candidate filter materials palladium, platinum, silver and gold. The case of the gold filter is looked upon in more detail by examining how bismuth pollution affects its capability to capture polonium and by studying the adsorption of the heavy diatomic molecules Po2, PoBi and PoPb on this gold filter.

  7. Behavior of noble metals upon fractional crystallization of copper-rich sulfide melts

    NASA Astrophysics Data System (ADS)

    Distler, V. V.; Sinyakova, E. F.; Kosyakov, V. I.

    2016-08-01

    Joint behavior of Pt, Pd, Au, As, Bi, Te, and Sn upon fractional crystallization was studied in a melt of cubanite composition with the following admixtures (mol %): Fe, 33.20; Cu, 16.55; S, 50.03; Pt, 0.03; Pd, 0.02; Au, 0.02; As, 0.02; Bi, 0.03; Te, 0.02; Sn, 0.08. The crystallized sample consisted of three zones: (I) a pyrrhotite solid solution POSS; (II) an isocubanite ICB; (III) a multiphase mixture. The behavior of admixtures was studied in the first and second zones. It was shown that pyrrhotite did not contain admixtures of noble metals and accessory elements, whereas Sn was dissolved in cubanite. Other admixtures occurred in the second zone as multiphase inclusions. PdBi x Te1- x , PtBiS3-δ, CuPtBiS3, Bi2S3- x , Au, Pt(As,S)2, (Pt,Pd)S, (Pt,Pd)(Bi,Te)2- x , and PdBi2 were the most abundant phases.

  8. Catalytic conversion of CHx and CO2 on non-noble metallic impurities in graphene.

    PubMed

    Tang, Yanan; Liu, Zhiyong; Chen, Weiguang; Ma, Dongwei; Chang, Shanshan; Dai, Xianqi

    2016-06-22

    Density functional theory (DFT) was applied to investigate the geometric, electronic, and magnetic properties of CHx (x = 0, 1, 2, 3, 4) species on non-noble metal embedded graphene (NNM-graphene). It was found that the different stabilities of CHx species can modify the electronic structures and magnetic properties of NNM-graphene systems. The carbonaceous reforming reactions include conversion of CHx (x = 0, 1, 2 and 3) species by hydrogen molecules (H2) to form CHx+2 species or oxidation of C atoms by oxygen molecules to form CO2. In the hydrogenation reactions, deposited C atoms can be converted easily into CHx species overcoming small energy barriers. In comparison, coadsorption of C and O2 to generate CO2 encounters relatively larger energy barriers on the NNM-graphene. Hence, the coadsorption of CHx and H2 as the starting state is energetically more favorable and formation of CHx species can reduce amounts of carbon deposition. Among the NNM-graphene substrates studied, moderate adsorption energies and low reaction barriers of CHx species are more likely to occur on the Co-graphene surface, thus the hydrogenation reaction is able to inhibit carbon deposition on the NNM-graphene surface while maintaining high activity. PMID:27296782

  9. Spin-Orbit Effects in the Quasiparticle Bandstructure of Noble Metals

    NASA Astrophysics Data System (ADS)

    Mustafa, Jamal; Louie, Steven

    2014-03-01

    Applications of the GW approximation to the electron self-energy have proven quite successful for calculating the quasiparticle properties of materials. We find that for the noble metals, in line with previous work in such calculations, the semicore states need to be taken into account. We show that, with these semicore states, a large cutoff must be used to describe the screening and, in turn, a large number of empty states must be included. Taking all of this into account, and carefully checking convergence, shows G0W0 can describe experimental results from angle-resolved photoemission spectroscopy quite well when the effects of spin-orbit coupling is also included. We compare our results to recent self-consistent GW calculations on gold. This work was supported by NSF grant No. DMR10-1006184 and U.S. DOE under Contract No. DE-AC02-05CH11231. Computational resources have been provided by DOE at LBNL's NERSC facility.

  10. The electronic properties of noble metal doped silicon nanocrystals using hybrid density functional theory

    NASA Astrophysics Data System (ADS)

    Mayfield, Cedric Leon

    One of the most challenging issues in semiconductor physics is to engineer band structures for a particular device. Contemporary photovoltaic (PV) and photoelectrochemical (PEC) devices rely on defect energy levels and nano-scaling to customize their band structures. As the length scale of a material becomes comparable to the exciton Bohr radius the free particle behavior of charge carriers transition to bound states where energy levels are quantized. In this thesis, hybrid density functional theory has been used to study the electronic properties of silicon nanocrystals (SiNCs) having 75, 150 and 300 silicon atoms. The atomic coordinates were defined by two geometries (diamond and wurtzite) of bulk phase silicon. The global minimum energy structures for both geometries at each size were found for particular variation on magnetic moments, dopant, dopant position, and surface passivation with hydrogen. We report our results on bond lengths, binding energies, formation energies, HOMO-LUMO gaps, and density of states. We also report results on electronic occupations derived from Mulliken population analysis. Our results show that the SiNCs have tunable HOMO-LUMO gaps with respect to size and that the inclusion of noble metals produces inter-gap defect levels. In addition, we have found that hydrogen passivation affected the doping behavior significantly. Contrary to the general expectation, hydrogen passivation contributed to the energy levels near the highest occupied orbital. Overall, our results suggest the SiNCs can be used to construct optimal photovoltaic applications or used individually as photocatalysts.

  11. Catalytic conversion of CHx and CO2 on non-noble metallic impurities in graphene.

    PubMed

    Tang, Yanan; Liu, Zhiyong; Chen, Weiguang; Ma, Dongwei; Chang, Shanshan; Dai, Xianqi

    2016-06-22

    Density functional theory (DFT) was applied to investigate the geometric, electronic, and magnetic properties of CHx (x = 0, 1, 2, 3, 4) species on non-noble metal embedded graphene (NNM-graphene). It was found that the different stabilities of CHx species can modify the electronic structures and magnetic properties of NNM-graphene systems. The carbonaceous reforming reactions include conversion of CHx (x = 0, 1, 2 and 3) species by hydrogen molecules (H2) to form CHx+2 species or oxidation of C atoms by oxygen molecules to form CO2. In the hydrogenation reactions, deposited C atoms can be converted easily into CHx species overcoming small energy barriers. In comparison, coadsorption of C and O2 to generate CO2 encounters relatively larger energy barriers on the NNM-graphene. Hence, the coadsorption of CHx and H2 as the starting state is energetically more favorable and formation of CHx species can reduce amounts of carbon deposition. Among the NNM-graphene substrates studied, moderate adsorption energies and low reaction barriers of CHx species are more likely to occur on the Co-graphene surface, thus the hydrogenation reaction is able to inhibit carbon deposition on the NNM-graphene surface while maintaining high activity.

  12. A noble-metal-free system for photocatalytic hydrogen production from water.

    PubMed

    Mejía, Esteban; Luo, Shu-Ping; Karnahl, Michael; Friedrich, Aleksej; Tschierlei, Stefanie; Surkus, Annette-Enrica; Junge, Henrik; Gladiali, Serafino; Lochbrunner, Stefan; Beller, Matthias

    2013-11-18

    A series of heteroleptic copper(I) complexes with bidentate PP and NN chelate ligands was prepared and successfully applied as photosensitizers in the light-driven production of hydrogen, by using [Fe3(CO)12] as a water-reduction catalyst (WRC). These systems efficiently reduces protons from water/THF/triethylamine mixtures, in which the amine serves as a sacrificial electron donor (SR). Turnover numbers (for H) up to 1330 were obtained with these fully noble-metal-free systems. The new complexes were electrochemically and photophysically characterized. They exhibited a correlation between the lifetimes of the MLCT excited state and their efficiency as photosensitizers in proton-reduction systems. Within these experiments, considerably long excited-state lifetimes of up to 54 μs were observed. Quenching studies with the SR, in the presence and absence of the WRC, showed that intramolecular deactivation was more efficient in the former case, thus suggesting the predominance of an oxidative quenching pathway. PMID:24123302

  13. Recent Advances in the Field of Bionanotechnology: An Insight into Optoelectric Bacteriorhodopsin, Quantum Dots, and Noble Metal Nanoclusters

    PubMed Central

    Knoblauch, Christopher; Griep, Mark; Friedrich, Craig

    2014-01-01

    Molecular sensors and molecular electronics are a major component of a recent research area known as bionanotechnology, which merges biology with nanotechnology. This new class of biosensors and bioelectronics has been a subject of intense research over the past decade and has found application in a wide variety of fields. The unique characteristics of these biomolecular transduction systems has been utilized in applications ranging from solar cells and single-electron transistors (SETs) to fluorescent sensors capable of sensitive and selective detection of a wide variety of targets, both organic and inorganic. This review will discuss three major systems in the area of molecular sensors and electronics and their application in unique technological innovations. Firstly, the synthesis of optoelectric bacteriorhodopsin (bR) and its application in the field of molecular sensors and electronics will be discussed. Next, this article will discuss recent advances in the synthesis and application of semiconductor quantum dots (QDs). Finally, this article will conclude with a review of the new and exciting field of noble metal nanoclusters and their application in the creation of a new class of fluorescent sensors. PMID:25340449

  14. Rational design of binder-free noble metal/metal oxide arrays with nanocauliflower structure for wide linear range nonenzymatic glucose detection.

    PubMed

    Li, Zhenzhen; Xin, Yanmei; Zhang, Zhonghai; Wu, Hongjun; Wang, Peng

    2015-01-01

    One-dimensional nanocomposites of metal-oxide and noble metal were expected to present superior performance for nonenzymatic glucose detection due to its good conductivity and high catalytic activity inherited from noble metal and metal oxide respectively. As a proof of concept, we synthesized gold and copper oxide (Au/CuO) composite with unique one-dimensional nanocauliflowers structure. Due to the nature of the synthesis method, no any foreign binder was needed in keeping either Au or CuO in place. To the best of our knowledge, this is the first attempt in combining metal oxide and noble metal in a binder-free style for fabricating nonenzymatic glucose sensor. The Au/CuO nanocauliflowers with large electrochemical active surface and high electrolyte contact area would promise a wide linear range and high sensitive detection of glucose with good stability and reproducibility due to its good electrical conductivity of Au and high electrocatalytic activity of CuO. PMID:26068705

  15. Rational design of binder-free noble metal/metal oxide arrays with nanocauliflower structure for wide linear range nonenzymatic glucose detection

    PubMed Central

    Li, Zhenzhen; Xin, Yanmei; Zhang, Zhonghai; Wu, Hongjun; Wang, Peng

    2015-01-01

    One-dimensional nanocomposites of metal-oxide and noble metal were expected to present superior performance for nonenzymatic glucose detection due to its good conductivity and high catalytic activity inherited from noble metal and metal oxide respectively. As a proof of concept, we synthesized gold and copper oxide (Au/CuO) composite with unique one-dimensional nanocauliflowers structure. Due to the nature of the synthesis method, no any foreign binder was needed in keeping either Au or CuO in place. To the best of our knowledge, this is the first attempt in combining metal oxide and noble metal in a binder-free style for fabricating nonenzymatic glucose sensor. The Au/CuO nanocauliflowers with large electrochemical active surface and high electrolyte contact area would promise a wide linear range and high sensitive detection of glucose with good stability and reproducibility due to its good electrical conductivity of Au and high electrocatalytic activity of CuO. PMID:26068705

  16. Non-noble electrocatalysts for alkaline fuel cells

    NASA Technical Reports Server (NTRS)

    Sarangapani, S.; Lessner, P.; Manoukian, M.; Giner, J.

    1989-01-01

    Carbons activated with macrocyclics have attracted increasing attention as alternative electrocatalysts for oxygen reduction. Initial activity of these catalysts is good, but performance declines rapidly. Pyrolyzing the macrocyclic on the carbon support leads to enhanced stability and the catalysts retain good activity. The approach described is designed to develop bulk doped catalysts with similar structures to pyrolyzed macrocyclic catalysts. The transition metal and coordinated ligands are dispersed throughout the bulk of the conductive carbon skeleton. Two approaches to realizing this concept are being pursued, both involving the doping of carbon precursors. In one approach, the precursor is a solid phase carbon-containing ion-exchange resin. The precursor is doped with a transition metal and/or nitrogen, and the resulting mixture is pyrolyzed. In the other approach, the precursor is a gas-phase hydrocarbon. This is introduced with a transition metal species and nitrogen species into a reactor and pyrolyzed. Several studies have been conducted to determine if there is a synergistic effect between the transition metal and nitrogen and the effect of different methods of introducing the metal-nitrogen (M-N) coordination on performance. One approach was to introduce the metal and nitrogen separately, for example, by sequentially doping FeCl3 and NH4OH into the resin. Catalysts were prepared from an undoped ion-exchange resin, a resin doped only with N, a resin doped only with Fe, and a resin doped with both Fe and N. Introduction of nitrogen alone has no beneficial effect on the performance of the catalysts. The introduction of the Fe alone significantly improves the performance in both the high and low current density regions. When both Fe and N are introduced, the performance at lower current densities (catalytic activity) is increased beyond that of the Fe-doped carbon, but the performance at higher current densities is similar to the carbon containing only Fe

  17. Preparation and evaluation of novel hydrous metal oxide (HMO)-supported noble metal catalysts

    SciTech Connect

    Gardner, T.J.; McLaughlin, L.I.; Evans, L.R.; Datye, A.K.

    1998-04-01

    Hydrous Metal Oxides (HMOs) are chemically synthesized materials that, because of their high cation exchange capacity, possess a unique ability to allow the preparation of highly dispersed supported-metal catalyst precursors with high metal loadings. This study evaluates high weight loading Rh/HMO catalysts with a wide range of HMO support compositions, including hydrous titanium oxide (HTO), silica-doped hydrous titanium oxide (HTO:Si), hydrous zirconium oxide (HZO), and silica-doped hydrous zirconium oxide (HZO:Si), against conventional oxide-supported Rh catalysts with similar weight loadings and support chemistries. Catalyst activity measurements for a structure-sensitive model reaction (n-butane hydrogenolysis) as a function of catalyst activation conditions show superior activity and stability for the ZrO{sub 2}, HZO, and HZO:Si supports, although all of the Rh/HMO catalysts have high ethane selectivity indicative of high Rh dispersion. For the TiO{sub 2}-, HTO-, and HTO:Si supported Rh catalysts, a significant loss of both catalyst activity and Rh dispersion is observed at more aggressive activation conditions, consistent with TiO{sub x} migration associated with SMSI phenomena. Of all the Rh/HMO catalysts, the Rh/HZO:Si catalysts appear to offer the best tradeoff in terms of high Rh dispersion, high activity, and high selectivity.

  18. Enantioselectivity of (321) chiral noble metal surfaces: a density functional theory study of lactate adsorption.

    PubMed

    Franke, J-H; Kosov, D S

    2013-12-14

    The adsorption of the chiral molecule lactate on the intrinsically chiral noble metal surfaces Pt(321), Au(321), and Ag(321) is studied by density functional theory calculations. We use the oPBE-vdW functional which includes van der Waals forces on an ab initio level. It is shown that the molecule binds via its carboxyl and the hydroxyl oxygen atoms to the surface. The binding energy is larger on Pt(321) and Ag(321) than on Au(321). An analysis of the contributions to the binding energy of the different molecular functional groups reveals that the deprotonated carboxyl group contributes most to the binding energy, with a much smaller contribution of the hydroxyl group. The Pt(321) surface shows considerable enantioselectivity of 0.06 eV. On Au(321) and Ag(321) it is much smaller if not vanishing. The chiral selectivity of the Pt(321) surface can be explained by two factors. First, it derives from the difference in van der Waals attraction of L- and D-lactate to the surface that we trace to differences in the binding energy of the methyl group. Second, the multi-point binding pattern for lactate on the Pt(321) surface is sterically more sensitive to surface chirality and also leads to large binding energy contributions of the hydroxyl group. We also calculate the charge transfer to the molecule and the work function to gauge changes in electronic structure of the adsorbed molecule. The work function is lowered by 0.8 eV on Pt(321) with much smaller changes on Au(321) and Ag(321). PMID:24329084

  19. Enantioselectivity of (321) chiral noble metal surfaces: A density functional theory study of lactate adsorption

    SciTech Connect

    Franke, J.-H.; Kosov, D. S.

    2013-12-14

    The adsorption of the chiral molecule lactate on the intrinsically chiral noble metal surfaces Pt(321), Au(321), and Ag(321) is studied by density functional theory calculations. We use the oPBE-vdW functional which includes van der Waals forces on an ab initio level. It is shown that the molecule binds via its carboxyl and the hydroxyl oxygen atoms to the surface. The binding energy is larger on Pt(321) and Ag(321) than on Au(321). An analysis of the contributions to the binding energy of the different molecular functional groups reveals that the deprotonated carboxyl group contributes most to the binding energy, with a much smaller contribution of the hydroxyl group. The Pt(321) surface shows considerable enantioselectivity of 0.06 eV. On Au(321) and Ag(321) it is much smaller if not vanishing. The chiral selectivity of the Pt(321) surface can be explained by two factors. First, it derives from the difference in van der Waals attraction of L- and D-lactate to the surface that we trace to differences in the binding energy of the methyl group. Second, the multi-point binding pattern for lactate on the Pt(321) surface is sterically more sensitive to surface chirality and also leads to large binding energy contributions of the hydroxyl group. We also calculate the charge transfer to the molecule and the work function to gauge changes in electronic structure of the adsorbed molecule. The work function is lowered by 0.8 eV on Pt(321) with much smaller changes on Au(321) and Ag(321)

  20. Strongly coupled hybrid nanostructures for selective hydrogen detection - understanding the role of noble metals in reducing cross-sensitivity

    NASA Astrophysics Data System (ADS)

    Liu, Bin; Cai, Daoping; Liu, Yuan; Wang, Dandan; Wang, Lingling; Xie, Wuyuan; Li, Qiuhong; Wang, Taihong

    2014-04-01

    Noble metal-semiconductor hybrid nanostructures can offer outperformance to gas sensors in terms of sensitivity and selectivity. In this work, a catalytically activated (CA) hydrogen sensor is realized based on strongly coupled Pt/Pd-WO3 hybrid nanostructures constructed by a galvanic replacement participated solvothermal procedure. The room-temperature operation and high selectivity distinguish this sensor from the traditional ones. It is capable of detecting dozens of parts per million (ppm) hydrogen in the presence of thousands of ppm methane gas. An insight into the role of noble metals in reducing cross-sensitivity is provided by comparing the sensing properties of this sensor with a traditional thermally activated (TA) one made from the same pristine WO3. Based on both experimental and density functional theory (DFT) calculation results, the cross-sensitivity of the TA sensor is found to have a strong dependence on the highest occupied molecular orbital (HOMO) level of the hydrocarbon molecules. The high selectivity of the CA sensor comes from the reduced impact of gas frontier orbitals on the charge transfer process by the nano-scaled metal-semiconductor (MS) interface. The methodology demonstrated in this work indicates that rational design of MS hybrid nanostructures can be a promising strategy for highly selective gas sensing applications.Noble metal-semiconductor hybrid nanostructures can offer outperformance to gas sensors in terms of sensitivity and selectivity. In this work, a catalytically activated (CA) hydrogen sensor is realized based on strongly coupled Pt/Pd-WO3 hybrid nanostructures constructed by a galvanic replacement participated solvothermal procedure. The room-temperature operation and high selectivity distinguish this sensor from the traditional ones. It is capable of detecting dozens of parts per million (ppm) hydrogen in the presence of thousands of ppm methane gas. An insight into the role of noble metals in reducing cross

  1. Synthesis, characterization and application of noble-metal nanoparticles and their Langmuir films

    NASA Astrophysics Data System (ADS)

    Sun, Yuan

    Noble-metal nanoparticles and their Langmuir films have attracted remarkable research interest due to their unique properties and potential applications in catalysis, hydrogen storage materials, and optical, magnetic and electronic devices. The properties of nanoparticles are affected not only by the size, but also by the shape. In this dissertation, highly crystalline rectangular palladium nanoparticles have been successfully synthesized via the reduction of K2PdCl 4 by ascorbic acid in the presence of a surfactant cetyltrimethylammonium bromide under room temperature. Trisodium citrate is a key factor for high yield of nanocubes and nanorods. The average length and aspect ratio of the nanorods can be tuned by varying the concentration of trisodium citrate. These rectangular nanoparticles were stable for months as colloids. However, after being exposed to air for about 100 days, the dry nanoparticles on TEM grids were oxidized to form shells of 1.6--3.8 nm thick covering the nanoparticle surfaces. This procedure is conducted under room temperature and requires no seed-mediated growth or nanoporous rigid template so that it is easier and more practical for large-scale synthesis. Alkanethiolate palladium nanoparticles can be synthesized by two routes: a one-phase method and a two-phase method. In order to understand the electronic and chemical properties of dodecanethiolate palladium nanoparticles, a systematic comparison between the particles obtained by these two synthetic techniques was conducted. From transmission electron microscopy (TEM) we determined that the particle sizes were 46 +/- 10 A and 20 +/- 5 A for the 1- and 2-phase particles, respectively. Electron diffraction confirmed that their structure was face-centered cubic (FCC). High-resolution TEM (HRTEM) showed that the 1-phase particles had an ordered core surrounded by a disordered shell structure while the 2-phase particles appeared to be crystalline throughout. The particles were also analyzed with

  2. Strategies and applications of combinatorial methods and high throughput screening to the discovery of non-noble metal catalyst

    NASA Astrophysics Data System (ADS)

    Bricker, Maureen L.; Sachtler, J. W. Adriaan; Gillespie, Ralph D.; McGonegal, Charles P.; Vega, Honorio; Bem, Dave S.; Holmgren, Jennifer S.

    2004-02-01

    The integrated End-to-End™ combinatorial process for catalyst preparation and screening, with emphasis on its capability to vary both process and compositional parameters will be demonstrated. Additionally, each step of the combinatorial screening process has been validated against results from traditional screening methods. The greatest challenge of all has been the adherence to the core concepts of the combinatorial approach. Catalyst libraries have been made and tested for naphthalene dehydrogenation chemistry. The preparation of these libraries has included the application of high throughput techniques for: metal impregnation; catalyst finishing; catalyst screening. The catalyst screening system has been used to find a non-noble metal catalyst system that can replace Pt in dehydrogenation applications in the petroleum industry. A proprietary catalytic composition was developed for the dehydrogenation of methylcyclohexane (MCH) to toluene starting with four non-noble metals of different proportions and four different supports (alumina, titania, zirconia and silica) prepared in different ways and applying a statistical design of experiments. These data demonstrate that all steps of catalyst preparation and screening are performed in a rapid, useful, high throughput manner. Data will be presented from the catalyst screening efforts will demonstrate that optimized metal composition is dependent on the support type.

  3. Optimization of Single and Bimetallic Noble Metal Catalysts by Strong Electrostatic Adsorption

    NASA Astrophysics Data System (ADS)

    Barnes, Sean E.

    Heterogeneous catalysts are used in over 90% of chemical processes today. These small metal particles maximize the number of active sites present, which leads to cheaper, more effective catalysts. However, the preparation of heterogeneous catalysts is still a "dark art". An alternate to dry impregnation is the method of Strong Electrostatic Adsorption (SEA). In this method the surface hydroxyl groups of the support can either protonate or deprotonate depending on the pH of the contacting solution. These surface groups then can then attract oppositely charged metal precursors. Preparation of catalysts by SEA leads to the anchoring of small, well dispersed, highly active metal particles. The aim of this work is to optimize the preparation via SEA of various supported catalysts systems, particularly Pt/carbon, Au supported on a variety of materials, and Au-Pd/carbon. Carbon supported metal catalysts are becoming increasingly important not just as electro catalyst in fuel cells, but for many aqueous phase biomass conversion reactions.

  4. Ice-templated synthesis of multifunctional three dimensional graphene/noble metal nanocomposites and their mechanical, electrical, catalytic, and electromagnetic shielding properties

    PubMed Central

    Sahoo, P. K.; Aepuru, Radhamanohar; Panda, Himanshu Sekhar; Bahadur, D.

    2015-01-01

    In-situ homogeneous dispersion of noble metals in three-dimensional graphene sheets is a key tactic for producing macroscopic architecture, which is desirable for practical applications, such as electromagnetic interference shielding and catalyst. We report a one-step greener approach for developing porous architecture of 3D-graphene/noble metal (Pt and Ag) nanocomposite monoliths. The resulting graphene/noble metal nanocomposites exhibit a combination of ultralow density, excellent elasticity, and good electrical conductivity. Moreover, in order to illuminate the advantages of the 3D-graphene/noble metal nanocomposites, their electromagnetic interference (EMI) shielding and electrocatalytic performance are further investigated. The as-synthesized 3D-graphene/noble metal nanocomposites exhibit excellent EMI shielding effectiveness when compared to bare graphene; the effectiveness has an average of 28 dB in the 8.2–12.4 GHz X-band range. In the electro-oxidation of methanol, the 3D-graphene/Pt nanocomposite also exhibits significantly enhanced electrocatalytic performance and stability than compared to reduced graphene oxide/Pt and commercial Pt/C. PMID:26638827

  5. Ice-templated synthesis of multifunctional three dimensional graphene/noble metal nanocomposites and their mechanical, electrical, catalytic, and electromagnetic shielding properties

    NASA Astrophysics Data System (ADS)

    Sahoo, P. K.; Aepuru, Radhamanohar; Panda, Himanshu Sekhar; Bahadur, D.

    2015-12-01

    In-situ homogeneous dispersion of noble metals in three-dimensional graphene sheets is a key tactic for producing macroscopic architecture, which is desirable for practical applications, such as electromagnetic interference shielding and catalyst. We report a one-step greener approach for developing porous architecture of 3D-graphene/noble metal (Pt and Ag) nanocomposite monoliths. The resulting graphene/noble metal nanocomposites exhibit a combination of ultralow density, excellent elasticity, and good electrical conductivity. Moreover, in order to illuminate the advantages of the 3D-graphene/noble metal nanocomposites, their electromagnetic interference (EMI) shielding and electrocatalytic performance are further investigated. The as-synthesized 3D-graphene/noble metal nanocomposites exhibit excellent EMI shielding effectiveness when compared to bare graphene; the effectiveness has an average of 28 dB in the 8.2-12.4 GHz X-band range. In the electro-oxidation of methanol, the 3D-graphene/Pt nanocomposite also exhibits significantly enhanced electrocatalytic performance and stability than compared to reduced graphene oxide/Pt and commercial Pt/C.

  6. Influence of the preparation method on the surface characteristics and activity of boron-nitride-supported noble metal catalysts.

    PubMed

    Postole, Georgeta; Gervasini, Antonella; Guimon, Claude; Auroux, Aline; Bonnetot, Bernard

    2006-06-29

    In this article, we report how variations in the preparation method of boron-nitride-supported noble metal catalysts may influence the surface characteristics of the active phase and consequently the potential applications as catalysts for oxidation reactions. The deposition and the dispersion of the active phase are strongly influenced by the preparation process and in particular by the protic or aprotic solvent used as the dispersing phase; in this study, benzene, glyme, water, tetrahydrofuran, diglyme, 2-propanol, and glycol have been investigated. Characterization techniques, such as Brunauer-Emmett-Teller, X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis, have been used to study the influence of the choice of a solvent phase on the particle size and dispersion of the metal deposited on the BN support. The modifications undergone by the support during the deposition of palladium in different solvents have also been studied. Through the use of the same deposition procedure, different noble metal coatings (Pt, Pd, Au, and Ag) have been prepared. The acidic and redox characteristics of the resulting samples were characterized by temperature-programmed reduction and adsorption microcalorimetry. The catalytic performances of these materials were tested in the total oxidation of methane in lean conditions (excess oxygen and presence of water). PMID:16800586

  7. Expeditious synthesis of noble metal nanoparticles using Vitamin B12 under microwave irradiation

    EPA Science Inventory

    A greener synthesis protocol for noble nanometals is developed using vitamin B12 as a reducing and capping agent in conjunction with the use of microwaves. Successful assembly of nanoparticles or microparticles with varied shapes and sizes have been demonstrated. The synthesized ...

  8. Reaction pathways of biomass-derived oxygenates on noble metal surfaces

    NASA Astrophysics Data System (ADS)

    McManus, Jesse R.

    As the global demand for energy continues to rise, the environmental concerns associated with increased fossil fuel consumption have motivated the use of biomass as an alternative, carbon-renewable energy feedstock. Controlling reactive chemistry of the sugars that comprise biomass through the use of catalysis becomes essential in effectively producing green fuels and value-added chemicals. Recent work on biomass conversion catalysts have demonstrated the efficacy of noble metal catalyst systems for the reforming of biomass to hydrogen fuel, and the hydrodeoxygenation of biomass-derived compounds to value-added chemicals. In particular, Pt and Pd surfaces have shown considerable promise as reforming catalysts in preliminary aqueous phase reforming studies. It becomes important to understand the mechanisms by which these molecules react on the catalyst surfaces in order to determine structure-activity relationships and bond scission energetics as to provide a framework for engineering more active and selective catalysts. Fundamental surface science techniques provide the tools to do this; however, work in this field has been so far limited to simple model molecules like ethanol and ethylene glycol. Herein, temperature programmed desorption and high resolution electron energy loss spectroscopy are utilized in an ultra-high vacuum surface science study of the biomass-derived sugar glucose on Pt and Pd single crystal catalysts. Overall, it was determined that the aldehyde function of a ring-open glucose molecule plays an integral part in the initial bonding and reforming reaction pathway, pointing to the use of aldoses glycolaldehyde and glyceraldehyde as the most appropriate model compounds for future studies. Furthermore, the addition of adatom Zn to a Pt(111) surface was found to significantly decrease the C-H and C-C bond scission activity in aldehyde containing compounds, resulting in a preferred deoxygenation pathway in opposition to the decarbonylation pathway

  9. Catalytic pyrolysis of wheat bran for hydrocarbons production in the presence of zeolites and noble-metals by using TGA-FTIR method.

    PubMed

    Lazdovica, K; Liepina, L; Kampars, V

    2016-05-01

    Pyrolysis of wheat bran with or without catalysts was investigated using TGA-FTIR method in order to determine the influence of zeolite and noble metal catalysts on the evolution profile and relative yield of the volatile compounds. The addition of all catalysts decreased the volatile matter of wheat bran from 76.3% to 75.9%, 73.9%, 73.5%, 69.7% and increased the solid residue from 18.0% to 18.4%, 20.4%, 20.8%, 24.6% under the catalyst of ZSM-5, 5% Pd/C, MCM-41, and 5% Pt/C. Noble-metal catalysts had higher activity for deoxygenation of compounds containing carbonyl, carboxyl, and hydroxyl groups than zeolites. Degradation of nitrogen containing compounds atom proceeded better in presence of zeolites. Noble-metal catalysts promoted formation of aromatics and changed the profiles of evolved compounds whereas zeolites advanced formation of aliphatics and olefins.

  10. General Self-Assembly Route toward Sparsely Studded Noble-Metal Nanocrystals inside Graphene Hollow Sphere Network for Ultrastable Electrocatalyst Utilization.

    PubMed

    Lou, Xinyuan; Wu, Ping; Zhang, Anping; Zhang, Ruoqing; Tang, Yawen

    2015-09-16

    Herein, we rationally design and construct a novel type of sparsely studded noble-metal nanocrystals inside graphene hollow sphere network (abbreviated as noble-metal@G HSN) through an electrostatic-attraction-directed self-assembly approach. The formation of Pt@G and Pd@G hollow sphere networks have been illustrated as examples using SiO2 spheres as templates. Moreover, the electrocatalytic performance of the Pt@G HSN for methanol oxidation reaction has been examined as a proof-of-concept demonstration of the compositional and structural superiorities of noble-metal@G HSN toward electrocatalyst utilization. The as-prepared Pt@G HSN manifests higher catalytic activity and markedly enhanced long-term durability in comparison with commercial Pt/C catalyst. PMID:26305582

  11. Synthesis and characterization of fluorescence-labelled silica core-shell and noble metal-decorated ceria nanoparticles

    PubMed Central

    Rennhak, Markus; Reller, Armin

    2014-01-01

    Summary The present review article covers work done in the cluster NPBIOMEM in the DFG priority programme SPP 1313 and focuses on synthesis and characterization of fluorescent silica and ceria nanoparticles. Synthetic methods for labelling of silica and polyorganosiloxane/silica core–shell nanoparticles with perylenediimide derivatives are described, as well as the modification of the shell with thiol groups. Photometric methods for the determination of the number of thiol groups and an estimate for the number of fluorescent molecules per nanoparticles, including a scattering correction, have been developed. Ceria nanoparticles decorated with noble metals (Pt, Pd, Rh) are models for the decomposition products of automobile catalytic converters which appear in the exhaust gases and finally interact with biological systems including humans. The control of the degree of agglomeration of small ceria nanoparticles is the basis for their synthesis. Almost monodisperse agglomerates (40 ± 4–260 ± 40 nm diameter) can be prepared and decorated with noble metal nanoparticles (2–5 nm diameter). Fluorescence labelling with ATTO 647N gave the model particles which are now under biophysical investigation. PMID:25671137

  12. Functionalized alkoxysilane mediated controlled synthesis of noble metal nanoparticles dispersible in aqueous and non-aqueous medium.

    PubMed

    Pandey, Prem C; Pandey, Ashish K; Pandey, G

    2014-09-01

    The synthesis of amphiphilic noble metal nanoparticles involving the functional role of 3-aminopropyltrimethoxysilane (3-APTMS) and 3-glycidoxypropyltrimethoxy-silane (3-GPTMS) is reported herein. The mechanistic approach on the reactivity of these functional alkoxysilane for the typical controlled synthesis of AuNPs as evidenced from UV-visible spectroscopy and transmission electron microscopy (TEM) is reported. The experimental findings demonstrate the followings; (1) Methanolic solution of 3-GPTMS undergo interaction with 3-APTMS and the same is facilitated in the presence of 3-APTMS treated noble metal ions, (2) The molar ratio of 3-GPTMS/3-APTMS control the nanogeometry as well as the dispersibility of AuNPs in both aqueous and non-aqueous media, (3) the dispersion ability of nanoparticles is found to be based on the hydrophobic alkyl chain of the reaction product of 3-GPTMS and 3-APTMS, and (4) AuNPs shows absorption maxima as a function of polarity and refractive index of the medium. A typical application of as synthesized AuNPs as peroxidase mimetic is reported.

  13. Noble metal-based bimetallic nanoparticles: the effect of the structure on the optical, catalytic and photocatalytic properties.

    PubMed

    Zaleska-Medynska, Adriana; Marchelek, Martyna; Diak, Magdalena; Grabowska, Ewelina

    2016-03-01

    Nanoparticles composed of two different metal elements show novel electronic, optical, catalytic or photocatalytic properties from monometallic nanoparticles. Bimetallic nanoparticles could show not only the combination of the properties related to the presence of two individual metals, but also new properties due to a synergy between two metals. The structure of bimetallic nanoparticles can be oriented in random alloy, alloy with an intermetallic compound, cluster-in-cluster or core-shell structures and is strictly dependent on the relative strengths of metal-metal bond, surface energies of bulk elements, relative atomic sizes, preparation method and conditions, etc. In this review, selected properties, such as structure, optical, catalytic and photocatalytic of noble metals-based bimetallic nanoparticles, are discussed together with preparation routes. The effects of preparation method conditions as well as metal properties on the final structure of bimetallic nanoparticles (from alloy to core-shell structure) are followed. The role of bimetallic nanoparticles in heterogeneous catalysis and photocatalysis are discussed. Furthermore, structure and optical characteristics of bimetallic nanoparticles are described in relation to the some features of monometallic NPs. Such a complex approach allows to systematize knowledge and to identify the future direction of research.

  14. IMPACT OF NOBLE METALS AND MERCURY ON HYDROGEN GENERATION DURING HIGH LEVEL WASTE PRETREATMENT AT THE SAVANNAH RIVER SITE

    SciTech Connect

    Stone, M; Tommy Edwards, T; David Koopman, D

    2009-03-03

    The Defense Waste Processing Facility (DWPF) at the Savannah River Site vitrifies radioactive High Level Waste (HLW) for repository internment. The process consists of three major steps: waste pretreatment, vitrification, and canister decontamination/sealing. HLW consists of insoluble metal hydroxides (primarily iron, aluminum, calcium, magnesium, manganese, and uranium) and soluble sodium salts (carbonate, hydroxide, nitrite, nitrate, and sulfate). The pretreatment process in the Chemical Processing Cell (CPC) consists of two process tanks, the Sludge Receipt and Adjustment Tank (SRAT) and the Slurry Mix Evaporator (SME) as well as a melter feed tank. During SRAT processing, nitric and formic acids are added to the sludge to lower pH, destroy nitrite and carbonate ions, and reduce mercury and manganese. During the SME cycle, glass formers are added, and the batch is concentrated to the final solids target prior to vitrification. During these processes, hydrogen can be produced by catalytic decomposition of excess formic acid. The waste contains silver, palladium, rhodium, ruthenium, and mercury, but silver and palladium have been shown to be insignificant factors in catalytic hydrogen generation during the DWPF process. A full factorial experimental design was developed to ensure that the existence of statistically significant two-way interactions could be determined without confounding of the main effects with the two-way interaction effects. Rh ranged from 0.0026-0.013% and Ru ranged from 0.010-0.050% in the dried sludge solids, while initial Hg ranged from 0.5-2.5 wt%, as shown in Table 1. The nominal matrix design consisted of twelve SRAT cycles. Testing included: a three factor (Rh, Ru, and Hg) study at two levels per factor (eight runs), three duplicate midpoint runs, and one additional replicate run to assess reproducibility away from the midpoint. Midpoint testing was used to identify potential quadratic effects from the three factors. A single sludge

  15. A highly efficient noble metal free photocatalytic hydrogen evolution system containing MoP and CdS quantum dots

    NASA Astrophysics Data System (ADS)

    Yin, Shengming; Han, Jianyu; Zou, Yinjun; Zhou, Tianhua; Xu, Rong

    2016-07-01

    We report the construction of a highly efficient noble metal free photocatalytic hydrogen (H2) evolution system using CdS quantum dots as the light absorber and metallic MoP as the cocatalyst. MoP can be prepared by a facile temperature programmed reduction method and small clusters of MoP nanoparticles sized 10-30 nm were obtained by probe ultrasonication. The effect of synthesis conditions on the electrocatalytic and photocatalytic H2 evolution activity of MoP was investigated. The highest H2 evolution rate of 1100 μmol h-1 can be achieved by the optimized system under visible light (λ >= 420 nm), which is comparable to that when Pt was used as the cocatalyst. A high quantum efficiency of 45% is obtained at 460 nm irradiation.We report the construction of a highly efficient noble metal free photocatalytic hydrogen (H2) evolution system using CdS quantum dots as the light absorber and metallic MoP as the cocatalyst. MoP can be prepared by a facile temperature programmed reduction method and small clusters of MoP nanoparticles sized 10-30 nm were obtained by probe ultrasonication. The effect of synthesis conditions on the electrocatalytic and photocatalytic H2 evolution activity of MoP was investigated. The highest H2 evolution rate of 1100 μmol h-1 can be achieved by the optimized system under visible light (λ >= 420 nm), which is comparable to that when Pt was used as the cocatalyst. A high quantum efficiency of 45% is obtained at 460 nm irradiation. Electronic supplementary information (ESI) available: SEM image with EDS, XPS survey spectrum, XRD and TEM images of MoP samples prepared under different conditions; XRD, TEM, UV-vis and photoluminescence spectra of CdS QDs; H2 evolution activity comparison for different MoP/CdS samples; the effect of pH value on H2 evolution activity of a MoP/CdS system; the XPS spectrum of MoP/CdS after photoreaction; table of literature studies on H2 evolution activity by different noble metal free photocatalytic systems

  16. The geochemical behavior of refractory noble metals and lithophile trace elements in refractory inclusions in carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Fegley, B., Jr.; Kornacki, A. S.

    1984-01-01

    Recent models of Ca, Al-rich (CAI) inclusion petrogenesis, and the recent availability of thermodynamic data have led to the reexamination of the geochemical behavior of the refractory noble metals (RNM) and several lithophile refractory trace elements in CAI's in the context of distillation models. Here, pertinent chemical and mineralogical properties of the various classes of refractory inclusions are reviewed, and calculations of the stability of LRTE-RNM alloys and several LRTE oxides under nebular conditions are presented. The calculations, observations and experimental results are applied to a new model of the origin of refractory metal nuggets, and a specific mechanism is identified for producing Group II chemical patterns in a cold star nebula by fractionating interstellar dust at low temperature on the basis of physical differences between different populations of pre-solar grains.

  17. Composition of solar wind noble gases released by surface oxidation of a metal separate from the Weston meteorite

    NASA Technical Reports Server (NTRS)

    Becker, R. H.; Pepin, R. O.

    1991-01-01

    The paper reports on a set of experiments intended to test the feasibility of determining elemental and isotopic ratios of the noble gases and nitrogen in the solar wind in metal separates from gas-rich ordinary chondrites. Helium, neon, and argon show clear evidence of a solar wind signature, while no solar component could be identified for xenon and nitrogen. Helium, neon, and argon elemental isotopic ratios appear to depend on depth within the metal grains. The ratios derived indicate that the Weston meteorite did not acquire its solar wind gases from a recent exposure to solar wind, but more probably at a time in the past similar to or even earlier than the exposure time of Apollo 17 breccias. The Ar-36/Ar-38 ratio, in tandem with other recent determinations of this value, indicates that the solar and terrestrial values can no longer be assumed to be equivalent.

  18. The geochemical behavior of refractory noble metals and lithophile trace elements in refractory inclusions in carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Fegley, B.; Kornacki, A. S.

    1984-05-01

    Recent models of Ca, Al-rich (CAI) inclusion petrogenesis, and the recent availability of thermodynamic data have led to the reexamination of the geochemical behavior of the refractory noble metals (RNM) and several lithophile refractory trace elements in CAI's in the context of distillation models. Here, pertinent chemical and mineralogical properties of the various classes of refractory inclusions are reviewed, and calculations of the stability of LRTE-RNM alloys and several LRTE oxides under nebular conditions are presented. The calculations, observations and experimental results are applied to a new model of the origin of refractory metal nuggets, and a specific mechanism is identified for producing Group II chemical patterns in a cold star nebula by fractionating interstellar dust at low temperature on the basis of physical differences between different populations of pre-solar grains.

  19. A highly efficient noble metal free photocatalytic hydrogen evolution system containing MoP and CdS quantum dots.

    PubMed

    Yin, Shengming; Han, Jianyu; Zou, Yinjun; Zhou, Tianhua; Xu, Rong

    2016-08-14

    We report the construction of a highly efficient noble metal free photocatalytic hydrogen (H2) evolution system using CdS quantum dots as the light absorber and metallic MoP as the cocatalyst. MoP can be prepared by a facile temperature programmed reduction method and small clusters of MoP nanoparticles sized 10-30 nm were obtained by probe ultrasonication. The effect of synthesis conditions on the electrocatalytic and photocatalytic H2 evolution activity of MoP was investigated. The highest H2 evolution rate of 1100 μmol h(-1) can be achieved by the optimized system under visible light (λ≥ 420 nm), which is comparable to that when Pt was used as the cocatalyst. A high quantum efficiency of 45% is obtained at 460 nm irradiation. PMID:27406067

  20. 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.

  1. CO oxidation over noble metals: The continuum from ultrahigh vaccuum to atmospheric pressures

    NASA Astrophysics Data System (ADS)

    Goodman, David

    2008-03-01

    Catalytic oxidation of CO has been investigated for many decades by numerous researchers and is considered to be one of the best understood catalytic reactions. Because of its importance in pollution control, fuel cells, etc., this reaction has received considerable attention for fundamental and practical reasons. Removal of CO from automobile exhaust is accomplished by catalytic converters using supported Pt-group metals of Pt, Pd and Rh catalysts. The catalytically removal of traces of CO from H2 by Pt-group metals to the few ppm level is required for efficient operation in fuel cells. Efforts in our laboratory have addressed the adsorption of CO and the kinetics of CO-oxidation on single crystals and supported metal catalysts over a wide temperature (400--650 K) and pressure (1x10-7˜500 Torr) range. Two active phases, CO-dominated and O-dominated, have been identified for which the mechanisms for CO catalytic oxidation are entirely different. The highly active phase formed in oxygen-rich reaction condition exhibits CO2 formation rates several orders higher than the rates found for stoichiometric reaction conditions. This highly active surface was determined to consist of approximate one monolayer of surface oxygen using Auger spectroscopy and X-ray photoemission spectroscopy.

  2. Non-Noble-Metal Nanoparticle Supported on Metal-Organic Framework as an Efficient and Durable Catalyst for Promoting H2 Production from Ammonia Borane under Visible Light Irradiation.

    PubMed

    Wen, Meicheng; Cui, Yiwen; Kuwahara, Yasutaka; Mori, Kohsuke; Yamashita, Hiromi

    2016-08-24

    In this work, we propose a straightforward method to enhance the catalytic activity of AB dehydrogenation by using non-noble-metal nanoparticle supported on chromium-based metal-organic framework (MIL-101). It was demonstrated to be effective for hydrogen generation from ammonia borane under assistance of visible light irradiation as a noble-metal-free catalyst. The catalytic activity of metal nanoparticles supported on MIL-101 under visible light irradiation is remarkably higher than that without light irradiation. The TOFs of Cu/MIL-101, Co/MIL-101, and Ni/MIL-101 are 1693, 1571, and 3238 h(-1), respectively. The enhanced activity of catalysts can be primarily attributed to the cooperative promoting effects from both non-noble-metal nanoparticles and photoactive metal-organic framework in activating the ammonia borane molecule and strong ability in the photocatalytic production of hydroxyl radicals, superoxide anions, and electron-rich non-noble-metal nanoparticle. This work sheds light on the exploration of active non-noble metals supported on photoactive porous materials for achieving high catalytic activity of various redox reactions under visible light irradiation. PMID:27478964

  3. Noble-metal-free BODIPY-cobaloxime photocatalysts for visible-light-driven hydrogen production.

    PubMed

    Luo, Geng-Geng; Fang, Kai; Wu, Ji-Huai; Dai, Jing-Cao; Zhao, Qing-Hua

    2014-11-21

    In this study a series of supramolecular BODIPY-cobaloxime systems Co-Bn (n = 1-4): [{Co(dmgH)2Cl}{4,4-difluoro-8-(4-pyridyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene}] (Co-B1), [{Co(dmgH)2Cl}{4,4-difluoro-8-(4-pyridyl)-1,3,5,7-tetramethyl-2,6-diiodo-4-bora-3a,4a-diaza-s-indacene}] (Co-B2), [{Co(dmgH)2Cl}{4,4-difluoro-8-(3-pyridyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene}] (Co-B3), and [{Co(dmgH)2Cl}{4,4-difluoro-8-(3-pyridyl)-1,3,5,7-tetramethyl-2,6-diiodo-4-bora-3a,4a-diaza-s-indacene}] (Co-B4) (BODIPY = boron dipyrromethene, dmgH = dimethylglyoxime) have been synthesized by replacing one axial chlorine of cobaloxime moieties with the pyridine residues of BODIPYs, and structurally characterized. Absorption spectra show that the optical properties of the BODIPY-cobaloximes are essentially the sum of their constituent components, indicating weak interactions between the cobaloxime units and BODIPY chromophores in the ground state. If any, electronic communications may take place through the intramolecular electron transfer across their orthogonal structures. The possibility of intramolecular electron transfer is further supported by the results of the density functional theory (DFT) calculations at UB3LYP/LANL2DZ levels on Co-B2˙(-) and Co-B4˙(-), which show that the highest occupied molecular orbitals (HOMOs) possess predominantly BODIPY character, while the lowest unoccupied molecular orbitals (LUMOs) are located on the cobalt centers. The HOMO → LUMO transition is an electron-transfer process (BODIPY˙(-) radical anions → cobaloxime fragments). In view of the possible occurrence of electron transfer, these noble-metal-free BODIPY-cobaloximes are studied as single-component homogeneous photocatalysts for H2 generation in aqueous media. Under optimized conditions, the 2,6-diiodo BODIPY-sensitized cobaloxime Co-B4 that contains a meta-pyridyl at the 8-position of BODIPY presents excellent H2 photoproduction catalytic activity with a

  4. Jingle-bell-shaped ferrite hollow sphere with a noble metal core: Simple synthesis and their magnetic and antibacterial properties

    SciTech Connect

    Li Siheng; Wang Enbo Tian Chungui; Mao Baodong; Kang Zhenhui; Li Qiuyu; Sun Guoying

    2008-07-15

    In this paper, a simple strategy is developed for rational fabrication of a class of jingle-bell-shaped hollow structured nanomaterials marked as Ag(MFe{sub 2}O{sub 4}) (M=Ni, Co, Mg, Zn), consisting of ferrite hollow shells and metal nanoparticle cores, using highly uniform colloidal Ag(C) microspheres as template. The final composites were obtained by direct adsorption of metal cations Fe{sup 3+} and M{sup 2+} on the surface of the Ag(C) spheres followed by calcination process to remove the middle carbon shell and transform the metal ions into pure phase ferrites. The as-prepared composites were characterized by X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray analysis (EDX), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis spectroscopy and SQUID magnetometer. The results showed that the composites possess the magnetic property of the ferrite shell and the optical together with antibacterial property of the Ag core. - Graphical abstract: MFe{sub 2}O{sub 4} (M=Ni, Co, Mg, Zn) hollow spheres with a noble metal nanoparticle core were successfully prepared by using colloidal metal(C) core-shell spheres as templates with no need of surface modification. The shell thickness and magnetic properties of the ferrite hollow spheres could be controlled by varying the synthetic parameters.

  5. Electronic and Magnetic Properties of Encapsulated MoS2 Quantum Dots: The Case of Noble Metal Nanoparticle Dopants.

    PubMed

    Loh, Guan Chee

    2016-04-18

    With the rise of 2D materials, such as graphene and transition metal dichalcogenides, as viable materials for numerous experimental applications, it becomes more necessary to maintain fine control of their properties. One expedient and efficacious technique to regulate their properties is surface functionalization. In this study, DFT calculations are performed on triangular MoS2 quantum dots (QDs) either partially or completely doped with nanoparticles (NPs) of the noble metals Au, Ag, and Pt. The effects of these dopants on the geometry, electronic properties, magnetic properties, and chemical bonding of the QDs are investigated. The calculations show that the structural stability of the QDs is reduced by Au or Ag dopants, whereas Pt dopants have a contrasting effect. The NPs diminish the metallicity of the QD, the extent of which is contingent on the number of NPs adsorbed on the QD. However, these NPs exert distinctly disparate charge transfer effects-Ag NPs n-dope the QDs, whereas Au and Pt NPs either n- or p-dope. The molecular electrostatic potential maps of the occupied states show that metallic states are removed from the doping sites. Notwithstanding the decrease of magnetization in all three types of hybrid QD, the distribution of spin density in the Pt-doped QD is inherently different from that in the other QDs. Bond analyses using the quantum theory of atoms in molecules and the crystal orbital Hamilton population suggest that bonds between the Pt NPs and the QDs are the most covalent and the strongest, followed by the Au-QD bonds, and then Ag-QD bonds. The versatility of these hybrid QDs is further examined by applying an external electric field in the three orthogonal orientations, and comparing their properties with those in the absence of the electric field. There are two primary observations: 1) dopants at the tail, head and tail, and in the fully encased configuration are most effective in modifying the distribution of metallic states if the

  6. Electronic and Magnetic Properties of Encapsulated MoS2 Quantum Dots: The Case of Noble Metal Nanoparticle Dopants.

    PubMed

    Loh, Guan Chee

    2016-04-18

    With the rise of 2D materials, such as graphene and transition metal dichalcogenides, as viable materials for numerous experimental applications, it becomes more necessary to maintain fine control of their properties. One expedient and efficacious technique to regulate their properties is surface functionalization. In this study, DFT calculations are performed on triangular MoS2 quantum dots (QDs) either partially or completely doped with nanoparticles (NPs) of the noble metals Au, Ag, and Pt. The effects of these dopants on the geometry, electronic properties, magnetic properties, and chemical bonding of the QDs are investigated. The calculations show that the structural stability of the QDs is reduced by Au or Ag dopants, whereas Pt dopants have a contrasting effect. The NPs diminish the metallicity of the QD, the extent of which is contingent on the number of NPs adsorbed on the QD. However, these NPs exert distinctly disparate charge transfer effects-Ag NPs n-dope the QDs, whereas Au and Pt NPs either n- or p-dope. The molecular electrostatic potential maps of the occupied states show that metallic states are removed from the doping sites. Notwithstanding the decrease of magnetization in all three types of hybrid QD, the distribution of spin density in the Pt-doped QD is inherently different from that in the other QDs. Bond analyses using the quantum theory of atoms in molecules and the crystal orbital Hamilton population suggest that bonds between the Pt NPs and the QDs are the most covalent and the strongest, followed by the Au-QD bonds, and then Ag-QD bonds. The versatility of these hybrid QDs is further examined by applying an external electric field in the three orthogonal orientations, and comparing their properties with those in the absence of the electric field. There are two primary observations: 1) dopants at the tail, head and tail, and in the fully encased configuration are most effective in modifying the distribution of metallic states if the

  7. 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.

  8. Evaluation of HWVP feed preparation chemistry for an NCAW simulant -- Fiscal year 1993: Effect of noble metals concentration on offgas generation and ammonia formation

    SciTech Connect

    Patello, G.K.; Wiemers, K.D.; Bell, R.D.; Smith, H.D.; Williford, R.E.; Clemmer, R.G.

    1995-03-01

    The High-Level Waste Vitrification Program is developing technology for the Department of Energy to immobilize high-level and transuranic wastes as glass for permanent disposal. Pacific Northwest Laboratory (PNL) is conducting laboratory-scale melter feed preparation studies using a HWVP simulated waste slurry, Neutralized Current Acid Waste (NCAW). A FY 1993 laboratory-scale study focused on the effects of noble metals (Pd, Rh, and Ru) on feed preparation offgas generation and NH{sub 3} production. The noble metals catalyze H{sub 2} and NH{sub 3} production, which leads to safety concerns. The information gained from this study is intended to be used for technology development in pilot scale testing and design of the Hanford High-Level Waste Vitrification Facility. Six laboratory-scale feed preparation tests were performed as part of the FY 1993 testing activities using nonradioactive NCAW simulant. Tests were performed with 10%, 25%, 50% of nominal noble metals content. Also tested were 25% of the nominal Rh and a repeat of 25% nominal noble metals. The results of the test activities are described. 6 refs., 28 figs., 12 tabs.

  9. The effect of dielectric constants on noble metal/semiconductor SERS enhancement: FDTD simulation and experiment validation of Ag/Ge and Ag/Si substrates.

    PubMed

    Wang, Tao; Zhang, Zhaoshun; Liao, Fan; Cai, Qian; Li, Yanqing; Lee, Shuit-Tong; Shao, Mingwang

    2014-02-11

    The finite-difference time-domain (FDTD) method was employed to simulate the electric field distribution for noble metal (Au or Ag)/semiconductor (Ge or Si) substrates. The simulation showed that noble metal/Ge had stronger SERS enhancement than noble metal/Si, which was mainly attributed to the different dielectric constants of semiconductors. In order to verify the simulation, Ag nanoparticles with the diameter of ca. 40 nm were grown on Ge or Si wafer (Ag/Ge or Ag/Si) and employed as surface-enhanced Raman scattering substrates to detect analytes in solution. The experiment demonstrated that both the two substrates exhibited excellent performance in the low concentration detection of Rhodamine 6G. Besides, the enhancement factor (1.3 × 10(9)) and relative standard deviation values (less than 11%) of Ag/Ge substrate were both better than those of Ag/Si (2.9 × 10(7) and less than 15%, respectively), which was consistent with the FDTD simulation. Moreover, Ag nanoparticles were grown in-situ on Ge substrate, which kept the nanoparticles from aggregation in the detection. To data, Ag/Ge substrates showed the best performance for their sensitivity and uniformity among the noble metal/semiconductor ones.

  10. Formation of Metal Selenide and Metal-Selenium Nanoparticles using Distinct Reactivity between Selenium and Noble Metals.

    PubMed

    Park, Se Ho; Choi, Ji Yong; Lee, Young Hwan; Park, Joon T; Song, Hyunjoon

    2015-07-01

    Small Se nanoparticles with a diameter of ≈20 nm were generated by the reduction of selenium chloride with NaBH4 at -10 °C. The reaction with Ag at 60 °C yielded stable Ag2 Se nanoparticles, which subsequently were transformed into M-Se nanoparticles (M=Cd, Zn, Pb) through cation exchange reactions with corresponding ions. The reaction with Pt formed Pt layers that were evenly coated on the surface of the Se nanoparticles, and the dissolution of the Se cores with hydrazine generated uniform Pt hollow nanoparticles. The reaction with Au generated tiny Au clusters on the Se surface, and eventually formed acorn-shaped Au-Se nanoparticles through heat treatment. These results indicate that small Se nanoparticles with diameters of ≈20 nm can be used as a versatile platform for the synthesis of metal selenide and metal-selenium hybrid nanoparticles with complex structures.

  11. Electrocatalysis of anodic, oxygen-transfer reactions at noble metal electrodes

    SciTech Connect

    Vitt, J.E.

    1992-06-09

    Voltammetry at rotated disk and rotated ring-disk electrodes was applied to the study of several aspects of anodic, oxygen-transfer reactions at noble electrodes. Anodic reactions which involve the transfer of oxygen from H{sub 2}O to the oxidation products generally exhibit a voltammetric response characterized by severe kinetic limitations. Mechanistic studies were performed at noble electrodes in order to contrive strategies for improving the kinetics of these reactions. Competitive adsorption studies were used to devise an adsorption hierarchy for Au rotated disk electrodes. It was concluded that adsorption was a prerequisite for oxidations involving the transfer of oxygen present on the electrodes surface as adsorbed hydroxyl radicals. The electrogenerated chemiluminescence (ECL) of luminol was studied at Au, Pt, Pd, glassy carbon, PbO{sub 2}, and Bi-doped PbO{sub 2} electrodes. The ECL intensity was determined to be inversely related to electrochemical activity for the oxidation of luminol. It was concluded that the oxygen-transfer oxidation of luminol to 3-aminophthalate ( n = 4 eq mol{sup {minus}1}) corresponded to the dark reaction, whereas the electron-transfer oxidation of luminol with n = 1 eq mol{sup {minus}1} initiated the chemiluminescent reaction in solution.

  12. A fully coherent electron beam from a noble-metal covered W(111) single-atom emitter.

    PubMed

    Chang, Che-Cheng; Kuo, Hong-Shi; Hwang, Ing-Shouh; Tsong, Tien T

    2009-03-18

    In quantum mechanics, a wavefunction contains two factors: the amplitude and the phase. Only when the probing beam is fully phase coherent, can complete information be retrieved from a particle beam based experiment. Here we use the electron beam field emitted from a noble-metal covered W(111) single-atom tip to image single-walled carbon nanotubes (SWNTs) in an electron point projection microscope (PPM). The interference fringes of an SWNT bundle exhibit a very high contrast and the fringe pattern extends throughout the entire beam width. This indicates good phase correlation at all points transverse to the propagation direction. Application of these sources can significantly improve the performance and expand the capabilities of current electron beam based techniques. New instrumentation based on the full spatial coherence may allow determination of the three-dimensional atomic structures of nonperiodic nanostructures and make many advanced experiments possible.

  13. Piezoelectric bimorph-based shear force microscopy for the construction of noble metal plasmonic structures in air

    NASA Astrophysics Data System (ADS)

    Cai, Wei; Yang, Mu; Wang, Yingjie; Shang, Guangyi

    2015-07-01

    In this article, we present an alternative method to directly manipulate the noble metal structures in air. The method is carried out based on a home-made shear force microscope, which mainly consists of a fiber probe-bimorph beam shear force sensor, a scanning probe microscope controller, and a nano-positioning stage. The magnitude of the probe-sample interaction forces as a function of the set-point ratio is estimated, which shows that the magnitude of the forces is inversely proportional to the set-point ratio. The microscopic imaging and manipulation can be realized at the higher and lower set-point values, respectively. Typical results of imaging at the set-point ratio of larger than 90% and manipulation at that of lower than 60% are demonstrated. The results suggest that this method would provide a promising way to study the relation between plasmonic structures and optical properties on the micro/nano scale.

  14. Fano effect in the angle-integrated valence band photoemission of the noble metals Cu, Ag, and Au

    SciTech Connect

    De Nadaie, C.; Brookes, N.B.; Minar, J.; Ebert, H.; Ghiringhelli, G.; Tagliaferri, A.

    2004-10-01

    Results of a combined experimental and theoretical investigation on the Fano-effect in the angle-integrated valence band photoemission of the noble metals are presented. In line with the fact that the Fano-effect is caused by the spin-orbit-coupling, the observed spin polarization of the photocurrent was found to be the more pronounced the higher the atomic number of the element investigated. The ratio of the normalized spin difference curves, however, agreed only for Cu and Ag with the ratio of the corresponding spin-orbit coupling strength parameters. The deviation from this expected behavior in the case of Au could be explained by the properties of individual d-p- and d-f-contributions to the total spin difference curves, that were found to be quite different for Au compared to Cu and Ag.

  15. A study of the dispersity of iron oxide and iron oxide-noble metal (Me = Pd, Pt) supported systems

    NASA Astrophysics Data System (ADS)

    Cherkezova-Zheleva, Z. P.; Shopska, M. G.; Krstić, J. B.; Jovanović, D. M.; Mitov, I. G.; Kadinov, G. B.

    2007-09-01

    Samples of one-(Fe) and two-component (Fe-Pd and Fe-Pt) catalysts were prepared by incipient wetness impregnation of four different supports: TiO2 (anatase), γ-Al2O3, activated carbon, and diatomite. The chosen synthesis conditions resulted in the formation of nanosized supported phases—iron oxide (in the one-component samples), or iron oxide-noble metal (in the two-component ones). Different agglomeration degrees of these phases were obtained as a result of thermal treatment. Ultradisperse size of the supported phase was maintained in some samples, while a process of partial agglomeration occurred in others, giving rise to nearly bidisperse (ultra-and highdisperse) supported particles. The different texture of the used supports and their chemical composition are the reasons for the different stability of the nanosized supported phases. The samples were tested as heterogeneous catalysts in total benzene oxidation reaction.

  16. Non-noble metal Cu-loaded TiO2 for enhanced photocatalytic H2 production.

    PubMed

    Foo, Wei Jian; Zhang, Chun; Ho, Ghim Wei

    2013-01-21

    Here we have demonstrated the preparation of high-quality, monodispersed and tunable phases of Cu nanoparticles. Structural and chemical composition studies depict the evolution of Cu-Cu(2)O-CuO nanoparticles at various process stages. The loading of Cu and Cu oxide nanoparticles on TiO(2) catalyst has enhanced the photocatalytic H(2) production. Comparatively, H(2) treatment produces well-dispersed Cu nanoparticles with thin oxide shells that show the highest H(2) production amongst the samples. The relatively higher photocatalytic performance is deemed to result from reduced structural defects, higher surface area and dispersivity as well as favorable charge transfer, which inhibits recombination. The Cu nanoparticles are shown to be a promising alternative to noble metal-loaded TiO(2) catalyst systems due to their low cost and high performance in photocatalytic applications. PMID:23228941

  17. Non-noble metal Cu-loaded TiO2 for enhanced photocatalytic H2 production

    NASA Astrophysics Data System (ADS)

    Foo, Wei Jian; Zhang, Chun; Ho, Ghim Wei

    2012-12-01

    Here we have demonstrated the preparation of high-quality, monodispersed and tunable phases of Cu nanoparticles. Structural and chemical composition studies depict the evolution of Cu-Cu2O-CuO nanoparticles at various process stages. The loading of Cu and Cu oxide nanoparticles on TiO2 catalyst has enhanced the photocatalytic H2 production. Comparatively, H2 treatment produces well-dispersed Cu nanoparticles with thin oxide shells that show the highest H2 production amongst the samples. The relatively higher photocatalytic performance is deemed to result from reduced structural defects, higher surface area and dispersivity as well as favorable charge transfer, which inhibits recombination. The Cu nanoparticles are shown to be a promising alternative to noble metal-loaded TiO2 catalyst systems due to their low cost and high performance in photocatalytic applications.

  18. Comparative study of the structural and electrochemical properties of noble metal inclusions in a UO2 matrix

    NASA Astrophysics Data System (ADS)

    Stumpf, S.; Petersmann, T.; Seibert, A.; Gouder, T.; Huber, F.; Brendebach, B.; Denecke, M. A.

    2010-03-01

    The intention of the presented study is to elucidate the influence of noble metal inclusions (fission products) on the structure as well as on the electrochemical properties of spent nuclear fuel (SNF). To this aim, thin UO2 films doped with metal inclusions such as Pd, Mo and Au are prepared by sputter deposition. The films are characterized by spectroscopic (XPS, EXAFS, XRD) as well as by microscopic (AFM, SEM) methods. In a next step the electrochemical properties of these model systems are comparatively investigated by cyclo voltammetry (CV). The sputter technique in combination with the heating treatment of the films allows the formation of a crystalline UO2 matrix as it is found in SNF. The co-deposition with Au results in the dispersion of the pure metal in the oxide matrix. Pd as well as Mo are oxidized due to the deposition at RT. Heating the films involves a further oxidation of MoO2 to MoO3. By contrast Pd agglomerates and forms metallic -phases as it is found in SNF. Electrochemical investigations of the UO2-Pd samples indicate an inhibiting influence of Pd on the oxidative dissolution of UO2. When it comes to the formation of secondary phases under reducing conditions such influence is passivated. The precipitates finally dominate the overall redox behaviour of the model system.

  19. Electrospinning-thermal treatment synthesis: a general strategy to decorate highly porous nanotubes on both internal and external side-walls with metal oxide/noble metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhao, Haitao; Lu, Bingan; Xu, Jing; Xie, Erqing; Wang, Taihong; Xu, Zhi

    2013-03-01

    The hybrid structure of nanoparticle-decorated highly porous nanotubes combines the advantages of large specific surface areas of nanoparticles and anisotropic properties of highly porous nanotubes, which is desirable for many applications, including batteries, photoelectrochemical water splitting, and catalysis. Here, we report a novel emulsion electrospinning-thermal treatment method to synthesize the nanoparticles deposited on both side walls of nanotubes with two unique characteristics: (1) large loading amount of nanoparticles per highly porous nanotubes (with the morphology of nanoparticles); (2) intimate contact between nanoparticles and highly porous nanotubes. Both features are advantageous for the above applications that involve both surface reactions and charge transportation processes. Moreover, the emulsion electrospinning-thermal treatment method is simple and straightforward, with which we have successfully decorated various highly porous metal oxide nanotubes with metal oxide or noble metal nanoparticles. The new method will have an impact on diverse technologies such as lithium ion batteries, catalysts, and photoelectrochemical devices.The hybrid structure of nanoparticle-decorated highly porous nanotubes combines the advantages of large specific surface areas of nanoparticles and anisotropic properties of highly porous nanotubes, which is desirable for many applications, including batteries, photoelectrochemical water splitting, and catalysis. Here, we report a novel emulsion electrospinning-thermal treatment method to synthesize the nanoparticles deposited on both side walls of nanotubes with two unique characteristics: (1) large loading amount of nanoparticles per highly porous nanotubes (with the morphology of nanoparticles); (2) intimate contact between nanoparticles and highly porous nanotubes. Both features are advantageous for the above applications that involve both surface reactions and charge transportation processes. Moreover, the

  20. Type I collagen-mediated synthesis of noble metallic nanoparticles networks and the applications in Surface-Enhanced Raman Scattering and electrochemistry.

    PubMed

    Sun, Yujing; Sun, Lanlan; Zhang, Baohua; Xu, Fugang; Liu, Zhelin; Guo, Cunlan; Zhang, Yue; Li, Zhuang

    2009-08-15

    In this paper, we demonstrated an effective environmentally friendly synthesis route to prepare noble metallic (Au, Ag, Pt and Pd) nanoparticles (NPs) networks mediated by type I collagen in the absence of any seeds or surfactants. In the reactions, type I collagen served as stabilizing agent and assembly template for the synthesized metallic NPs. The hydrophobic interaction between collagen and mica interface as well as the hydrogen bonds between inter- and intra-collagen molecules play important roles in the formation of collagen-metallic NPs networks. The noble metallic NPs networks have many advantages in the applications of Surface-Enhanced Raman Scattering (SERS) and electrochemistry detection. Typically, the as-prepared Ag NPs networks reveal great Raman enhancement activity for 4-ATP, and can even be used to detect low concentration of DNA base, adenine, without any label step. Furthermore, the cyclic voltammograms showed Pt NPs networks have good electrocatalytic ability for the reduction of O(2).

  1. Noble Hybrid Nanostructures as Efficient Anti-Proliferative Platforms for Human Breast Cancer Cell.

    PubMed

    Tavangar, Amirhossein; Premnath, Priyatha; Tan, Bo; Venkatakrishnan, Krishnan

    2016-04-27

    Nanomaterials have proven to possess great potential in biomaterials research. Recently, they have suggested considerable promise in cancer diagnosis and therapy. Among others, silicon (Si) nanomaterials have been extensively employed for various biomedical applications; however, the utilization of Si for cancer therapy has been limited to nanoparticles, and its potential as anticancer substrates has not been fully explored. Noble nanoparticles have also received considerable attention owing to unique anticancer properties to improve the efficiency of biomaterials for numerous biological applications. Nevertheless, immobilization and control over delivery of the nanoparticles have been challenge. Here, we develop hybrid nanoplatforms to efficiently hamper breast cancer cell adhesion and proliferation. Platforms are synthesized by femtosecond laser processing of Si into multiphase nanostructures, followed by sputter-coating with gold (Au)/gold-palladium (Au-Pd) nanoparticles. The performance of the developed platforms was then examined by exploring the response of normal fibroblast and metastatic breast cancer cells. Our results from the quantitative and qualitative analyses show a dramatic decrease in the number of breast cancer cells on the hybrid platform compared to untreated substrates. Whereas, fibroblast cells form stable adhesion with stretched and elongated cytoskeleton and actin filaments. The hybrid platforms perform as dual-acting cytophobic/cytostatic stages where Si nanostructures depress breast cancer cell adhesion while immobilized Au/Au-Pd nanoparticles are gradually released to affect any surviving cell on the nanostructures. The nanoparticles are believed to be taken up by breast cancer cells via endocytosis, which subsequently alter the cell nucleus and may cause cell death. The findings suggest that the density of nanostructures and concentration of coated nanoparticles play critical roles on cytophobic/cytostatic properties of the platforms on

  2. Optical properties of MgF2 nano-composite films dispersed with noble metal nanoparticles synthesized by sol-gel method

    NASA Astrophysics Data System (ADS)

    Wakaki, Moriaki; Soujima, Nobuaki; Shibuya, Takehisa

    2015-03-01

    Porous MgF2 films synthesized by a sol-gel method exhibit the lowest refractive index among the dielectric optical materials and are the most useful materials for the anti-reflection coatings. On the other hand, surface plasmon resonance (SPR) absorptions of noble metal nanoparticles in various solid matrices have been extensively studied. New functional materials like a SERS (Surface Enhanced Raman Spectroscopy) tips are expected by synthesizing composite materials between porous MgF2 films featured by the network of MgF2 nanoparticles and noble metal nanoparticles introduced within the network. In this study, fundamental physical properties including morphology and optical properties are characterized for these materials to make clear the potential of the composite system. Composite materials of MgF2 films dispersed with noble metal (Ag, Au) nanoparticles were prepared using the sol-gel technique with various annealing temperatures and densities of noble metal nanoparticles. The structural morphology was analyzed by an X-ray diffractometer (XRD) and a scanning electron microscope (SEM). The size and shape distributions of the metal nanoparticles were observed using a transmission electron microscope (TEM). The optical properties of fabricated composite films were characterized by UV-Vis-NIR and FT-IR spectrophotometers. The absorption spectra due to the surface plasmon resonance (SPR) of the metal nanoparticles were analyzed using the dielectric function considering the effective medium approximation, typically Maxwell-Garnett model. The Raman scattering spectra were also studied to check the enhancement effect of specimen dropped on the MgF2: Ag nano-composite films deposited on Si substrate. Enhancement of the Raman intensity of pyridine solution specimen was observed.

  3. Base-free non-noble-metal-catalyzed hydrogen generation from formic acid: scope and mechanistic insights.

    PubMed

    Mellmann, Dörthe; Barsch, Enrico; Bauer, Matthias; Grabow, Kathleen; Boddien, Albert; Kammer, Anja; Sponholz, Peter; Bentrup, Ursula; Jackstell, Ralf; Junge, Henrik; Laurenczy, Gábor; Ludwig, Ralf; Beller, Matthias

    2014-10-13

    The iron-catalyzed dehydrogenation of formic acid has been studied both experimentally and mechanistically. The most active catalysts were generated in situ from cationic Fe(II) /Fe(III) precursors and tris[2-(diphenylphosphino)ethyl]phosphine (1, PP3 ). In contrast to most known noble-metal catalysts used for this transformation, no additional base was necessary. The activity of the iron catalyst depended highly on the solvent used, the presence of halide ions, the water content, and the ligand-to-metal ratio. The optimal catalytic performance was achieved by using [FeH(PP3 )]BF4 /PP3 in propylene carbonate in the presence of traces of water. With the exception of fluoride, the presence of halide ions in solution inhibited the catalytic activity. IR, Raman, UV/Vis, and EXAFS/XANES analyses gave detailed insights into the mechanism of hydrogen generation from formic acid at low temperature, supported by DFT calculations. In situ transmission FTIR measurements revealed the formation of an active iron formate species by the band observed at 1543 cm(-1) , which could be correlated with the evolution of gas. This active species was deactivated in the presence of chloride ions due to the formation of a chloro species (UV/Vis, Raman, IR, and XAS). In addition, XAS measurements demonstrated the importance of the solvent for the coordination of the PP3 ligand. PMID:25196789

  4. Base-free non-noble-metal-catalyzed hydrogen generation from formic acid: scope and mechanistic insights.

    PubMed

    Mellmann, Dörthe; Barsch, Enrico; Bauer, Matthias; Grabow, Kathleen; Boddien, Albert; Kammer, Anja; Sponholz, Peter; Bentrup, Ursula; Jackstell, Ralf; Junge, Henrik; Laurenczy, Gábor; Ludwig, Ralf; Beller, Matthias

    2014-10-13

    The iron-catalyzed dehydrogenation of formic acid has been studied both experimentally and mechanistically. The most active catalysts were generated in situ from cationic Fe(II) /Fe(III) precursors and tris[2-(diphenylphosphino)ethyl]phosphine (1, PP3 ). In contrast to most known noble-metal catalysts used for this transformation, no additional base was necessary. The activity of the iron catalyst depended highly on the solvent used, the presence of halide ions, the water content, and the ligand-to-metal ratio. The optimal catalytic performance was achieved by using [FeH(PP3 )]BF4 /PP3 in propylene carbonate in the presence of traces of water. With the exception of fluoride, the presence of halide ions in solution inhibited the catalytic activity. IR, Raman, UV/Vis, and EXAFS/XANES analyses gave detailed insights into the mechanism of hydrogen generation from formic acid at low temperature, supported by DFT calculations. In situ transmission FTIR measurements revealed the formation of an active iron formate species by the band observed at 1543 cm(-1) , which could be correlated with the evolution of gas. This active species was deactivated in the presence of chloride ions due to the formation of a chloro species (UV/Vis, Raman, IR, and XAS). In addition, XAS measurements demonstrated the importance of the solvent for the coordination of the PP3 ligand.

  5. Determination of noble metals in biological samples by electrothermal vaporization inductively coupled plasma mass spectrometry, following cloud point extraction

    NASA Astrophysics Data System (ADS)

    Andreia Mesquita da Silva, Márcia; Lúcia Azzolin Frescura, Vera; José Curtius, Adilson

    2001-10-01

    A simple separation procedure for noble metals based on cloud point extraction is proposed. The analyte ions in aqueous acidic solution, obtained by the acid digestion of the samples, were complexed with O, O-diethyl-dithiophosphate and Triton X-114 was added as a non-ionic surfactant. By increasing the temperature up to the cloud point, a phase separation occurs, resulting in an aqueous phase and a surfactant-rich phase containing most of the analytes that were complexed. The metals in the surfactant-rich phase were determined by electrothermal vaporization inductively coupled plasma mass spectrometry. The extraction conditions as well as the instrumental parameters were optimized. Enrichment factors ranging from 7 (Rh) to 60 (Pt) and limits of detection from 0.6 (Pt) to 3.0 ng l -1 (Rh) were obtained in the digested samples. The extraction was not efficient for Ir. Among the reference materials analyzed in this work, only one (SRM 2670, urine) presented recommended values for Au and Pt. Due to the non-availability of adequate CRMs, accuracy was assessed by spiking known analyte amounts to the acid digests. Recoveries close to 100% were observed for all the studied elements but Ru. Poor agreement between found and recommended values was observed for non-digested urine sample, probably due to the carrier effect of co-extracted residual matrix components. However, good agreement was reached after urine acid mineralization.

  6. General synthesis of noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS2 nanosheets and the enhanced catalytic activity of Pd-MoS2 for methanol oxidation.

    PubMed

    Yuwen, Lihui; Xu, Fei; Xue, Bing; Luo, Zhimin; Zhang, Qi; Bao, Biqing; Su, Shao; Weng, Lixing; Huang, Wei; Wang, Lianhui

    2014-06-01

    A general and facile method for water-dispersed noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS2 nanosheets (NM-MoS2 NSs) has been developed. By using sodium carboxymethyl cellulose as a stabilizer, well-dispersed NM-MoS2 NSs with homogeneously deposited noble metal nanocrystals (NM NCs) can be synthesized in aqueous solutions. Due to the transition from the semiconducting 2H phase to the metallic 1T phase, the chemically exfoliated MoS2 (ce-MoS2) NSs have improved electrochemical activity. The partially metallic nature of the ce-MoS2 NSs and the catalytic activity of the NM NCs synergistically make NM-MoS2 NSs a potential electrochemical catalyst. For the first time, Pd-MoS2 NSs were used as an electrocatalyst for methanol oxidation in alkaline media. The results showed that Pd-MoS2 NSs have enhanced catalytic activity with 2.8-fold anodic peak current mass density compared to a commercial Pd/C catalyst, suggesting potential for application in direct methanol fuel cells (DMFCs).

  7. Combined Photothermal and Surface-Enhanced Raman Spectroscopy Effect from Spiky Noble Metal Nanoparticles Wrapped within Graphene-Polymer Layers: Using Layer-by-layer Modified Reduced Graphene Oxide as Reactive Precursors.

    PubMed

    Li, Xiangming; Zhang, Yihe; Wu, Yaling; Duan, Yang; Luan, Xinglong; Zhang, Qian; An, Qi

    2015-09-01

    To fabricate functionally integrated hybrid nanoparticles holds high importance in biomedical applications and is still a challenging task. In this study, we report the first reduced graphene oxide (rGO)-nobel metal hybrid particles that present simultaneously the photothermal and surface-enhanced Raman spectroscopy (SERS) effect from the inorganic part and drug loading, dispersibility, and controllability features from LbL polyelectrolyte multilayers. The hybrid particles where spiky noble metal particles were wrapped within rGO-polyelectrolyte layers were prepared by a facile and controllable method. rGO template modified using polyethylenimine (PEI) and poly(acrylic acid) (PAA) via layer-by-layer technology served as the reactive precursors, and the morphologies of the particles could be facilely controlled via controlling the number of bilayers around the rGO template. The hybrid particle presented low cytotoxicity. After loading doxorubicin hydrochloride, the particles effectively induced cell death, and photothermal treatment further decreased cell viability. rGO-Ag hybrid particles could be prepared similarly. We expect the reported method provides an effective strategy to prepare rGO-noble metal hybrid nanoparticles that find potential biomedical applications. PMID:26269466

  8. Combined Photothermal and Surface-Enhanced Raman Spectroscopy Effect from Spiky Noble Metal Nanoparticles Wrapped within Graphene-Polymer Layers: Using Layer-by-layer Modified Reduced Graphene Oxide as Reactive Precursors.

    PubMed

    Li, Xiangming; Zhang, Yihe; Wu, Yaling; Duan, Yang; Luan, Xinglong; Zhang, Qian; An, Qi

    2015-09-01

    To fabricate functionally integrated hybrid nanoparticles holds high importance in biomedical applications and is still a challenging task. In this study, we report the first reduced graphene oxide (rGO)-nobel metal hybrid particles that present simultaneously the photothermal and surface-enhanced Raman spectroscopy (SERS) effect from the inorganic part and drug loading, dispersibility, and controllability features from LbL polyelectrolyte multilayers. The hybrid particles where spiky noble metal particles were wrapped within rGO-polyelectrolyte layers were prepared by a facile and controllable method. rGO template modified using polyethylenimine (PEI) and poly(acrylic acid) (PAA) via layer-by-layer technology served as the reactive precursors, and the morphologies of the particles could be facilely controlled via controlling the number of bilayers around the rGO template. The hybrid particle presented low cytotoxicity. After loading doxorubicin hydrochloride, the particles effectively induced cell death, and photothermal treatment further decreased cell viability. rGO-Ag hybrid particles could be prepared similarly. We expect the reported method provides an effective strategy to prepare rGO-noble metal hybrid nanoparticles that find potential biomedical applications.

  9. Rational Design of Biomolecular Templates for Synthesizing Multifunctional Noble Metal Nanoclusters toward Personalized Theranostic Applications.

    PubMed

    Yu, Yong; Mok, Beverly Y L; Loh, Xian Jun; Tan, Yen Nee

    2016-08-01

    Biomolecule-templated or biotemplated metal nanoclusters (NCs) are ultrasmall (<2 nm) metal (Au, Ag) particles stabilized by a certain type of biomolecular template (e.g., peptides, proteins, and DNA). Due to their unique physiochemical properties, biotemplated metal NCs have been widely used in sensing, imaging, delivery and therapy. The overwhelming applications in these individual areas imply the great promise of harnessing biotemplated metal NCs in more advanced biomedical aspects such as theranostics. Although applications of biotemplated metal NCs as theranostic agents are trending, the rational design of biomolecular templates suitable for the synthesis of multifunctional metal NCs for theranostics is comparatively underexplored. This progress report first identifies the essential attributes of biotemplated metal NCs for theranostics by reviewing the state-of-art applications in each of the four modalities of theranostics, namely sensing, imaging, delivery and therapy. To achieve high efficacy in these modalities, we elucidate the design principles underlying the use of biomolecules (proteins, peptides and nucleic acids) to control the NC size, emission color and surface chemistries for post-functionalization of therapeutic moieties. We then propose a unified strategy to engineer biomolecular templates that combine all these modalities to produce multifunctional biotemplated metal NCs that can serve as the next-generation personalized theranostic agents. PMID:27377035

  10. Rational Design of Biomolecular Templates for Synthesizing Multifunctional Noble Metal Nanoclusters toward Personalized Theranostic Applications.

    PubMed

    Yu, Yong; Mok, Beverly Y L; Loh, Xian Jun; Tan, Yen Nee

    2016-08-01

    Biomolecule-templated or biotemplated metal nanoclusters (NCs) are ultrasmall (<2 nm) metal (Au, Ag) particles stabilized by a certain type of biomolecular template (e.g., peptides, proteins, and DNA). Due to their unique physiochemical properties, biotemplated metal NCs have been widely used in sensing, imaging, delivery and therapy. The overwhelming applications in these individual areas imply the great promise of harnessing biotemplated metal NCs in more advanced biomedical aspects such as theranostics. Although applications of biotemplated metal NCs as theranostic agents are trending, the rational design of biomolecular templates suitable for the synthesis of multifunctional metal NCs for theranostics is comparatively underexplored. This progress report first identifies the essential attributes of biotemplated metal NCs for theranostics by reviewing the state-of-art applications in each of the four modalities of theranostics, namely sensing, imaging, delivery and therapy. To achieve high efficacy in these modalities, we elucidate the design principles underlying the use of biomolecules (proteins, peptides and nucleic acids) to control the NC size, emission color and surface chemistries for post-functionalization of therapeutic moieties. We then propose a unified strategy to engineer biomolecular templates that combine all these modalities to produce multifunctional biotemplated metal NCs that can serve as the next-generation personalized theranostic agents.

  11. Method and electrochemical cell for synthesis and treatment of metal monolayer electrocatalysts metal, carbon, and oxide nanoparticles ion batch, or in continuous fashion

    DOEpatents

    Adzic, Radoslav; Zhang, Junliang; Sasaki, Kotaro

    2015-04-28

    An apparatus and method for synthesis and treatment of electrocatalyst particles in batch or continuous fashion is provided. In one embodiment, the apparatus comprises a sonication bath and a two-compartment chamber submerged in the sonication bath. The upper and lower compartments are separated by a microporous material surface. The upper compartment comprises a cover and a working electrode (WE) connected to a Pt foil contact, with the foil contact connected to the microporous material. The upper chamber further comprises reference counter electrodes. The lower compartment comprises an electrochemical cell containing a solution of metal ions. In one embodiment, the method for synthesis of electrocatalysts comprises introducing a plurality of particles into the apparatus and applying sonication and an electrical potential to the microporous material connected to the WE. After the non-noble metal ions are deposited onto the particles, the non-noble metal ions are displaced by noble-metal ions by galvanic displacement.

  12. GREENER PRODUCTION OF NOBLE METAL NANOSTRUCTURES AND NANOCOMPOSITES: RISK REDUCTION AND APPLICATIONS

    EPA Science Inventory

    The synthesis of nanometal/nano metal oxide/nanostructured polymer and their stabilization (through dispersant, biodegradable polymer) involves the use of natural renewable resources such plant material extract, biodegradable polymers, sugars, vitamins and finally efficient and s...

  13. Release of Implanted Noble Gases from Metallic Glass Vitreloy During Pyrolysis

    NASA Technical Reports Server (NTRS)

    Meshik, A. P.; Hohenberg, C. M.; Burnett, D. S.; Woolum, D. S.

    2000-01-01

    Vitreloy, a metallic vitreous glass, was examined as a potential target material for the Genesis Mission solar wind collector. Stepped pyrolysis revealed that He and Ne implanted in Vitreloy were efficiently re-trapped during phase transitions.

  14. Effect of three adhesive primers for a noble metal on the shear bond strengths of three resin cements.

    PubMed

    Yoshida, K; Kamada, K; Sawase, T; Atsuta, M

    2001-01-01

    The purpose of this study was to evaluate the durability and shear bond strengths of the different combinations of three adhesive primers and three resin cements to a silver-palladium-copper-gold (Ag-Pd-Cu-Au) alloy. The adhesive primers Alloy Primer (AP), Metal PrimerII (MPII) and Metaltite (MT), and the resin cements BistiteII (BRII), Panavia Fluoro Cement (PFC) and Super-Bond C&B (SB) were used. Two sizes of casting alloy disks were either non-primed or primed and cemented with each of the three resin cements. The specimens were stored in a 37 degrees C water bath for 24 h and then immersed alternately in 4 and 60 degrees C water baths for 1 min each for up to 100,000 thermal cycles. Shear mode testing at a crosshead speed of 0.5 mm/min was then performed. The application of MPII or MT was effective for improving the shear bond strength between each of the three resin cements and the Ag-Pd-Cu-Au alloy compared with non-primed specimens. However, when primed with MPII or MT and cemented with SB, the bond strength at 100,000 thermal cycles was significantly lower than that at thermal cycle 0. When primed with AP, the specimens cemented with BRII or PFC showed lower bond strength than non-primed specimens and failed at the metal-resin cement interface at 100,000 thermal cycles. On the other hand, AP was effective in enhancing the shear bond strength of SB to the Ag-Pd-Cu-Au alloy. The five combined uses of an adhesive metal primer and resin cement (combinations of MPII or MT and BRII or PFC and AP and SB) are applicable to the cementation of prosthodontic restorations without complicated surface modification of the noble alloy.

  15. Chronology and shock history of the Bencubbin meteorite: A nitrogen, noble gas, and Ar-Ar investigation of silicates, metal and fluid inclusions

    NASA Astrophysics Data System (ADS)

    Marty, Bernard; Kelley, Simon; Turner, Grenville

    2010-11-01

    We have investigated the distribution and isotopic composition of nitrogen and noble gases, and the Ar-Ar chronology of the Bencubbin meteorite. Gases were extracted from different lithologies by both stepwise heating and vacuum crushing. Significant amounts of gases were found to be trapped within vesicles present in silicate clasts. Results indicate a global redistribution of volatile elements during a shock event caused by an impactor that collided with a planetary regolith. A transient atmosphere was created that interacted with partially or totally melted silicates and metal clasts. This atmosphere contained 15N-rich nitrogen with a pressure ⩾3 × 10 5 hPa, noble gases, and probably, although not analyzed here, other volatile species. Nitrogen and noble gases were re-distributed among bubbles, metal, and partly or totally melted silicates, according to their partition coefficients among these different phases. The occurrence of N 2 trapped in vesicles and dissolved in silicates indicates that the oxygen fugacity ( fO2) was greater than the iron-wüstite buffer during the shock event. Ar-Ar dating of Bencubbin glass gives an age of 4.20 ± 0.05 Ga, which probably dates this impact event. The cosmic-ray exposure age is estimated at ˜40 Ma with two different methods. Noble gases present isotopic signatures similar to those of "phase Q" (the major host of noble gases trapped in chondrites) but elemental patterns enriched in light noble gases (He, Ne and Ar) relative to Kr and Xe, normalized to the phase Q composition. Nitrogen isotopic data together with 40Ar/ 36Ar ratios indicate mixing between a 15N-rich component (δ 15N = +1000‰), terrestrial N, and an isotopically normal, chondritic N. Bencubbin and related 15N-rich meteorites of the CR clan do not show stable isotope (H and C) anomalies, precluding contribution of a nucleosynthetic component as the source of 15N enrichments. This leaves two possibilities, trapping of an ancient, highly fractionated

  16. A hybrid of titanium nitride and nitrogen-doped amorphous carbon supported on SiC as a noble metal-free electrocatalyst for oxygen reduction reaction.

    PubMed

    Jia, Yingdan; Wang, Yanhui; Dong, Liang; Huang, Junjie; Zhang, Yan; Su, Jing; Zang, Jianbing

    2015-02-14

    A novel noble metal-free catalyst, with nitrogen-doped amorphous carbon and titanium nitride particles supported on SiC (NC-TiN/SiC), was synthesized. The NC-TiN/SiC catalyst exhibited excellent oxygen reduction reaction activities as well as superior stability and methanol tolerance. The catalytic activities were attributed to the synergistic effect of TiN and NC. PMID:25574526

  17. Pulsed laser deposited indium tin oxides as alternatives to noble metals in the near-infrared region

    NASA Astrophysics Data System (ADS)

    Fang, Xu; Mak, C. L.; Zhang, Shiyu; Wang, Zhewei; Yuan, Wenjia; Ye, Hui

    2016-06-01

    Transparent conductive indium tin oxide thin films with thickness around 200 nm were deposited on glass substrates by pulsed laser deposition technology. The microstructure and the electrical and optical properties of the ITO films deposited under different oxygen pressures and substrate temperatures were systematically investigated. Distinct different x-ray diffraction patterns revealed that the crystallinity of ITO films was highly influenced by deposition conditions. The highest carrier concentration of the ITO films was obtained as 1.34  ×  1021 cm‑3 with the lowest corresponding resistivity of 2.41  ×  10‑4 Ω cm. Spectroscopic ellipsometry was applied to retrieve the dielectric permittivity of the ITO films to estimate their potential as plasmonic materials in the near-infrared region. The crossover wavelength (the wavelength where the real part of the permittivity changes from positive to negative) of the ITO films exhibited high dependence on the deposition conditions and was optimized to as low as 1270 nm. Compared with noble metals (silver or gold etc), the lower imaginary part of the permittivity (<3) of ITO films suggests the potential application of ITO in the near-infrared range.

  18. Pulsed laser deposited indium tin oxides as alternatives to noble metals in the near-infrared region.

    PubMed

    Fang, Xu; Mak, C L; Zhang, Shiyu; Wang, Zhewei; Yuan, Wenjia; Ye, Hui

    2016-06-01

    Transparent conductive indium tin oxide thin films with thickness around 200 nm were deposited on glass substrates by pulsed laser deposition technology. The microstructure and the electrical and optical properties of the ITO films deposited under different oxygen pressures and substrate temperatures were systematically investigated. Distinct different x-ray diffraction patterns revealed that the crystallinity of ITO films was highly influenced by deposition conditions. The highest carrier concentration of the ITO films was obtained as 1.34  ×  10(21) cm(-3) with the lowest corresponding resistivity of 2.41  ×  10(-4) Ω cm. Spectroscopic ellipsometry was applied to retrieve the dielectric permittivity of the ITO films to estimate their potential as plasmonic materials in the near-infrared region. The crossover wavelength (the wavelength where the real part of the permittivity changes from positive to negative) of the ITO films exhibited high dependence on the deposition conditions and was optimized to as low as 1270 nm. Compared with noble metals (silver or gold etc), the lower imaginary part of the permittivity (<3) of ITO films suggests the potential application of ITO in the near-infrared range. PMID:27054885

  19. Morphological Evolution of Noble Metal Nanoparticles in Chloroform: Mechanism of Switching on/off by Protic Species

    PubMed Central

    Douglas-Gallardo, O. A.; Gomez, C. G.; Macchione, M. A.; Cometto, F. P.; Coronado, E. A.; Macagno, V. A.; Pérez, M. A.

    2015-01-01

    The morphological stability/morphological reshaping of noble metal nanoparticles are studied experimentally in order to unravel the chemical mechanisms lying beneath. Gold and silver nanoparticles (AuNPs and AgNPs, respectively) formed in chloroformic environment are used, as model synthetic systems, to study phenomena of morphological change. The morphological evolution of NPs that follows their formation, is characterized by spectroscopy (UV-Visible, Raman and FTIR) and TEM (Transmission Electron Microscopy). The change of NP morphology involves the increase of the average NP size and the broadening of size distribution, in a close resemblance with the effect characteristically obtained from the Ostwald ripening. The effect of the poor solvating properties of chloroform in stabilizing small charged species (H+, Ag+, Au+) as well as the principle of electroneutrality of matter are analyzed in order to formulate a feasible reaction scheme consisting of a three-step processes: the generation of soluble intermediary species by corrosion of nanoparticles, the diffusion of intermediary species from one nanoparticle to another, and the re-deposition process involving the reduction of intermediary species. This basic reaction scheme is used as hypothesis to plan and perform experiments, which reveal that molecular oxygen dissolved in the dispersive medium can drive NP corrosion, however, protic species are also required as co-reactant. The polarity of the hydrogen bond and the ligand properties of the anions produced by deprotonation are feature of the protic species that enable/disable the corrosion and, in turn, the NP morphological evolution. PMID:26889378

  20. Striving toward noble-metal-free photocatalytic water splitting: The hydrogenated-graphene-TiO2 prototype

    DOE PAGESBeta

    Nguyen-Phan, Thuy -Duong; Luo, Si; Liu, Zongyuan; Gamalski, Andrew D.; Tao, Jing; Xu, Wenqian; Stach, Eric A.; Polyansky, Dmitry E.; Senanayake, Sanjaya D.; Fujita, Etsuko; et al

    2015-08-20

    Graphane, graphone and hydrogenated graphene (HG) have been extensively studied in recent years due to their interesting properties and potential use in commercial and industrial applications. The present study reports investigation of hydrogenated graphene/TiO2-x (HGT) nanocomposites as photocatalysts for H2 and O2 production from water without the assistance of a noble metal co-catalyst. By combination of several techniques, the morphologies, bulk/atomic structure and electronic properties of all the powders were exhaustively interrogated. Hydrogenation treatment efficiently reduces TiO2 nanoparticles, while the graphene oxide sheets undergo the topotactic transformation from a graphene-like structure to a mixture of graphitic and turbostratic carbon (amorphous/disordered)more » upon altering the calcination atmosphere from a mildly reducing to a H2-abundant environment. Remarkably, the hydrogenated graphene-TiO2-x composite that results upon H2-rich reduction exhibits the highest photocatalytic H2 evolution performance equivalent to low loading of Pt (~0.12 wt%), whereas the addition of HG suppresses the O2 production. As a result, we propose that such an enhancement can be attributed to a combination of factors including the introduction of oxygen vacancies and Ti3+ states, retarding the recombination of charge carriers and thus, facilitating the charge transfer from TiO2-x to the carbonaceous sheet.« less

  1. Pulsed laser deposited indium tin oxides as alternatives to noble metals in the near-infrared region

    NASA Astrophysics Data System (ADS)

    Fang, Xu; Mak, C. L.; Zhang, Shiyu; Wang, Zhewei; Yuan, Wenjia; Ye, Hui

    2016-06-01

    Transparent conductive indium tin oxide thin films with thickness around 200 nm were deposited on glass substrates by pulsed laser deposition technology. The microstructure and the electrical and optical properties of the ITO films deposited under different oxygen pressures and substrate temperatures were systematically investigated. Distinct different x-ray diffraction patterns revealed that the crystallinity of ITO films was highly influenced by deposition conditions. The highest carrier concentration of the ITO films was obtained as 1.34  ×  1021 cm-3 with the lowest corresponding resistivity of 2.41  ×  10-4 Ω cm. Spectroscopic ellipsometry was applied to retrieve the dielectric permittivity of the ITO films to estimate their potential as plasmonic materials in the near-infrared region. The crossover wavelength (the wavelength where the real part of the permittivity changes from positive to negative) of the ITO films exhibited high dependence on the deposition conditions and was optimized to as low as 1270 nm. Compared with noble metals (silver or gold etc), the lower imaginary part of the permittivity (<3) of ITO films suggests the potential application of ITO in the near-infrared range.

  2. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding.

    PubMed

    Zhao, X J; Xue, X L; Guo, Z X; Jia, Yu; Li, S F; Zhang, Zhenyu; Gao, Y F

    2015-11-01

    Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal PtN nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for PtN, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D6h symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). However, the magic number of PtN clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt57 motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d(9)6s(1)) of Pt, which result in a delicate balance between the enhanced Pt-Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. These findings about PtN clusters are also applicable to IrN clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. The findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.

  3. Development of a general non-noble metal catalyst for the benign amination of alcohols with amines and ammonia.

    PubMed

    Cui, Xinjiang; Dai, Xingchao; Deng, Youquan; Shi, Feng

    2013-03-11

    The N-alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N-alkyl amines. However, as a potentially clean and economic choice for N-alkyl amine synthesis, non-noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCuFeOx catalyst was designed and prepared for the N-alkylation of ammonia or amines with alcohol or primary amines. N-alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N-heterocyclic compounds, and secondary amines could be N-alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one-pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation.

  4. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

    NASA Astrophysics Data System (ADS)

    Zhao, X. J.; Xue, X. L.; Guo, Z. X.; Jia, Yu; Li, S. F.; Zhang, Zhenyu; Gao, Y. F.

    2015-11-01

    Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal PtN nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for PtN, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D6h symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). However, the magic number of PtN clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt57 motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d96s1) of Pt, which result in a delicate balance between the enhanced Pt-Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. These findings about PtN clusters are also applicable to IrN clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. The findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.

  5. Self-Supported Cu-Based Nanowire Arrays as Noble-Metal-Free Electrocatalysts for Oxygen Evolution.

    PubMed

    Hou, Chun-Chao; Fu, Wen-Fu; Chen, Yong

    2016-08-23

    Crystalline Cu-based nanowire arrays (NWAs) including Cu(OH)2 , CuO, Cu2 O, and CuOx are facilely grown on Cu foil and are found to act as highly efficient, low-cost, and robust electrocatalysts for the oxygen evolution reaction (OER). Impressively, this noble-metal-free 3 D Cu(OH)2 -NWAs/Cu foil electrode shows the highest catalytic activity with a Tafel slope of 86 mV dec(-1) , an overpotential (η) of about 530 mV at ∼10 mA cm(-2) (controlled-potential electrolysis method without iR correction) and almost 100 % Faradic efficiency, paralleling the performance of the state-of-the-art RuO2 OER catalyst in 0.1 m NaOH solution (pH 12.8). To the best of our knowledge, this work represents one of the best results ever reported on Cu-based OER systems. PMID:27440473

  6. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

    PubMed Central

    Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

    2016-01-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm−2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production. PMID:26839148

  7. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction.

    PubMed

    Vij, Varun; Tiwari, Jitendra N; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S

    2016-01-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp(2) carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm(-2) at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production. PMID:26839148

  8. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

    2016-02-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

  9. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction.

    PubMed

    Vij, Varun; Tiwari, Jitendra N; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S

    2016-02-03

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp(2) carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm(-2) at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

  10. Fabrication of silicon nanowire arrays by macroscopic galvanic cell-driven metal catalyzed electroless etching in aerated HF solution.

    PubMed

    Liu, Lin; Peng, Kui-Qing; Hu, Ya; Wu, Xiao-Ling; Lee, Shuit-Tong

    2014-03-01

    Macroscopic galvanic cell-driven metal catalyzed electroless etching (MCEE) of silicon in aqueous hydrofluoric acid (HF) solution is devised to fabricate silicon nanowire (SiNW) arrays with dissolved oxygen acting as the one and only oxidizing agent. The key aspect of this strategy is the use of a graphite or other noble metal electrode that is electrically coupled with silicon substrate.

  11. Closed cell metal foam method

    DOEpatents

    Patten, James W.

    1978-01-01

    Foamed metals and metal alloys which have a closed cellular structure are prepared by heating a metal body containing entrapped inert gas uniformly distributed throughout to a temperature above the melting point of the metal and maintaining the body at this temperature a period of time sufficient to permit the entrapped gas to expand, forming individual cells within the molten metal, thus expanding and foaming the molten metal. After cell formation has reached the desired amount, the foamed molten metal body is cooled to below the melting temperature of the metal. The void area or density of the foamed metal is controlled by predetermining the amount of inert gas entrapped in the metal body and by the period of time the metal body is maintained in the molten state. This method is useful for preparing foamed metals and metal alloys from any metal or other material of which a body containing entrapped inert gas can be prepared.

  12. Organic phase synthesis of noble metal-zinc chalcogenide core-shell nanostructures.

    PubMed

    Kumar, Prashant; Diab, Mahmud; Flomin, Kobi; Rukenstein, Pazit; Mokari, Taleb

    2016-10-15

    Multi-component nanostructures have been attracting tremendous attention due to their ability to form novel materials with unique chemical, optical and physical properties. Development of hybrid nanostructures that are composed of metal-semiconductor components using a simple approach is of interest. Herein, we report a robust and general organic phase synthesis of metal (Au or Ag)-Zinc chalcogenide (ZnS or ZnSe) core-shell nanostructures. This synthetic protocol also enabled the growth of more compositionally complex nanostructures of Au-ZnSxSe1-x alloys and Au-ZnS-ZnSe core-shell-shell. The optical and structural properties of these hybrid nanostructures are also presented. PMID:27428852

  13. Organic phase synthesis of noble metal-zinc chalcogenide core-shell nanostructures.

    PubMed

    Kumar, Prashant; Diab, Mahmud; Flomin, Kobi; Rukenstein, Pazit; Mokari, Taleb

    2016-10-15

    Multi-component nanostructures have been attracting tremendous attention due to their ability to form novel materials with unique chemical, optical and physical properties. Development of hybrid nanostructures that are composed of metal-semiconductor components using a simple approach is of interest. Herein, we report a robust and general organic phase synthesis of metal (Au or Ag)-Zinc chalcogenide (ZnS or ZnSe) core-shell nanostructures. This synthetic protocol also enabled the growth of more compositionally complex nanostructures of Au-ZnSxSe1-x alloys and Au-ZnS-ZnSe core-shell-shell. The optical and structural properties of these hybrid nanostructures are also presented.

  14. One-Pot Synthesis of Monodisperse Noble Metal @ Resorcinol-Formaldehyde (M@RF) and M@Carbon Core-Shell Nanostructure and Their Catalytic Applications.

    PubMed

    Yang, Peipei; Xu, Yong; Chen, Lei; Wang, Xuchun; Zhang, Qiao

    2015-10-27

    We demonstrate that noble metal @ RF core-shell nanostructures can be obtained through a facile one-pot synthesis approach in the absence of any additional surfactants. Monodisperse metal@RF core-shell nanostructures can be produced within 1 h on a large scale. Both the core size and shell thickness can be readily tuned by altering the reaction parameters. Systematic studies reveal that resorcinol could have several functions: it could act as a reactant to form RF resin, and it also could passivate the surface of metallic nanoparticles to prevent them from aggregating. Additionally, for the first time, our results suggest that resorcinol may act as a reducing agent that can reduce metal salts to form metal nanoparticles. The core-shell nanoparticles can be carbonized into M@carbon nanostructures, which have shown great performance in the catalytic hydrogenation of chlorobenzene. This work not only will help to achieve the controllable synthesis of noble metal@RF resin and M@carbon core-shell nanostructures but also will promote research into other RF-based nanostructures and their catalytic applications.

  15. Non-noble metal vanadium phosphites with broad absorption for photocatalytic hydrogen evolution

    NASA Astrophysics Data System (ADS)

    Song, Jun-Ling; Zhang, Jian-Han; Mao, Jiang-Gao

    2016-05-01

    We reported the synthesis and crystal structures of alkali metal and alkali-earth metal phosphite, namely, CsV2(H3O)(HPO3)4 (1), and Ba3V2(HPO3)6 (2). Both compounds were prepared by hydrothermal reactions and feature unique new structures. They both exhibit 3D complicated frameworks based on VO6 octahedra which are connected by HPO3 tetrahedra via corner-sharing. Alkali or alkali earth metal cations are filled in the different channels of the frameworks. Topological analysis shows that the framework of CsV2(H3O) (HPO3)4 (1) is a new 3,3,3,4,5-connected network with the Schläfli symbol of {4.62}2{42.66.82}{63}{65.8}. The investigations of X-ray photoelectron spectroscopy (XPS) and magnetic measurement on CsV2(H3O)(HPO3)4 suggest a +3 oxidation state of the vanadium ions in compound 1. Photocatalytic performance was evaluated by photocatalytic H2 evolution and degradation of methylene blue, which shows that both compounds exhibit activity under visible-light irradiation. IR spectrum, UV-vis-NIR spectrum and thermogravimetric analysis (TGA) of compounds were also investigated.

  16. Decoration of size-tunable CuO nanodots on TiO2 nanocrystals for noble metal-free photocatalytic H2 production

    NASA Astrophysics Data System (ADS)

    Moon, Geon Dae; Joo, Ji Bong; Lee, Ilkeun; Yin, Yadong

    2014-09-01

    We report a simple yet effective approach for the decoration of the TiO2 nanocrystal surface with size-tunable CuO nanodots for high-performance noble metal-free photocatalytic H2 production. Modification with polyacrylic acid enables the surface of TiO2 nanocrystals to be selectively deposited with Cu(OH)2 nanodots, which can be subsequently converted to CuO through dehydration without changing their morphologies. UV irradiation of the nanocomposite solution in the presence of a hole scavenger produces photogenerated electrons which reduce CuO to metallic Cu nanodots, making them effective co-catalysts in a role similar to Pt for promoting photocatalytic H2 production. Due to the considerably high work function of Cu, the formation of a metal-semiconductor Schottky junction induces efficient charge separation and transfer. As a result, the TiO2 nanocrystals decorated with an optimal amount of CuO nanodots (1.7 wt%) could reach ~50% of the photocatalytic activity achievable by the Pt-TiO2 counterparts (1 wt%), clearly demonstrating the great potential of such composite catalysts for efficient noble metal-free photocatalytic H2 production.We report a simple yet effective approach for the decoration of the TiO2 nanocrystal surface with size-tunable CuO nanodots for high-performance noble metal-free photocatalytic H2 production. Modification with polyacrylic acid enables the surface of TiO2 nanocrystals to be selectively deposited with Cu(OH)2 nanodots, which can be subsequently converted to CuO through dehydration without changing their morphologies. UV irradiation of the nanocomposite solution in the presence of a hole scavenger produces photogenerated electrons which reduce CuO to metallic Cu nanodots, making them effective co-catalysts in a role similar to Pt for promoting photocatalytic H2 production. Due to the considerably high work function of Cu, the formation of a metal-semiconductor Schottky junction induces efficient charge separation and transfer. As a

  17. Noble Gases

    NASA Astrophysics Data System (ADS)

    Podosek, F. A.

    2003-12-01

    The noble gases are the group of elements - helium, neon, argon, krypton, xenon - in the rightmost column of the periodic table of the elements, those which have "filled" outermost shells of electrons (two for helium, eight for the others). This configuration of electrons results in a neutral atom that has relatively low electron affinity and relatively high ionization energy. In consequence, in most natural circumstances these elements do not form chemical compounds, whence they are called "noble." Similarly, much more so than other elements in most circumstances, they partition strongly into a gas phase (as monatomic gas), so that they are called the "noble gases" (also, "inert gases"). (It should be noted, of course, that there is a sixth noble gas, radon, but all isotopes of radon are radioactive, with maximum half-life a few days, so that radon occurs in nature only because of recent production in the U-Th decay chains. The factors that govern the distribution of radon isotopes are thus quite different from those for the five gases cited. There are interesting stories about radon, but they are very different from those about the first five noble gases, and are thus outside the scope of this chapter.)In the nuclear fires in which the elements are forged, the creation and destruction of a given nuclear species depends on its nuclear properties, not on whether it will have a filled outermost shell when things cool off and nuclei begin to gather electrons. The numerology of nuclear physics is different from that of chemistry, so that in the cosmos at large there is nothing systematically special about the abundances of the noble gases as compared to other elements. We live in a very nonrepresentative part of the cosmos, however. As is discussed elsewhere in this volume, the outstanding generalization about the geo-/cosmochemistry of the terrestrial planets is that at some point thermodynamic conditions dictated phase separation of solids from gases, and that the

  18. Plasmon‐Mediated Solar Energy Conversion via Photocatalysis in Noble Metal/Semiconductor Composites

    PubMed Central

    Wang, Mengye; Ye, Meidan; Iocozzia, James

    2016-01-01

    Plasmonics has remained a prominent and growing field over the past several decades. The coupling of various chemical and photo phenomenon has sparked considerable interest in plasmon‐mediated photocatalysis. Given plasmonic photocatalysis has only been developed for a relatively short period, considerable progress has been made in improving the absorption across the full solar spectrum and the efficiency of photo‐generated charge carrier separation. With recent advances in fundamental (i.e., mechanisms) and experimental studies (i.e., the influence of size, geometry, surrounding dielectric field, etc.) on plasmon‐mediated photocatalysis, the rational design and synthesis of metal/semiconductor hybrid nanostructure photocatalysts has been realized. This review seeks to highlight the recent impressive developments in plasmon‐mediated photocatalytic mechanisms (i.e., Schottky junction, direct electron transfer, enhanced local electric field, plasmon resonant energy transfer, and scattering and heating effects), summarize a set of factors (i.e., size, geometry, dielectric environment, loading amount and composition of plasmonic metal, and nanostructure and properties of semiconductors) that largely affect plasmonic photocatalysis, and finally conclude with a perspective on future directions within this rich field of research.

  19. Thermo-electrochemical selective growth of ZnO nanorods on any noble metal electrodes

    NASA Astrophysics Data System (ADS)

    You, Xueqiu; Park, Jungil; Choi, Jae-hoon; Pak, James Jungho

    2010-10-01

    Selective growth of ZnO nanorods has been successfully performed on the patterned Au/Ti metal electrode regions on a glass substrate by using a seeded thermo-electrochemical method in an acidic growth solution. The selective growth mechanism of the thermo-electrochemical method was proposed by using a series of chemical reactions for the first time. The thermo-electrochemical selective ZnO growth was performed on the cathode electrode at a temperature below 90 °C. A ZnO seed layer was precoated and selectively etched away from the non-metal regions in order to create the patterned selective nucleation sites on which the precursors are transferred and crystallized into ZnO nanorods. Both the dimensions and the placements of the ZnO nanorods have been simultaneously controlled. Energy dispersive X-ray spectrometry showed that the selectively grown ZnO nanorods consist of only Zn and O, indicating that the selectively grown ZnO nanorods are pure and contamination free. XRD and electron diffraction patterns revealed that the obtained ZnO nanorods have a wurtzite single-crystal structure.

  20. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

    DOE PAGESBeta

    Zhao, X. J.; Xue, X. L.; Guo, Z. X.; Jia, Yu; Li, S. F.; Zhang, Zhenyu; Gao, Y. F.

    2015-11-02

    Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal PtN nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for PtN, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D6h symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). But, the magic number of PtN clusters around 55 ismore » shifted to a new odd number of 57. The high symmetric three-layered Pt-57 motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d96s1) of Pt, which result in a delicate balance between the enhanced Pt-Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. Our findings about PtN clusters are also applicable to IrN clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. Finally, the findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.« less

  1. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

    SciTech Connect

    Zhao, X. J.; Xue, X. L.; Guo, Z. X.; Jia, Yu; Li, S. F.; Zhang, Zhenyu; Gao, Y. F.

    2015-11-02

    Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal PtN nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for PtN, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D6h symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). But, the magic number of PtN clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt-57 motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d96s1) of Pt, which result in a delicate balance between the enhanced Pt-Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. Our findings about PtN clusters are also applicable to IrN clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. Finally, the findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.

  2. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

    SciTech Connect

    Zhao, X. J.; Xue, X. L.; Jia, Yu; Guo, Z. X.; Li, S. F.; Zhang, Zhenyu; Gao, Y. F.

    2015-11-07

    Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal Pt{sub N} nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for Pt{sub N}, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D{sub 6h} symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). However, the magic number of Pt{sub N} clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt{sub 57} motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d{sup 9}6s{sup 1}) of Pt, which result in a delicate balance between the enhanced Pt–Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. These findings about Pt{sub N} clusters are also applicable to Ir{sub N} clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. The findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.

  3. Striving toward noble-metal-free photocatalytic water splitting: The hydrogenated-graphene-TiO2 prototype

    SciTech Connect

    Nguyen-Phan, Thuy -Duong; Luo, Si; Liu, Zongyuan; Gamalski, Andrew D.; Tao, Jing; Xu, Wenqian; Stach, Eric A.; Polyansky, Dmitry E.; Senanayake, Sanjaya D.; Fujita, Etsuko; Rodriguez, Jose A.

    2015-08-20

    Graphane, graphone and hydrogenated graphene (HG) have been extensively studied in recent years due to their interesting properties and potential use in commercial and industrial applications. The present study reports investigation of hydrogenated graphene/TiO2-x (HGT) nanocomposites as photocatalysts for H2 and O2 production from water without the assistance of a noble metal co-catalyst. By combination of several techniques, the morphologies, bulk/atomic structure and electronic properties of all the powders were exhaustively interrogated. Hydrogenation treatment efficiently reduces TiO2 nanoparticles, while the graphene oxide sheets undergo the topotactic transformation from a graphene-like structure to a mixture of graphitic and turbostratic carbon (amorphous/disordered) upon altering the calcination atmosphere from a mildly reducing to a H2-abundant environment. Remarkably, the hydrogenated graphene-TiO2-x composite that results upon H2-rich reduction exhibits the highest photocatalytic H2 evolution performance equivalent to low loading of Pt (~0.12 wt%), whereas the addition of HG suppresses the O2 production. As a result, we propose that such an enhancement can be attributed to a combination of factors including the introduction of oxygen vacancies and Ti3+ states, retarding the recombination of charge carriers and thus, facilitating the charge transfer from TiO2-x to the carbonaceous sheet.

  4. EFFECTS OF ALTERNATE ANTIFOAM AGENTS, NOBLE METALS, MIXING SYSTEMS AND MASS TRANSFER ON GAS HOLDUP AND RELEASE FROM NONNEWTONIAN SLURRIES

    SciTech Connect

    Guerrero, H; Mark Fowley, M; Charles Crawford, C; Michael Restivo, M; Robert Leishear, R

    2007-12-24

    Gas holdup tests performed in a small-scale mechanically-agitated mixing system at the Savannah River National Laboratory (SRNL) were reported in 2006. The tests were for a simulant of waste from the Hanford Tank 241-AZ-101 and featured additions of DOW Corning Q2-3183A Antifoam agent. Results indicated that this antifoam agent (AFA) increased gas holdup in the waste simulant by about a factor of four and, counter intuitively, that the holdup increased as the simulant shear strength decreased (apparent viscosity decreased). These results raised questions about how the AFA might affect gas holdup in Hanford Waste Treatment and Immobilization Plant (WTP) vessels mixed by air sparging and pulse-jet mixers (PJMs). And whether the WTP air supply system being designed would have the capacity to handle a demand for increased airflow to operate the sparger-PJM mixing systems should the AFA increase retention of the radiochemically generated flammable gases in the waste by making the gas bubbles smaller and less mobile, or decrease the size of sparger bubbles making them mix less effectively for a given airflow rate. A new testing program was developed to assess the potential effects of adding the DOW Corning Q2-3183A AFA to WTP waste streams by first confirming the results of the work reported in 2006 by Stewart et al. and then determining if the AFA in fact causes such increased gas holdup in a prototypic sparger-PJM mixing system, or if the increased holdup is just a feature of the small-scale agitation system. Other elements of the new program include evaluating effects other variables could have on gas holdup in systems with AFA additions such as catalysis from trace noble metals in the waste, determining mass transfer coefficients for the AZ-101 waste simulant, and determining whether other AFA compositions such as Dow Corning 1520-US could also increase gas holdup in Hanford waste. This new testing program was split into two investigations, prototypic sparger

  5. Improved ex vivo blood compatibility of central venous catheter with noble metal alloy coating

    PubMed Central

    Vafa Homann, Manijeh; Johansson, Dorota; Wallen, Håkan

    2015-01-01

    Abstract Central line associated bloodstream infections (CLABSIs) are a serious cause of morbidity and mortality induced by the use of central venous catheters (CVCs). Nobel metal alloy (NMA) coating is an advanced surface modification that prevents microbial adhesion and growth on catheters and thereby reduces the risk of infection. In vitro microbiological analyses have shown up to 90% reduction in microbial adhesion on coated CVC compared to uncoated ones. This study aimed to assess the blood compatibility of NMA‐coated CVC according to ISO 10993‐4. Hemolysis, thrombin–antithrombin (TAT) complex, platelet counts, fibrin deposition, and C3a and SC5b‐9 complement activation were analyzed in human blood exposed to the NMA‐coated and control CVCs using a Chandler‐loop model. NMA‐coated CVC did not induce hemolysis and fell in the “nonhemolytic” category according to ASTM F756‐00. Significantly lower amounts of TAT were generated and less fibrin was deposited on NMA‐coated CVC than on uncoated ones. Slightly higher platelet counts and lower complement markers were observed for NMA‐coated CVC compared to uncoated ones. These data suggest that the NMA‐coated CVC has better ex vivo blood compatibility compared to uncoated CVC. © 2015 The Authors Journal of Biomedical Materials Research Part B: Applied Biomaterials Published by Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1359–1365, 2016. PMID:26698606

  6. Improved ex vivo blood compatibility of central venous catheter with noble metal alloy coating.

    PubMed

    Vafa Homann, Manijeh; Johansson, Dorota; Wallen, Håkan; Sanchez, Javier

    2016-10-01

    Central line associated bloodstream infections (CLABSIs) are a serious cause of morbidity and mortality induced by the use of central venous catheters (CVCs). Nobel metal alloy (NMA) coating is an advanced surface modification that prevents microbial adhesion and growth on catheters and thereby reduces the risk of infection. In vitro microbiological analyses have shown up to 90% reduction in microbial adhesion on coated CVC compared to uncoated ones. This study aimed to assess the blood compatibility of NMA-coated CVC according to ISO 10993-4. Hemolysis, thrombin-antithrombin (TAT) complex, platelet counts, fibrin deposition, and C3a and SC5b-9 complement activation were analyzed in human blood exposed to the NMA-coated and control CVCs using a Chandler-loop model. NMA-coated CVC did not induce hemolysis and fell in the "nonhemolytic" category according to ASTM F756-00. Significantly lower amounts of TAT were generated and less fibrin was deposited on NMA-coated CVC than on uncoated ones. Slightly higher platelet counts and lower complement markers were observed for NMA-coated CVC compared to uncoated ones. These data suggest that the NMA-coated CVC has better ex vivo blood compatibility compared to uncoated CVC. © 2015 The Authors Journal of Biomedical Materials Research Part B: Applied Biomaterials Published by Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1359-1365, 2016. PMID:26698606

  7. The energy barrier at noble metal/TiO{sub 2} junctions

    SciTech Connect

    Hossein-Babaei, F. E-mail: fhbabaei@yahoo.com; Lajvardi, Mehdi M. Alaei-Sheini, Navid

    2015-02-23

    Nobel metal/TiO{sub 2} structures are used as catalysts in chemical reactors, active components in TiO{sub 2}-based electronic devices, and connections between such devices and the outside circuitry. Here, we investigate the energy barrier at the junctions between vacuum-deposited Ag, Au, and Pt thin films and TiO{sub 2} layers by recording their electrical current vs. voltage diagrams and spectra of optical responses. Deposited Au/, Pt/, and Ag/TiO{sub 2} behave like contacts with zero junction energy barriers, but the thermal annealing of the reverse-biased devices for an hour at 523 K in air converts them to Schottky diodes with high junction energy barriers, decreasing their reverse electric currents up to 10{sup 6} times. Similar thermal processing in vacuum or pure argon proved ineffective. The highest energy barrier and the lowest reverse current among the devices examined belong to the annealed Ag/TiO{sub 2} contacts. The observed electronic features are described based on the physicochemical parameters of the constituting materials. The formation of higher junction barriers with rutile than with anatase is demonstrated.

  8. The energy barrier at noble metal/TiO2 junctions

    NASA Astrophysics Data System (ADS)

    Hossein-Babaei, F.; Lajvardi, Mehdi M.; Alaei-Sheini, Navid

    2015-02-01

    Nobel metal/TiO2 structures are used as catalysts in chemical reactors, active components in TiO2-based electronic devices, and connections between such devices and the outside circuitry. Here, we investigate the energy barrier at the junctions between vacuum-deposited Ag, Au, and Pt thin films and TiO2 layers by recording their electrical current vs. voltage diagrams and spectra of optical responses. Deposited Au/, Pt/, and Ag/TiO2 behave like contacts with zero junction energy barriers, but the thermal annealing of the reverse-biased devices for an hour at 523 K in air converts them to Schottky diodes with high junction energy barriers, decreasing their reverse electric currents up to 106 times. Similar thermal processing in vacuum or pure argon proved ineffective. The highest energy barrier and the lowest reverse current among the devices examined belong to the annealed Ag/TiO2 contacts. The observed electronic features are described based on the physicochemical parameters of the constituting materials. The formation of higher junction barriers with rutile than with anatase is demonstrated.

  9. Noble metal-free reduced graphene oxide-ZnxCd₁-xS nanocomposite with enhanced solar photocatalytic H₂-production performance.

    PubMed

    Zhang, Jun; Yu, Jiaguo; Jaroniec, Mietek; Gong, Jian Ru

    2012-09-12

    Design and preparation of efficient artificial photosynthetic systems for harvesting solar energy by production of hydrogen from water splitting is of great importance from both theoretical and practical viewpoints. ZnS-based solid solutions have been fully proved to be an efficient visible-light driven photocatalysts, however, the H(2)-production rate observed for these solid solutions is far from exciting and sometimes an expensive Pt cocatalyst is still needed in order to achieve higher quantum efficiency. Here, for the first time we report the high solar photocatalytic H(2)-production activity over the noble metal-free reduced graphene oxide (RGO)-Zn(x)Cd(1-x)S nanocomposite prepared by a facile coprecipitation-hydrothermal reduction strategy. The optimized RGO-Zn(0.8)Cd(0.2)S photocatalyst has a high H(2)-production rate of 1824 μmol h(-1) g(-1) at the RGO content of 0.25 wt % and the apparent quantum efficiency of 23.4% at 420 nm (the energy conversion efficiency is ca. 0.36% at simulated one-sun (AM 1.5G) illumination). The results exhibit significantly improved photocatalytic hydrogen production by 450% compared with that of the pristine Zn(0.8)Cd(0.2)S, and are better than that of the optimized Pt-Zn(0.8)Cd(0.2)S under the same reaction conditions, showing that the RGO-Zn(0.8)Cd(0.2)S nanocomposite represents one of the most highly active metal sulfide photocatalyts in the absence of noble metal cocatalysts. This work creates a green and simple way for using RGO as a support to enhance the photocatalytic H(2)-production activity of Zn(x)Cd(1-x)S, and also demonstrates that RGO is a promising substitute for noble metals in photocatalytic H(2)-production.

  10. Thermal metamorphism of mantle chromites and the stability of noble-metal nanoparticles

    NASA Astrophysics Data System (ADS)

    González-Jiménez, José M.; Reich, Martin; Camprubí, Antoni; Gervilla, Fernando; Griffin, William L.; Colás, Vanessa; O'Reilly, Suzanne Y.; Proenza, Joaquín A.; Pearson, Norman J.; Centeno-García, Elena

    2015-08-01

    The Loma Baya complex in south-western Mexico is a volume of chromitite-bearing oceanic mantle that records a complex metamorphic history, defined by a first stage of hydrous metamorphism overprinted by a short-lived thermal event associated with an Eocene granite intrusion. During the hydrous metamorphism, the primary magmatic chromite-olivine assemblage was replaced by a secondary, porous intergrowth of Fe2+-rich chromite and chlorite. The heat supplied by an Eocene-age granite intrusion reversed the hydration reaction, producing chromite rims with perfectly developed crystal faces. This third-generation chromite is in equilibrium with highly magnesian (neoformed) olivine and defines a chemical trend analogous to the original magmatic one. The preservation of both reactions in the Loma Baya chromitite provides compelling evidence that the hydration of chromite can be reversed by either prograde metamorphism or any heating event, confirming previous thermodynamic predictions. Understanding these complex features is of particular interest due to the fact that changes in temperature and variable degrees of fluid/rock interaction during metamorphism and intrusion have also significantly affected the chromite-hosted IPGE carrier phases. Here, we propose that the metamorphic fluids involved in the hydrous metamorphism have caused the desulphurization of laurite RuS2, releasing minute particles of Ru-Os-Ir alloys <50 nm in diameter. The following short-lived thermal event that promoted dehydration in the chromitite had the opposite effect on nanoparticle stability, producing a significant coarsening of metal nanoparticles to dimensions larger than a micron. Based on such observations, we argue that IPGE nanoparticles can be exsolved and grown (or coarsen) from sulphide matrices during prograde metamorphism or heating and not exclusively upon cooling under magmatic conditions as it has been previously suggested. These results provide new insights on the relevant role of

  11. Vacancy formation enthalpy of filled d-band noble metals by hybrid functionals

    NASA Astrophysics Data System (ADS)

    Xing, Weiwei; Liu, Peitao; Cheng, Xiyue; Niu, Haiyang; Ma, Hui; Li, Dianzhong; Li, Yiyi; Chen, Xing-Qiu

    2014-10-01

    First-principles determination of the vacancy formation enthalpies has been long-term believed to be highly successful for metals. However, a widely known fact is that the various conventional density functional theory (DFT) calculations with the typical semilocal approximations show apparent failures to yield accurate enthalpies of Ag and Au. Recently, the previously commonly assumed linear Arrhenius extrapolation to determine the vacancy formation enthalpies at T =0 K from the high-temperature measured concentration of thermally created vacancies has been demonstrated to have to be replaced by the non-Arrhenius local Grüneisen theory (LGT) [A. Glensk, B. Grabowski, T. Hickel, and J. Neugebauer, Phys. Rev. X 4, 011018 (2014), 10.1103/PhysRevX.4.011018]. The large discrepancies between the conventional DFT-PBE data and the unrevised experimental vacancy formation enthalpies disappear for Cu and Al. Even by following the same LGT revisions for Ag, the large discrepancies still remain substantial at T =0 K. Here, we show that the hybrid functional (HSE), by including nonlocal exchange interactions to extend the conventional DFT method, can further correct these substantial failures. Upon a comparison of the experimental valence-band spectra for Cu, Ag, and Au, we have determined the HSE exchange-correlated mixing parameters α of 0.1, 0.25, and 0.4, and further derived the HSE enthalpies of vacancy formation of 1.09, 0.94, and 0.72 eV, respectively; in nice agreement with available LGT-revised experimental data. Our HSE results shed light on how to improve the theoretical predictions to accurately determine the defect formation energies and related thermodynamical properties.

  12. Modeling and simulation of optical properties of noble metals triangular nanoprisms

    NASA Astrophysics Data System (ADS)

    Alsheheri, Soad

    Gold and silver has gained huge attention across the scientific community for its applications arising from its plasmonic properties. The optical properties achieved by these materials via excitation of plasmons is very unique to these materials and used as diagnostic and therapeutic agents in the field of medicine, and as sensors in a gamut of disciplines such as energy and environmental protection to name a few. Surface plasmon resonance (SPR) properties of the gold and silver are size and shape dependent. Of the various shapes reported in literature, triangular nanoprisms has tunable optical properties in the visible and near IR region by manipulating the structural features such as thickness, edge length, and morphology of tip. To understand the effect of these parameters on dipole surface plasmon resonance we have constructed triangular silver nanoprism and sandwich of gold and triangular nanoprism using Optiwave FDTD. Silver triangular nanoprism has exhibited blue shift on introduction of truncation and the blue shift continued further with depth of truncation. Similar observations were made for increase in thickness of nanoprism. In contrast, increase in edge length of the nanoprism has introduced a blue shift in dipole surface plasmon resonance. Coupling of gold and silver as sandwich with a dielectric material has introduced two plasmon resonance peaks in the visible and near IR region. In contrast to individual silver triangular nanoprism, increasing the edge length and thickness of gold and silver has introduced a red shift. Interestingly, thickness of the dielectric layer controls the wavelength of the dipole plasmon resonance of metals in the sandwich and its strength.

  13. Quantum mechanical origin of the plasmonic properties of noble metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Guidez, Emilie Brigitte

    Small silver and gold clusters (less than 2 nm) display a discrete absorption spectrum characteristic of molecular systems whereas larger particles display a strong, broad absorption band in the visible. The latter feature is due to the surface plasmon resonance, which is commonly explained by the collective dipolar motion of free electrons across the particle, creating charged surface states. The evolution between molecular properties and plasmon is investigated. Time-dependent density functional theory (TDDFT) calculations are performed to study the absorption spectrum of cluster-size silver and gold nanorods. The absorption spectrum of these silver nanorods exhibits high-intensity longitudinal and transverse modes (along the long and short axis of the nanorod respectively), similar to the plasmons observed experimentally for larger nanoparticles. These plasmon modes result from a constructive addition of the dipole moments of nearly degenerate single-particle excitations. The number of single-particle transitions involved increases with increasing system size, due to the growing density of states available. Gold nanorods exhibit a broader absorption spectrum than their silver counterpart due to enhanced relativistic effects, affecting the onset of the longitudinal plasmon mode. The high-energy, high-intensity beta-peak of acenes also results from a constructive addition of single-particle transitions and I show that it can be assigned to a plasmon. I also show that the plasmon modes of both acenes and metallic nanoparticles can be described with a simple configuration interaction (CI) interpretation. The evolution between molecular absorption spectrum and plasmon is also investigated by computing the density of states of spherical thiolate-protected gold clusters using a charge-perturbed particle-in-a-sphere model. The electronic structure obtained with this model gives good qualitative agreement with DFT calculations at a fraction of the cost. The progressive

  14. From hydrogenases to noble metal-free catalytic nanomaterials for H2 production and uptake.

    PubMed

    Le Goff, Alan; Artero, Vincent; Jousselme, Bruno; Tran, Phong Dinh; Guillet, Nicolas; Métayé, Romain; Fihri, Aziz; Palacin, Serge; Fontecave, Marc

    2009-12-01

    Interconversion of water and hydrogen in unitized regenerative fuel cells is a promising energy storage framework for smoothing out the temporal fluctuations of solar and wind power. However, replacement of presently available platinum catalysts by lower-cost and more abundant materials is a requisite for this technology to become economically viable. Here, we show that the covalent attachment of a nickel bisdiphosphine-based mimic of the active site of hydrogenase enzymes onto multiwalled carbon nanotubes results in a high-surface area cathode material with high catalytic activity under the strongly acidic conditions required in proton exchange membrane technology. Hydrogen evolves from aqueous sulfuric acid solution with very low overvoltages (20 millivolts), and the catalyst exhibits exceptional stability (more than 100,000 turnovers). The same catalyst is also very efficient for hydrogen oxidation in this environment, exhibiting current densities similar to those observed for hydrogenase-based materials.

  15. In Situ Studies of Surface Mobility on Noble Metal Model Catalysts Using STM and XPS at Ambient Pressure

    SciTech Connect

    Butcher, Derek Robert

    2010-06-01

    High Pressure Scanning Tunneling Microscopy (HP-STM) and Ambient Pressure X-ray Photoelectron Spectroscopy were used to study the structural properties and catalytic behavior of noble metal surfaces at high pressure. HP-STM was used to study the structural rearrangement of the top most atomic surface layer of the metal surfaces in response to changes in gas pressure and reactive conditions. AP-XPS was applied to single crystal and nanoparticle systems to monitor changes in the chemical composition of the surface layer in response to changing gas conditions. STM studies on the Pt(100) crystal face showed the lifting of the Pt(100)-hex surface reconstruction in the presence of CO, H2, and Benzene. The gas adsorption and subsequent charge transfer relieves the surface strain caused by the low coordination number of the (100) surface atoms allowing the formation of a (1 x 1) surface structure commensurate with the bulk terminated crystal structure. The surface phase change causes a transformation of the surface layer from hexagonal packing geometry to a four-fold symmetric surface which is rich in atomic defects. Lifting the hex reconstruction at room temperature resulted in a surface structure decorated with 2-3 nm Pt adatom islands with a high density of step edge sites. Annealing the surface at a modest temperature (150 C) in the presence of a high pressure of CO or H2 increased the surface diffusion of the Pt atoms causing the adatom islands to aggregate reducing the surface concentration of low coordination defect sites. Ethylene hydrogenation was studied on the Pt(100) surface using HP-STM. At low pressure, the lifting of the hex reconstruction was observed in the STM images. Increasing the ethylene pressure to 1 Torr, was found to regenerate the hexagonally symmetric reconstructed phase. At room temperature ethylene undergoes a structural rearrangement to form ethylidyne. Ethylidyne preferentially binds at the three-fold hollow sites, which

  16. Dependence of intermediated noble metals on the optical and electrical properties of ITO/metal/ITO multilayers

    NASA Astrophysics Data System (ADS)

    Lee, J. Y.; Yang, J. W.; Chae, J. H.; Park, J. H.; Choi, J. I.; Park, H. J.; Kim, Daeil

    2009-06-01

    Sn doped In 2O 3 (ITO) single layer and a sandwich structure of ITO/metal/ITO (IMI) multilayer films were deposited on a polycarbonate substrate using radio-frequency and direct-current magnetron sputtering process without substrate heating. The intermediated metal films in the IMI structure were Au and Cu films and the thickness of each layer in the IMI films was kept constant at 50 nm/10 nm/40 nm. In this study, the ITO/Au/ITO films show the lowest resistivity of 5.6 × 10 -5 Ω cm. However the films show the lower optical transmission of 71% at 550 nm than that (81%) of as deposited ITO films. The ITO/Cu/ITO films show an optical transmittance of 54% and electrical resistivity of 1.5 × 10 -4 Ω cm. Only the ITO/Au/ITO films showed the diffraction peaks in the XRD pattern. The figure of merit indicated that the ITO/Au/ITO films performed better in a transparent conducting electrode than in ITO single layer films and ITO/Cu/ITO films.

  17. Mono- and bimetallic Rh and Pt NSR-catalysts prepared by controlled deposition of noble metals on support or storage component.

    PubMed

    Büchel, Robert; Pratsinis, Sotiris E; Baiker, Alfons

    2012-02-22

    Mono- and bimetallic Rh and Pt based NOx storage-reduction (NSR) catalysts, where the noble metals were deposited on the Al2O3 support or BaCO3 storage component, have been prepared using a twin flame spray pyrolysis setup. The catalysts were characterized by nitrogen adsorption, CO chemisorption combined with diffuse reflectance infrared Fourier transform spectroscopy, X-ray diffraction, and scanning transmission electron microscopy combined with energy dispersive X-ray spectroscopy. The NSR performance of the catalysts was investigated by fuel lean/rich cycling in the absence and presence of SO2 (25 ppm) as well as after H2 desulfation at 750 °C. The performance increased when Rh was located on BaCO3 enabling good catalyst regeneration during the fuel rich phase. Best performance was observed for bimetallic catalysts where the noble metals were separated, with Pt on Al2O3 and Rh on BaCO3. The Rh-containing catalysts generally showed much higher tolerance to SO2 during fuel rich conditions and lost only little activity during thermal aging at 750 °C. PMID:23741085

  18. A general approach to fabricate diverse noble-metal (Au, Pt, Ag, Pt/Au)/Fe2O3 hybrid nanomaterials.

    PubMed

    Zhang, Jun; Liu, Xianghong; Guo, Xianzhi; Wu, Shihua; Wang, Shurong

    2010-07-19

    A novel, facile, and general one-pot strategy is explored for the synthesis of diverse noble-metal (Au, Pt, Ag, or Pt/Au)/Fe(2)O(3) hybrid nanoparticles with the assistance of lysine (which is a nontoxic, user friendly amino acid that is compatible with organisms) and without using any other functionalization reagents. Control experiments show that lysine, which contains both amino and carboxylic groups, plays dual and crucial roles as both linker and capping agents in attaching noble metals with a small size and uniform distribution onto an Fe(2)O(3) support. Considering the perfect compatibility of lysine with organism, this approach may find potentials in biochemistry and biological applications. Furthermore, this novel route is also an attractive alternative and supplement to the current methods using a silane coupling agent or polyelectrolyte for preparing hybrid nanomaterials. To demonstrate the usage of such hybrid nanomaterials, a chemical gas sensor has been fabricated from the as-synthesized Au/Fe(2)O(3) nanoparticles and investigated for ethanol detection. Results show that the hybrid sensor exhibits significantly improved sensor performances in terms of high sensitivity, low detection limit, better selectivity, and good reproducibility in comparison with pristine Fe(2)O(3). Most importantly, this general approach can be further employed to fabricate other hybrid nanomaterials based on different support materials.

  19. Decoration of Micro-/Nanoscale Noble Metal Particles on 3D Porous Nickel Using Electrodeposition Technique as Electrocatalyst for Hydrogen Evolution Reaction in Alkaline Electrolyte.

    PubMed

    Qian, Xin; Hang, Tao; Shanmugam, Sangaraju; Li, Ming

    2015-07-29

    Micro-/nanoscale noble metal (Ag, Au, and Pt) particle-decorated 3D porous nickel electrodes for hydrogen evolution reaction (HER) in alkaline electrolyte are fabricated via galvanostatic electrodeposition technique. The developed electrodes are characterized by field emission scanning electron microscopy and electrochemical measurements including Tafel polarization curves, cyclic voltammetry, and electrochemical impedance spectroscopy. It is clearly shown that the enlarged real surface area caused by 3D highly porous dendritic structure has greatly reinforced the electrocatalytic activity toward HER. Comparative analysis of electrodeposited Ag, Au, and Pt particle-decorated porous nickel electrodes for HER indicates that both intrinsic property and size of the noble metal particles can lead to distinct catalytic activities. Both nanoscale Au and Pt particles have further reinforcement effect toward HER, whereas microscale Ag particles exhibit the reverse effect. As an effective 3D hydrogen evolution cathode, the nanoscale Pt-particle-decorated 3D porous nickel electrode demonstrates the highest catalytic activity with an extremely low overpotential of -0.045 V for hydrogen production, a considerable exchange current density of 9.47 mA cm(-2) at 25 °C, and high durability in long-term electrolysis, all of which are attributed to the intrinsic catalytic property and the extremely small size of Pt particles.

  20. PARAMETRIC EFFECTS OF ANTI-FOAM COMPOSITION, SIMULANT PROPERTIES AND NOBLE METALS ON THE GAS HOLDUP AND RELEASE OF A NON-NEWTONIAN WASTE SLURRY SIMULANT

    SciTech Connect

    Guerrero, H; Charles Crawford, C; Mark Fowley, M

    2008-08-07

    Gas holdup tests were performed in bench-scale and small-scale mechanically-agitated mixing systems at the Savannah River National Laboratory (SRNL) for a simulant of waste from the Hanford Tank 241-AZ-101. These featured additions of DOW Corning Q2-3183A anti-foam agent. Results indicated that this anti-foam agent (AFA) increased gas holdup in the waste simulant by about a factor of four and, counter-intuitively, that the holdup increased as the non-newtonian simulant shear strength decreased (apparent viscosity decreased). Such results raised the potential of increased flammable gas retention in Hanford Waste Treatment and Immobilization Plant (WTP) vessels mixed by air sparging and pulse-jet mixers (PJMs) during a Design Basis Event (DBE). Additional testing was performed to determine the effects of simulant properties, composition of alternate AFAs, and presence of trace noble metals. Key results are that: (1) Increased gas holdup resulting from addition of Q2-3183A is due to a decrease in surface tension that supports small bubbles which have low rise velocities. (2) Dow Corning 1520-US AFA shows it to be a viable replacement to Dow Corning Q2-3183A AFA. This alternative AFA, however, requires significantly higher dosage for the same anti-foam function. (3) Addition of noble metals to the AZ-101 waste simulant does not produce a catalytic gas retention effect with the AFA.

  1. Sources of metals in the Porgera gold deposit, Papua New Guinea: Evidence from alteration, isotope, and noble metal geochemistry

    NASA Astrophysics Data System (ADS)

    Richards, Jeremy P.; McCulloch, Malcolm T.; Chappell, Bruce W.; Kerrich, Robert

    1991-02-01

    The Porgera gold deposit is spatially and temporally associated with the Late Miocene, mafic, alkalic, epizonal Porgera Intrusive Complex (PIC), located in the highlands of Papua New Guinea (PNG). The highlands region marks the site of a Tertiary age continent-island-arc collision zone, located on the northeastern edge of the Australasian craton. The PIC was emplaced within continental crust near the Lagaip Fault Zone, which represents an Oligocene suture between the craton and volcano-sedimentary rocks of the Sepik terrane. Magmatism at Porgera probably occurred in response to the Late Miocene elimination of an oceanic microplate, and subsequent Early Pliocene collision between the craton margin and an arc system located on the Bismarck Sea plate. Gold mineralization occurred within 1 Ma of the time of magmatism. Metasomatism accompanying early disseminated Au mineralization in igneous host rocks resulted in additions of K, Rb, Mn, S, and CO 2, and depletions of Fe, Mg, Ca, Na, Ba, and Sr; rare-earth and high-field-strength elements remained largely immobile. Pervasive development of illite-K-feldspar-quartz-carbonate alteration assemblages suggests alteration by mildly acidic, 200 to 350°C fluids, at high water/ rock ratios. Strontium and lead isotopic compositions of minerals from early base-metal sulphide veins associated with K-metasomatism, and later quartz-roscoelite veins carrying abundant free gold and tellurides, are remarkably uniform (e.g., 87Sr /86Sr = 0.70745 ± 0.00044 [n = 10] , 207Pb /204Pb = 15.603 ± 0.004 [n = 15] ). These compositions fall between those of unaltered igneous and sedimentary host rocks, and specifically sedimentary rocks from the Jurassic Om Formation which underlies the deposit (igneous rocks: 87Sr /86Sr ≈ 0.7035 , 207Pb /204Pb ≈ 15.560 ; Om Formation: 87Sr /86Sr |t~ 0.7153 , 207Pb /204Pb ≈ 15.636 ). It is therefore suggested that the hydrothermal fluids acquired their Sr and Pb isotopic signatures by interaction with, or

  2. Metal bioremediation through growing cells.

    PubMed

    Malik, Anushree

    2004-04-01

    Heavy-metal pollution represents an important environmental problem due to the toxic effects of metals, and their accumulation throughout the food chain leads to serious ecological and health problems. Metal remediation through common physico-chemical techniques is expensive and unsuitable in case of voluminous effluents containing complexing organic matter and low metal contamination. Biotechnological approaches that are designed to cover such niches have, therefore, received great deal of attention in the recent years. Biosorption studies involving low-cost and often dead/pretreated biomass have dominated the literature and, subsequently, extensive reviews focusing on equilibrium and kinetics of metal biosorption have also come up. However, the low binding capacity of biomass for certain recalcitrant metals such as Ni and failure to effectively remove metals from real industrial effluents due to presence of organic or inorganic ligands limit this approach. At times, when pure biosorptive metal removal is not feasible, application of a judicious consortium of growing metal-resistant cells can ensure better removal through a combination of bioprecipitation, biosorption and continuous metabolic uptake of metals after physical adsorption. Such approach may lead to simultaneous removal of toxic metals, organic loads and other inorganic impurities, as well as allow optimization through development of resistant species. However, sensitivity of living cells to extremes of pH or high metal concentration and need to furnish metabolic energy are some of the major constraints of employing growing cells for bioremediation. The efforts to meet such challenges via isolation of metal-resistant bacterial/fungal strains and exploitation of organic wastes as carbon substrates have began. Recent studies show that the strains (bacteria, yeast and fungi) isolated from contaminated sites possess excellent capability of metal scavenging. Some bacterial strains possess high tolerance to

  3. Noble Gases in the Earth's Core?

    NASA Astrophysics Data System (ADS)

    Jephcoat, A. P.; Bouhifd, M. A.; Heber, V.; Kelley, S. P.

    2004-12-01

    Chemical inertness, surface volatility and low abundance have made the noble gases a unique trace elemental and isotopic system for constraining the formation and evolution of the solid Earth and its atmosphere. This geochemical role parallels extensive physical-property measurements on the condensed rare gases alone at the pressures equivalent to those of the Earth's deep mantle and core from diamond-anvil cell (DAC) experiments. Traditional geochemical approaches to the processes of planetary evolution have involved crystal-melt partitioning at low pressures relevant more to near-surface degassing. The degree of compatibility has fluctuated among different studies and largely rests with the conclusion that, for common upper mantle phases, the noble gases are highly incompatible. But the long-known high 3He/4He ratios for some ocean-island basalts and more recent observations for some of the rare gases (Ne, Ar and possibly Xe) that there is a solar component emanating from the Earth, continue to raise questions on the source reservoir as well as on accretionary and incorporation processes. Changes in models of mantle convection style have made it harder to rely on the deep mantle as a reservoir, and the core has remained a particularly unfavourable location either because of difficulty in constructing a retention mechanism during planetary accretion or simply because of lack of data: Partitioning studies at pressure are rare and complicated by the difficulty in reproducing not only absolute concentrations, but confinement of gas in high-pressure apparatus and post-run analysis. We have investigated noble gas solubility in silicate liquids at high pressures in a DAC (relevant to a magma-ocean model of the early Earth) that suggests that the detailed composition and structure of silicate liquids may act as an important control on the level of incompatibility. The long-held idea of partial melting as a single-stage, efficient process for extracting noble gases from

  4. Noble-metal-free carbon nanotube-Cd0.1Zn0.9S composites for high visible-light photocatalytic H2-production performance.

    PubMed

    Yu, Jiaguo; Yang, Bin; Cheng, Bei

    2012-04-21

    Visible light photocatalytic H(2) production from water splitting using solar light is of great importance from the viewpoint of solar energy conversion and storage. In this study, a novel visible-light-driven photocatalyst multiwalled carbon nanotube modified Cd(0.1)Zn(0.9)S solid solution (CNT/Cd(0.1)Zn(0.9)S) was prepared by a simple hydrothermal method. The prepared samples exhibited enhanced photocatalytic H(2)-production activity under visible light. CNT content had a great influence on photocatalytic activity and an optimum amount of CNT was determined to be ca. 0.25 wt%, at which the CNT/Cd(0.1)Zn(0.9)S displayed the highest photocatalytic activity under visible light, giving an H(2)-production rate of 78.2 μmol h(-1) with an apparent quantum efficiency (QE) of 7.9% at 420 nm, even without any noble metal cocatalysts, exceeding that of pure Cd(0.1)Zn(0.9)S by more than 3.3 times. The enhanced photocatalytic activity was due to CNT as an excellent electron acceptor and transporter, thus reducing the recombination of charge carriers and enhancing the photocatalytic activity. Furthermore, the prepared sample was photostable and no photocorrosion was observed after photocatalytic recycling. Our findings demonstrated that CNT/Cd(0.1)Zn(0.9)S composites were a promising candidate for the development of high-performance photocatalysts in photocatalytic H(2) production. This work not only shows a possibility for the utilization of low cost CNT as a substitute for noble metals (such as Pt) in the photocatalytic H(2)-production but also for the first time shows a significant enhancement in the H(2)-production activity by using metal-free carbon materials as effective co-catalysts. PMID:22422167

  5. Demonstration of neutron detection utilizing open cell foam and noble gas scintillation

    SciTech Connect

    Lavelle, C. M. Miller, E. C.; Coplan, M.; Thompson, Alan K.; Vest, Robert E.; Yue, A. T.; Kowler, A. L.; Koeth, T.; Al-Sheikhly, M.; Clark, Charles W.

    2015-03-02

    We present results demonstrating neutron detection via a closely spaced converter structure coupled to low pressure noble gas scintillation instrumented by a single photo-multiplier tube (PMT). The converter is dispersed throughout the gas volume using a reticulated vitreous carbon foam coated with boron carbide (B{sub 4}C). A calibrated cold neutron beam is used to measure the neutron detection properties, using a thin film of enriched {sup 10}B as a reference standard. Monte Carlo computations of the ion energy deposition are discussed, including treatment of the foam random network. Results from this study indicate that the foam shadows a significant portion of the scintillation light from the PMT. The high scintillation yield of Xe appears to overcome the light loss, facilitating neutron detection and presenting interesting opportunities for neutron detector design.

  6. Photochemical synthesis of noble metal (Ag, Pd, Au, Pt) on graphene/ZnO multihybrid nanoarchitectures as electrocatalysis for H2O2 reduction.

    PubMed

    Gu, Hui; Yang, Yan; Tian, Jixiang; Shi, Guoyue

    2013-07-24

    For the first time, a series of noble metal (Ag, Au, Pd, and Pt) nanoparticles (NPs) based on new functional graphene were successfully achieved via UV-assisted photocatalytic reduction by ZnO nanorods. The whole preparation strategy for constructing noble metal deposited graphene sheets/ZnO (GS/ZnO) was elucidated in detail in this work. First, graphene oxide based two-dimensional carbon nanostructures served as a support to disperse ZnO nanorods through a hydrothermal route. The ZnO nanorods were self-assembled onto the surface of graphene sheets, forming GS/ZnO nanocomposite, and the graphene oxide was reduced, yielding reduced graphene sheets in this synthetic procedure. Second, the GS/ZnO films were further employed as supporting materials for the dispersion of metal nanoparticles. Photogenerated electrons from UV-irradiated ZnO were transported across GS to stepwise and respectively reduce v μL metal ions (Ag(+), Pd(2+), AuCl4(-), PtCl6(2-), 20 mg/mL) into metal (Ag, Pd, Au, Pt) NPs at a location distinct from the ZnO anchored site, forming five graphene-based hybrid nanocomposites designated as GS/ZnO, GS/ZnO@Agv, GS/ZnO@Pdv, GS/ZnO@Auv, GS/ZnO@Ptv, respectively. The obtained mutihybrid nanoarchitectured materials were clearly characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). According to the diameters and distribution, the four metal NPs on GS/ZnO were divided into two categories: Ag&Au and Pd&Pt. Their difference was rooted in the rival abilities of gathering electron between graphene and different metal islands in the photochemical reduction process. The electrochemical behaviors of the five resultant hybrid nanocomposites were investigated in H2O2 as well as in potassium ferricyanide (Fe(CN)6(3-/4-)) and displayed distinct electrocatalytic activity. PMID:23790187

  7. A one-pot protocol for synthesis of non-noble metal-based core-shell nanoparticles under ambient conditions: toward highly active and cost-effective catalysts for hydrolytic dehydrogenation of NH3BH3.

    PubMed

    Jiang, Hai-Long; Akita, Tomoki; Xu, Qiang

    2011-10-21

    A one-pot synthesis of non-noble transition metal-based core-shell nanoparticles (NPs) has been developed under ambient conditions. The obtained Cu@M (M = Co, Fe, Ni) NPs exhibit superior catalytic activity for hydrolytic dehydrogenation of NH(3)BH(3), compared to the alloy and monometallic counterparts. PMID:21909589

  8. Noble gases in meteorites and terrestrial planets

    NASA Technical Reports Server (NTRS)

    Wacker, J. F.

    1985-01-01

    Terrestrial planets and chondrites have noble gas platforms that are sufficiently alike, especially Ne/Ar, that they may have acquired their noble gases by similar processes. Meteorites presumably obtained their noble gases during formation in the solar nebula. Adsorption onto C - the major gas carrier in chondrites - is the likely mechanism for trapping noble gases; recent laboratory simulations support this hypothesis. The story is more complex for planets. An attractive possibility is that the planets acquired their noble gases in a late accreting veneer of chondritic material. In chondrites, noble gases correlate with C, N, H, and volatile metals; by Occam's Razor, we would expect a similar coupling in planets. Indeed, the Earth's crust and mantle contain chondritic like trace volatiles and PL group metals, respectively and the Earth's oceans resemble C chondrites in their enrichment of D (8X vs 8-10X of the galactic D/H ratio). Models have been proposed to explain some of the specific noble gas patterns in planets. These include: (1) noble gases may have been directly trapped by preplanetary material instead of arriving in a veneer; (2) for Venus, irradiation of preplanetary material, followed by diffusive loss of Ne, could explain the high concentration of AR-36; (3) the Earth and Venus may have initially had similar abundances of noble gases, but the Earth lost its share during the Moon forming event; (4) noble gases could have been captured by planetestimals, possibly leading to gravitational fractionation, particularly of Xe isotopes and (5) noble gases may have been dissolved in the hot outer portion of the Earth during contact with a primordial atmosphere.

  9. Surface Functionalization of g-C3 N4 : Molecular-Level Design of Noble-Metal-Free Hydrogen Evolution Photocatalysts.

    PubMed

    Chen, Yin; Lin, Bin; Yu, Weili; Yang, Yong; Bashir, Shahid M; Wang, Hong; Takanabe, Kazuhiro; Idriss, Hicham; Basset, Jean-Marie

    2015-07-13

    A stable noble-metal-free hydrogen evolution photocatalyst based on graphite carbon nitride (g-C3 N4 ) was developed by a molecular-level design strategy. Surface functionalization was successfully conducted to introduce a single nickel active site onto the surface of the semiconducting g-C3 N4 . This catalyst family (with less than 0.1 wt % of Ni) has been found to produce hydrogen with a rate near to the value obtained by using 3 wt % platinum as co-catalyst. This new catalyst also exhibits very good stability under hydrogen evolution conditions, without any evidence of deactivation after 24 h. PMID:26073972

  10. Surface Functionalization of g-C3 N4 : Molecular-Level Design of Noble-Metal-Free Hydrogen Evolution Photocatalysts.

    PubMed

    Chen, Yin; Lin, Bin; Yu, Weili; Yang, Yong; Bashir, Shahid M; Wang, Hong; Takanabe, Kazuhiro; Idriss, Hicham; Basset, Jean-Marie

    2015-07-13

    A stable noble-metal-free hydrogen evolution photocatalyst based on graphite carbon nitride (g-C3 N4 ) was developed by a molecular-level design strategy. Surface functionalization was successfully conducted to introduce a single nickel active site onto the surface of the semiconducting g-C3 N4 . This catalyst family (with less than 0.1 wt % of Ni) has been found to produce hydrogen with a rate near to the value obtained by using 3 wt % platinum as co-catalyst. This new catalyst also exhibits very good stability under hydrogen evolution conditions, without any evidence of deactivation after 24 h.

  11. Genesis Noble Gas Measurements

    NASA Technical Reports Server (NTRS)

    Hohenberg, Charles M.

    2005-01-01

    The original thrust of our Genesis funding was to extend and refine the noble gas analytical capabilities of this laboratory to improve the precision and accuracy of noble gas measurements in order to optimize the scientific return from the Genesis Mission. This process involved both instrumental improvement (supplemented by a SRLIDAP instrument grant) and refinement of technique. The Genesis landing mishap shifted our emphasis to the irregular aluminum heat shield material from the flat collector wafers. This has required redesign of our laser extraction cells to accommodate the longer focal lengths required for laser extraction from non-flat surfaces. Extraction of noble gases from solid aluminum surfaces, rather than thin coatings on transparent substrates has required refinement of controlled-depth laser ablation techniques. Both of these bring new problems, both with potentially higher blanks form larger laser cells and the larger quantities of evaporated aluminum which can coat the sapphire entrance ports. This is mainly a problem for the heavy noble gases where larger extraction areas are required, necessitating the new aluminum vapor containment techniques described below. With the Genesis Mission came three new multiple multiplier noble gas mass spectrometers to this laboratory, one built solely by us (Supergnome-M), one built in collaboration with Nu-Instruments (Noblesse), and one built in collaboration with GVI (Helix). All of these have multiple multiplier detection sections with the Nu-Instruments using a pair of electrostatic quad lenses for isotope spacing and the other two using mechanically adjustable positions for the electron multipliers. The Supergnome-M and Noblesse are installed and running. The GVI instrument was delivered a year late (in March 2005) and is yet to be installed by GVI. As with all new instruments there were some initial development issues, some of which are still outstanding. The most serious of these are performance issues

  12. Noble metals can have different effects on photocatalysis over metal-organic frameworks (MOFs): a case study on M/NH₂-MIL-125(Ti) (M=Pt and Au).

    PubMed

    Sun, Dengrong; Liu, Wenjun; Fu, Yanghe; Fang, Zhenxing; Sun, Fangxiang; Fu, Xianzhi; Zhang, Yongfan; Li, Zhaohui

    2014-04-14

    M-doped NH2-MIL-125(Ti) (M=Pt and Au) were prepared by using the wetness impregnation method followed by a treatment with H2 flow. The resultant samples were characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analyses, N2-sorption BET surface area, and UV/Vis diffuse reflectance spectroscopy (DRS). The photocatalytic reaction carried out in saturated CO2 with triethanolamine (TEOA) as sacrificial agent under visible-light irradiations showed that the noble metal-doping on NH2-MIL-125(Ti) promoted the photocatalytic hydrogen evolution. Unlike that over pure NH2-MIL-125(Ti), in which only formate was produced, both hydrogen and formate were formed over Pt- and Au-loaded NH2-MIL-125(Ti). However, Pt and Au have different effects on the photocatalytic performance for formate production. Compared with pure NH2-MIL-125(Ti), Pt/NH2-MIL-125(Ti) showed an enhanced activity for photocatalytic formate formation, whereas Au has a negative effect on this reaction. To elucidate the origin of the different photocatalytic performance, electron spin resonance (ESR) analyses and density functional theory (DFT) calculations were carried out over M/NH2-MIL-125(Ti).The photocatalytic mechanisms over M/NH2-MIL-125(Ti) (M=Pt and Au) were proposed. For the first time, the hydrogen spillover from the noble metal Pt to the framework of NH2-MIL-125(Ti) and its promoting effect on the photocatalytic CO2 reduction is revealed. The elucidation of the mechanism on the photocatalysis over M/NH2-MIL-125(Ti) can provide some guidance in the development of new photocatalysts based on MOF materials. This study also demonstrates the potential of using noble metal-doped MOFs in photocatalytic reactions involving hydrogen as a reactant, like hydrogenation reactions.

  13. Van Der Waals-Corrected Density Functional Theory Simulation of Adsorption Processes on Noble-Metal Surfaces: Xe on Ag(111), Au(111), and Cu(111)

    NASA Astrophysics Data System (ADS)

    Silvestrelli, Pier Luigi; Ambrosetti, Alberto

    2016-10-01

    The DFT/vdW-WF2s1 method based on the generation of localized Wannier functions, recently developed to include the van der Waals interactions in the density functional theory and describe adsorption processes on metal surfaces by taking metal-screening effects into account, is applied to the case of the interaction of Xe with noble-metal surfaces, namely Ag(111), Au(111), and Cu(111). The study is also repeated by adopting the DFT/vdW-QHO-WF variant relying on the quantum harmonic oscillator model which describes well many body effects. Comparison of the computed equilibrium binding energies and distances, and the C_3 coefficients characterizing the adatom-surface van der Waals interactions, with available experimental and theoretical reference data shows that the methods perform well and elucidates the importance of properly including screening effects. The results are also compared with those obtained by other vdW-corrected DFT schemes, including PBE-D, vdW-DF, vdW-DF2, rVV10, and by the simpler local density approximation and semi-local (PBE) generalized gradient approximation approaches.

  14. Comparative Study on the Sulfur Tolerance and Carbon Resistance of Supported Noble Metal Catalysts in Steam Reforming of Liquid Hydrocarbon Fuel

    SciTech Connect

    Xie, Chao; Chen, Yongsheng; Engelhard, Mark H.; Song, Chunshan

    2012-04-18

    This work was conducted to clarify the influence of the type of metal and support on the sulfur tolerance and carbon resistance of supported noble metal catalysts in steam reforming of liquid hydrocarbons. Al2O3-supported noble metal catalysts (Rh, Ru, Pt, and Pd), Rh catalysts on different supports (Al2O3, CeO2, SiO2, and MgO), and Pt catalyst supported on CeO2 and Al2O3, were examined for steam reforming of a liquid hydrocarbon fuel (Norpar13 from Exxon Mobil) at 800 C for 55 h. The results indicate that (1) Rh/Al2O3 shows higher sulfur tolerance than the Ru, Pt, and Pd catalysts on the same support; (2) both Al2O3 and CeO2 are promising supports for Rh catalyst to process sulfur-containing hydrocarbons; and (3) Pt/CeO2 exhibits better catalytic performance than Pt/Al2O3 in the reaction with sulfur. TEM results demonstrate that the metal particles in Rh/Al2O3 were better dispersed (mostly in 1-3 nm) compared with the other catalysts after reforming the sulfur-containing feed. As revealed by XPS, the binding energy of Rh 3d for Rh/Al2O3 is notably higher than that for Rh/CeO2, implying the formation of electron-deficient Rh particles in the former. The strong sulfur tolerance of Rh/Al2O3 may be related to the formation of well-dispersed electron-deficient Rh particles on the Al2O3 support. Sulfur K-edge XANES illustrates the preferential formation of sulfonate and sulfate on Rh/Al2O3, which is believed to be beneficial for improving its sulfur tolerance as their oxygen-shielded sulfur structure may hinder direct Rh-S interaction. Due to its strong sulfur tolerance, the carbon deposition on Rh/Al2O3 was significantly lower than that on the Al2O3-supported Ru, Pt, and Pd catalysts after the reaction with sulfur. The superior catalytic performance of CeO2-supported Rh and Pt catalysts in the presence of sulfur can be ascribed mainly to the promotion effect of CeO2 on carbon gasification, leading to much lower carbon deposition compared with the Rh/Al2O3, Rh/MgO, Rh

  15. A Comparison between Shear Bond Strength of VMK Master Porcelain with Three Base-metal Alloys (Ni-cr-T3, VeraBond, Super Cast) and One Noble Alloy (X-33) in Metal-ceramic Restorations

    PubMed Central

    Ahmadzadeh, A; Neshati, A; Mousavi, N; Epakchi, S; Dabaghi Tabriz, F; Sarbazi, AH

    2013-01-01

    Statement of Problem: The increase in the use of metal-ceramic restorations and a high prevalence of porcelain chipping entails introducing an alloy which is more compatible with porcelain and causes a stronger bond between the two. This study is to compare shear bond strength of three base-metal alloys and one noble alloy with the commonly used VMK Master Porcelain. Materials and Method: Three different groups of base-metal alloys (Ni-cr-T3, Super Cast, and VeraBond) and one group of noble alloy (X-33) were selected. Each group consisted of 15 alloy samples. All groups went through the casting process and change from wax pattern into metal disks. The VMK Master Porcelain was then fired on each group. All the specimens were put in the UTM; a shear force was loaded until a fracture occurred and the fracture force was consequently recorded. The data were analyzed by SPSS Version 16 and One-Way ANOVA was run to compare the shear strength between the groups. Furthermore, the groups were compared two-by-two by adopting Tukey test. Results: The findings of this study revealed shear bond strength of Ni-Cr-T3 alloy was higher than the three other alloys (94 MPa or 330 N). Super Cast alloy had the second greatest shear bond strength (80. 87Mpa or 283.87 N). Both VeraBond (69.66 MPa or 245 N) and x-33 alloys (66.53 MPa or 234 N) took the third place. Conclusion: Ni-Cr-T3 with VMK Master Porcelain has the greatest shear bond strength. Therefore, employment of this low-cost alloy is recommended in metal-ceramic restorations. PMID:24724144

  16. Poly(vinyl pyrrolidone): a dual functional reductant and stabilizer for the facile synthesis of noble metal nanoplates in aqueous solutions.

    PubMed

    Xiong, Yujie; Washio, Isao; Chen, Jingyi; Cai, Honggang; Li, Zhi-Yuan; Xia, Younan

    2006-09-26

    Poly(vinyl pyrrolidone) (PVP) has been extensively used in the solution-phase synthesis of many types of colloidal particles, where it is mainly considered as a steric stabilizer or capping agent with a major role to protect the product from agglomeration. In a recent study, we discovered that the hydroxyl end groups of PVP could also serve as a very mild reductant for kinetically controlled synthesis of Ag nanoplates with yields as high as 75%. Here we further demonstrate that hydroxyl-terminated PVP is also a well-suited reductant for the aqueous synthesis of circular, triangular, and hexagonal nanoplates made of other noble metals including Pd, Au, and Pt. The reduction kinetics of a metal salt by the hydroxyl end groups of PVP can be maneuvered in at least two different ways to facilitate the evolution of plate morphology: (i) by adjusting the molar ratio of PVP to the salt precursor and (ii) by altering the molecular weight of PVP. Unlike previously reported studies of Ag and Au thin plates, light was found to have a negligible role in the present synthesis. PMID:16981776

  17. Interfacial properties of Ce0.75Zr0.25O2 supported noble metals (Pd, Pt) from first principles

    NASA Astrophysics Data System (ADS)

    Lu, Z.; Yang, Z.

    2008-06-01

    First-principles electronic structure calculations of noble metals (NM=Pd, Pt)/Ce0.75Zr0.25O2 systems are presented. It is found that: the NM adatoms do not prefer to stay at the atop or the bridge sites of the cations (Ce and Zr), but prefer to be adsorbed at or around the anion sites. The most preferable adsorption sites for both the Pd and Pt adatoms are the O-bridge sites neighboring the Zr dopant. The Pt adatom show much stronger interaction with the Ce0.75Zr0.25O2(111) surface than does the Pd adatom. The interactions of the NM/Ce0.75Zr0.25O2(111) interfaces are stronger than those of the corresponding NM/ceria(111) interfaces. There are some metal induced gap states (MIGS) appeared in the gaps of the NM/Ce0.75Zr0.25O2(111) interfaces, which are important to catalytic properties of the NM/Ce0.75Zr0.25O2(111) catalysts.

  18. Cohesive properties of noble metals by van der Waals-corrected density functional theory: Au, Ag, and Cu as case studies

    NASA Astrophysics Data System (ADS)

    Ambrosetti, Alberto; Silvestrelli, Pier Luigi

    2016-07-01

    The cohesive energy, equilibrium lattice constant, and bulk modulus of Au, Ag, and Cu noble metals are computed by different van der Waals (vdW)-corrected density functional theory (DFT) methods, including vdW-DF, vdW-DF2, vdW-DF-cx, rVV10, and PBE-D. Two specifically designed methods are also developed in order to effectively include dynamical screening effects: the DFT/vdW-WF2p method, based on the generation of maximally localized Wannier functions, and the RPAp scheme (in two variants), based on a single-oscillator model of the localized electron response. Comparison with results obtained without explicit inclusion of van der Waals effects, such as with the local density approximation (LDA), PBE, PBEsol, or the hybrid PBE0 functional, elucidates the importance of a suitable description of screened van der Waals interactions even in the case of strong metal bonding. Many-body effects are also quantitatively evaluated within the RPAp approach.

  19. The noble gas argon modifies extracellular signal-regulated kinase 1/2 signaling in neurons and glial cells.

    PubMed

    Fahlenkamp, Astrid V; Rossaint, Rolf; Haase, Hajo; Al Kassam, Hussam; Ryang, Yu-Mi; Beyer, Cordian; Coburn, Mark

    2012-01-15

    Recently, the noble gas argon has been identified as a potent neuroprotective agent, but little is known about its cellular effects. In this in vitro study, we investigated argon's influence on the extracellular signal-regulated kinase (ERK) 1/2, a ubiquitous enzyme with numerous functions in cell proliferation and survival. Primary neuronal and astroglial cell cultures and the microglial cell line BV-2 were exposed to 50 vol.% argon. Further possible effects were studied following stimulation of microglia with 50 ng/ml LPS. ERK 1/2 activation was assessed by phosphorylation state-specific western blotting, cytokine levels by real-time PCR and western blotting. Total phosphotyrosine phosphatase activity was examined with p-nitrophenylphosphate. After 30 min exposure, argon significantly activated ERK 1/2 signaling in microglia. Enhanced phosphorylation of ERK 1/2 was also found in astrocytes and neurons following argon exposure, but it lacked statistical significance. In microglia, argon did not substantially interfere with LPS-induced ERK1/2 activation and inflammatory cytokine induction. Addition of the MEK-Inhibitor U0126 abolished the induced ERK 1/2 phosphorylation. Cellular phosphatase activity and the inactivation of phosphorylated ERK 1/2 were not altered by argon. In conclusion, argon enhanced ERK 1/2 activity in microglia via the upstream kinase MEK, probably through a direct mode of activation. ERK 1/2 signaling in astrocytes and neurons in vitro was also influenced, although not with statistical significance. Whether ERK 1/2 activation by argon affects cellular functions like differentiation and survival in the brain in vivo will have to be determined in future experiments.

  20. 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

  1. Mo2 C as Non-Noble Metal Co-Catalyst in Mo2 C/CdS Composite for Enhanced Photocatalytic H2 Evolution under Visible Light Irradiation.

    PubMed

    Ma, Baojun; Xu, Haojie; Lin, Keying; Li, Jie; Zhan, Haijuan; Liu, Wanyi; Li, Can

    2016-04-21

    Co-catalysts are a major factor to enhance photocatalytic H2 activity; they are mainly composed of expensive noble metals. Here, we reported a new non-noble-metal co-catalyst Mo2 C that efficiently improves the photocatalytic H2 evolution of CdS under visible light irradiation. Mo2 C is prepared by temperature-programmed reaction with molybdenum oxide as precursor, and the Mo2 C/CdS composite is prepared by deposition of CdS on Mo2 C. The optimum composite 2.0 % Mo2 C/CdS shows a high H2 evolution rate of 161 μmol h(-1) , which is ten times higher than that of CdS alone and 2.3 times higher than the optimum for 1.0 % Pt/CdS. Moreover, the Mo2 C/CdS is stable for 50 h. This study presents a new low-cost non-noble-metal co-catalyst as a photocatalyst to achieve highly efficient H2 evolution.

  2. Free MoS2 Nanoflowers Grown on Graphene by Microwave-Assisted Synthesis as Highly Efficient Non-Noble-Metal Electrocatalysts for the Hydrogen Evolution Reaction.

    PubMed

    Cao, Jiamu; Zhang, Xuelin; Zhang, Yufeng; Zhou, Jing; Chen, Yinuo; Liu, Xiaowei

    2016-01-01

    Advanced approaches to preparing non-noble-metal electrocatalysts for the hydrogen evolution reaction (HER) are considered to be a significant breakthrough in promoting the exploration of renewable resources. In this work, a hybrid material of MoS2 nanoflowers (NFs) on reduced graphene oxide (rGO) was synthesized as a HER catalyst via an environmentally friendly, efficient approach that is also suitable for mass production. Small-sized MoS2 NFs with a diameter of ca. 190 nm and an abundance of exposed edges were prepared by a hydrothermal method and were subsequently supported on rGO by microwave-assisted synthesis. The results show that MoS2 NFs were distributed uniformly on the remarkably reduced GO and preserved the outstanding original structural features perfectly. Electrochemical tests show that the as-prepared hybrid material exhibited excellent HER activity, with a small Tafel slope of 80 mV/decade and a low overpotential of 170 mV. PMID:27556402

  3. Sub-0.5 nm equivalent oxide thickness scaling for Si-doped Zr1-xHfxO2 thin film without using noble metal electrode.

    PubMed

    Ahn, Ji-Hoon; Kwon, Se-Hun

    2015-07-22

    The dielectric properties of the Si-doped Zr1-xHfxO2 thin films were investigated over a broad compositional range with the goal of improving their properties for use as DRAM capacitor materials. The Si-doped Zr1-xHfxO2 thin films were deposited on TiN bottom electrodes by atomic layer deposition using a TEMA-Zr/TEMA-Hf mixture precursor for deposition of Zr1-xHfxO2 film and Tris-EMASiH as a Si precursor. The Si stabilizer increased the tetragonality and the dielectric constant; however, at high fractions of Si, the crystal structure degraded to amorphous and the dielectric constant decreased. Doping with Si exhibited a larger influence on the dielectric constant at higher Hf content. A Si-doped Hf-rich Zr1-xHfxO2 thin film, with tetragonal structure, exhibited a dielectric constant of about 50. This is the highest value among all reported results for Zr and Hf oxide systems, and equivalent oxide thickness (EOT) value of under 0.5 nm could be obtained with a leakage current of under 10(-7) A·cm(-2), which is the lowest EOT value ever reported for a DRAM storage capacitor system without using a noble-metal-based electrode. PMID:26125098

  4. Free MoS2 Nanoflowers Grown on Graphene by Microwave-Assisted Synthesis as Highly Efficient Non-Noble-Metal Electrocatalysts for the Hydrogen Evolution Reaction

    PubMed Central

    Cao, Jiamu; Zhang, Xuelin; Zhang, Yufeng; Zhou, Jing; Chen, Yinuo; Liu, Xiaowei

    2016-01-01

    Advanced approaches to preparing non-noble-metal electrocatalysts for the hydrogen evolution reaction (HER) are considered to be a significant breakthrough in promoting the exploration of renewable resources. In this work, a hybrid material of MoS2 nanoflowers (NFs) on reduced graphene oxide (rGO) was synthesized as a HER catalyst via an environmentally friendly, efficient approach that is also suitable for mass production. Small-sized MoS2 NFs with a diameter of ca. 190 nm and an abundance of exposed edges were prepared by a hydrothermal method and were subsequently supported on rGO by microwave-assisted synthesis. The results show that MoS2 NFs were distributed uniformly on the remarkably reduced GO and preserved the outstanding original structural features perfectly. Electrochemical tests show that the as-prepared hybrid material exhibited excellent HER activity, with a small Tafel slope of 80 mV/decade and a low overpotential of 170 mV. PMID:27556402

  5. Activity of double wash-coat monolith catalyst with noble metals and zeolites in selective catalytic reduction of NO(x) with C3H6.

    PubMed

    Lee, Jung-Dae; Kim, Ki-Joong; Kim, Yong-Hwa; Jeon, Gyung-Soo; Choi, Young-Key; Ahn, Ho-Geun

    2008-10-01

    The selective catalytic reduction (SCR) of NO(x) with C3H6 was studied in the presence of oxygen. The double wash-coat monolith catalysts for SCR comprised a lower layer of Au (or Pt)/Al2O3 and a upper layer of zeolites. The catalytic performance of the double wash-coated catalyst was remarkably improved to broaden the temperature window. The Au and Pt particles were dispersed uniformly on the monolith with particle sizes range of 3 approximately 5 nm and 5 approximately 10 nm, respectively. The catalyst binders used were colloidal silica, potassium silicate and tetraethyl orthosilicate, and the best catalyst activity was achieved with using colloidal silica as a binder. The zeolites used for the catalyst upper layer were MCM-41, FER, Y5.3-Zeolite and ZSM5, among which the NH4-ZSM5-coated catalyst showed the highest activity. The experimental results confirmed the promising potential of the double wash-coat, monolith catalyst for SCR of NO(x) with C3H6 due to the effective combination of noble metal monolith catalyst with zeolite for the removal of NO(x) by SCR with hydrocarbons.

  6. Aerosol assisted chemical vapour deposition of ZnO films on glass with noble metal and p-type dopants; use of dopants to influence preferred orientation

    NASA Astrophysics Data System (ADS)

    Walters, G.; Parkin, I. P.

    2009-04-01

    The use of aerosol assisted chemical vapour deposition (AACVD) for the formation of zinc oxide and doped ZnO films with control of preferred orientation on glass is reported. Undoped and doped ZnO host matrix films were highly transparent with visible transmission >85%. The Cu (CuO/Cu 2O) doped ZnO thin films were highly coloured and opaque. Undoped and noble metal doped ZnO films had mainly spherical morphology. Aluminium oxide/ZnO composite films had a range of morphologies from spherical to cubic. The XRD patterns for both doped and undoped ZnO films grown at substrate temperatures less than 500 °C showed strong preferred (0 0 2) crystal lattice orientation. The undoped ZnO film at 500 °C exhibited a random crystal orientation pattern for hexagonal ZnO. The introduction of small amounts of Al 2O 3 within the ZnO to form a composite significantly altered the preferred crystal orientation to (1 0 1).

  7. Synthesis and characterization of a Noble metal Enhanced Optical Nanohybrid (NEON): a high brightness detection platform based on a dye-doped silica nanoparticle.

    PubMed

    Roy, Shibsekhar; Dixit, Chandra K; Woolley, Robert; O'Kennedy, Richard; McDonagh, Colette

    2012-05-29

    A highly bright and photostable, fluorescent nanohybrid particle is presented which consists of gold nanoparticles (GNPs) embedded in dye-doped silica in a core-shell configuration. The dye used is the near-infrared emitting 4,5-benzo-5'-(iodoacetaminomethyl)-1',3,3,3',3'-pentamethyl-1-(4-sulfobutyl) indodicarbo cyanine. The nanohybrid architecture comprises a GNP core which is separated from a layer of dye molecules by a 15 nm buffer layer and has an outer protective, undoped silica shell. Using this architecture, a brightness factor of 550 has been achieved compared to the free dye. This hybrid system, referred to as Noble metal Enhanced Optical Nanohybrid (NEON) in this paper, is the first nanohybrid construct to our knowledge which demonstrates such tunable fluorescence property. NEON has enhanced photostability compared to the free dye and compared to a control particle without GNPs. Furthermore, the NEON particle, when used as a fluorescent label in a model bioassay, shows improved performance over assays using a conventional single dye molecule label.

  8. Barrierless growth of precursor-free, ultrafast laser-fragmented noble metal nanoparticles by colloidal atom clusters - A kinetic in situ study.

    PubMed

    Jendrzej, Sandra; Gökce, Bilal; Amendola, Vincenzo; Barcikowski, Stephan

    2016-02-01

    Unintended post-synthesis growth of noble metal colloids caused by excess amounts of reactants or highly reactive atom clusters represents a fundamental problem in colloidal chemistry, affecting product stability or purity. Hence, quantified kinetics could allow defining nanoparticle size determination in dependence of the time. Here, we investigate in situ the growth kinetics of ps pulsed laser-fragmented platinum nanoparticles in presence of naked atom clusters in water without any influence of reducing agents or surfactants. The nanoparticle growth is investigated for platinum covering a time scale of minutes to 50days after nanoparticle generation, it is also supplemented by results obtained from gold and palladium. Since a minimum atom cluster concentration is exceeded, a significant growth is determined by time resolved UV/Vis spectroscopy, analytical disc centrifugation, zeta potential measurement and transmission electron microscopy. We suggest a decrease of atom cluster concentration over time, since nanoparticles grow at the expense of atom clusters. The growth mechanism during early phase (<1day) of laser-synthesized colloid is kinetically modeled by rapid barrierless coalescence. The prolonged slow nanoparticle growth is kinetically modeled by a combination of coalescence and Lifshitz-Slyozov-Wagner kinetic for Ostwald ripening, validated experimentally by the temperature dependence of Pt nanoparticle size and growth quenching by Iodide anions.

  9. Adsorption of inert gases including element 118 on noble metal and inert surfaces from ab initio Dirac-Coulomb atomic calculations.

    PubMed

    Pershina, V; Borschevsky, A; Eliav, E; Kaldor, U

    2008-10-14

    The interaction of the inert gases Rn and element 118 with various surfaces has been studied on the basis of fully relativistic ab initio Dirac-Coulomb CCSD(T) calculations of atomic properties. The calculated polarizability of element 118, 46.3 a.u., is the largest in group 18, the ionization potential is the lowest at 8.91 eV, and the estimated atomic radius is the largest, 4.55 a.u. These extreme values reflect, in addition to the general trends in the Periodic Table, the relativistic expansion and destabilization of the outer valence 7p(3/2) orbital. Van der Waals coefficients C(3) and adsorption enthalpies DeltaH(ads) of Ne through element 118 on noble metals and inert surfaces, such as quartz, ice, Teflon, and graphite, were calculated in a physisorption model using the atomic properties obtained. The C(3) coefficients were shown to steadily increase in group 18, while the increase in DeltaH(ads) from Ne to Rn does not continue to element 118: The large atomic radius of the latter element is responsible for a decrease in the interaction energy. We therefore predict that experimental distinction between Rn and 118 by adsorption on these types of surfaces will not be feasible. A possible candidate for separating the two elements is charcoal; further study is needed to test this possibility.

  10. Economic Hydrophobicity Triggering of CO2 Photoreduction for Selective CH4 Generation on Noble-Metal-Free TiO2-SiO2.

    PubMed

    Dong, Chunyang; Xing, Mingyang; Zhang, Jinlong

    2016-08-01

    On the basis of the fact that the competitive adsorption between CO2 and H2O on the catalyst plays an important role in the CO2 photoreduction process, here we develop an economic NH4F-induced hydrophobic modification strategy to enhance the CO2 competitive adsorption on the mesoporous TiO2-SiO2 composite surface via a simple solvothermal method. After the hydrophobic modification, the CO2 photoreduction for the selective generation of CH4 over the noble-metal-free TiO2-SiO2 composite can be greatly enhanced (2.42 vs 0.10 μmol/g in 4h). The enhanced CO2 photoreduction efficiency is assigned to the rational hydrophobic modification on TiO2-SiO2 surface by replacing Si-OH to hydrophobic Si-F bonds, which will improve the CO2 competitive adsorption and trigger the eight-electron CO2 photoreduction on the reaction kinetics. PMID:27415144

  11. Theory of plasmon-enhanced high-order harmonic generation in the vicinity of metal nanostructures in noble gases

    SciTech Connect

    Husakou, A.; Im, S.-J.; Herrmann, J.

    2011-04-15

    We present a semiclassical model for plasmon-enhanced high-order harmonic generation (HHG) in the vicinity of metal nanostructures. We show that, besides the field enhancement, both the inhomogeneity of the enhanced local fields and electron absorption by the metal surface play an important role in the HHG process and lead to the generation of even harmonics and a significantly increased cutoff. For the examples of silver-coated nanocones and bowtie antennas, we predict that the required intensity reduces by up to three orders of magnitude due to plasmonic field enhancement. The study of the enhanced high-order harmonic generation is connected with a finite-element simulation of the electric field enhancement due to the excitation of the plasmonic modes.

  12. Non-noble catalysts and catalyst supports for phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Mcalister, A. J.

    1981-01-01

    Tungsten carbide, which is active for hydrogen oxidation, is CO tolerant and has a hexagonal structure is discussed. Titanium carbide is inactive and has a cubic structure. Four different samples of the cubic alloys W sub x-1Ti sub XC sub 1-y were found to be active and CO tolerant. When the activities of these cubic alloys are weighted by the reciprocal of the square to those of highly forms of WC. They offer important insight into the nature of the active sites on W-C anode catalysts for use in phosphoric acid fuel cells.

  13. Non-noble catalysts and catalyst supports for phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Mcalister, A. J.

    1981-01-01

    Four different samples of the cubic alloys W sub x-1 Ti sub x C sub 1-y were prepared and found to be active and CO tolerant. When the activities of these cubic alloys were weighted by the reciprocal of the square of the W exchange, they displayed magnitudes and dependence on bulk C deficiency comparable to those of highly active forms of WC. It is concluded that they may offer important insight into the nature of the active sites on, and means for improving the performance of, W-C anode catalysts for use in phosphoric acid fuel cells.

  14. Non-noble catalysts and catalyst supports for phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Mcalister, A. J.

    1980-01-01

    Tungsten carbide, which is known to be active for hydrogen oxidation and CO tolerant has a hexagonal structure. Titanium carbide is inactive and has a cubic structure. Four different samples of the cubic alloys Wx-1TixC were prepared and found to be active and CO tolerant. These alloys are of interest as possible phosphoric acid fuel cell catalysts. They also are of interest as opportunities to study the activity of W in a different crystalline environment and to correlate the activities of the surface sites with surface composition.

  15. Layer-by-layer coating of bacteria with noble metal nanoparticles for surface-enhanced Raman scattering.

    PubMed

    Kahraman, Mehmet; Zamaleeva, Alsu I; Fakhrullin, Rawil F; Culha, Mustafa

    2009-12-01

    A simple layer-by-layer method to coat the bacterial cells with gold and silver nanoparticles (AuNPs and AgNPs) for the acquisition of surface-enhanced Raman scattering (SERS) spectra is reported. First, the bacteria cell wall is coated with poly (allylamine hydrochloride) (PAH), a positively charged polymer, and then with citrate reduced Au or AgNPs. In order to increase the stability of the coating, another layer of PAH is prepared on the surface. The SEM and AFM images indicate that the nanoparticles are in the form of both isolated and aggregated nanoparticles on the bacterial wall. The coating of bacterial cells with AgNPs or AuNPs not only serves for their preparation for SERS measurement but also helps to visualize the coated of bacterial cells under the ordinary white-light microscope objective due to efficient light-scattering properties of Au and AgNPs. A comparative study single versus aggregates of bacterial cells is also demonstrated for possible single bacterial detection with SERS. The two bacteria that differ in shape and cell wall biochemical structure, Escherichia coli and Staphylococcus cohnii, Gram-negative and -positive, respectively, are used as models. The preliminary results reveal that the approach could be used for single bacterial cell identification.

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

    PubMed

    Baksi, Ananya; Pradeep, T

    2013-12-21

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

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

    PubMed

    Baksi, Ananya; Pradeep, T

    2013-12-21

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

  18. Noble gas magnetic resonator

    DOEpatents

    Walker, Thad Gilbert; Lancor, Brian Robert; Wyllie, Robert

    2014-04-15

    Precise measurements of a precessional rate of noble gas in a magnetic field is obtained by constraining the time averaged direction of the spins of a stimulating alkali gas to lie in a plane transverse to the magnetic field. In this way, the magnetic field of the alkali gas does not provide a net contribution to the precessional rate of the noble gas.

  19. Theoretical Study on Surface-Enhanced Raman Spectra of Water Adsorbed on Noble Metal Cathodes of Nanostructures

    NASA Astrophysics Data System (ADS)

    Wu, De-Yin; Pang, Ran; Tian, Zhong-Qun

    2016-06-01

    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. The basis is the change of the electrochemical vibrational Stark tuning rates and the relative Raman intensity of the stretching and bending modes. How it is not completely understood the reason why the relative Raman intensity ratio of the bending and stretching vibrations of interfacial water increases 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 theoretical results allow us to propose that interfacial water molecules exist on these metal cathodes with different hydrogen bonding interactions, the HO-H…Ag(Au) for silver and gold. In acidic solution, a surface electron-hydronium ion-pair was proposed as an adsorption configuration of interfacial water structures on silver and gold cathodes based on density functional theory (DFT) calculations. The EHIP is in the configuration of H3O+(H2O)ne-, where the hydronium H3O+ and the surface electron is separated by water layers. The electron bound in the EHIP can first be excited under light irradiation, subsequently inducing a structural relaxation into a hydrated hydrogen atom. Thus, Raman intensities of the interfacial water in the EHIP species are signifcantly enhanced due to the cathodic polarization on silver and gold electrodes.

  20. The Thermochemical Stability of Ionic Noble Gas Compounds.

    ERIC Educational Resources Information Center

    Purser, Gordon H.

    1988-01-01

    Presents calculations that suggest stoichiometric, ionic, and noble gas-metal compounds may be stable. Bases calculations on estimated values of electron affinity, anionic radius for the noble gases and for the Born exponents of resulting crystals. Suggests the desirability of experiments designed to prepare compounds containing anionic,…

  1. Metal-gas fuel cell

    SciTech Connect

    Struthers, R.C.

    1984-10-16

    A metal-gas fuel cell comprising an anode chamber filled with a base anolyte solution, a metallic anode plate immersed in the anolyte; an ion exchange chamber filled with a base ionolyte solution adjacent the anode chamber; a cationic membrane between the anode and ion exchange chambers separating the anolyte and ionolyte; a cathode plate adjacent the ion exchange chamber remote from the cationic membrane with one surface in contact with the ionolyte and another surface in contact with a cathode fuel gas. The cathode plate is a laminated structure including a layer of hydrophyllic material in contact with the ionolyte, a layer of gas permeable hydrophobic material in contact with the gas and a gas and liquid permeable current collector of inert material with catalytic surfaces within the layer of hydrophyllic material. The anode and cathode plates are connected with an external electric circuit which effects the flow of electrons from the anode plate to the cathode plate.

  2. Toward control of the metal-organic interfacial electronic structure in molecular electronics: a first-principles study on self-assembled monolayers of pi-conjugated molecules on noble metals.

    PubMed

    Heimel, Georg; Romaner, Lorenz; Zojer, Egbert; Brédas, Jean-Luc

    2007-04-01

    Self-assembled monolayers (SAMs) of organic molecules provide an important tool to tune the work function of electrodes in plastic electronics and significantly improve device performance. Also, the energetic alignment of the frontier molecular orbitals in the SAM with the Fermi energy of a metal electrode dominates charge transport in single-molecule devices. On the basis of first-principles calculations on SAMs of pi-conjugated molecules on noble metals, we provide a detailed description of the mechanisms that give rise to and intrinsically link these interfacial phenomena at the atomic level. The docking chemistry on the metal side of the SAM determines the level alignment, while chemical modifications on the far side provide an additional, independent handle to modify the substrate work function; both aspects can be tuned over several eV. The comprehensive picture established in this work provides valuable guidelines for controlling charge-carrier injection in organic electronics and current-voltage characteristics in single-molecule devices.

  3. Investigation of the new sorption preconcentration systems for determination of noble metals in rocks by inductively coupled plasma-mass spectrometry.

    PubMed

    Dubenskiy, A S; Seregina, I F; Blinnikova, Z K; Tsyurupa, M P; Pavlova, L A; Davankov, V A; Bolshov, M A

    2016-06-01

    The reversible sorption preconcentration of noble metals (NMs) prior to their determination by inductively coupled plasma-mass spectrometry (ICP-MS) was investigated. Six new hypercrosslinked polystyrene sorbents were tested. The dependence of the degree of NMs sorption on the average degree of polymer network crosslinking and pore diameters was investigated. It was found that sorbents HP-100/6, HP-300/6 and HP-500/6 have low efficiency of NMs chlorocomplexes extraction. Among Stirosorb sorbents (Stirosorb-2, Stirosorb-514 and Stirosorb-584) the highest efficiency of the extraction of NMs' chlorocomplexes has Stirosorb-514. Tributylamine (TBA), N-methylbenzylamine (MBA), N,N-dimethylbenzylamine (DMBA), N,N-dibenzylmetylamine (DBMA) were studied as the reagents for extraction of Ru, Rh, Pd, Ir, Pt and Au chlorocomplexes from hydrochloric acid solutions in the form of ion associates by reversed-phase mechanism. The reversible quantitative extraction of Ru, Pd, Pt and Au in system Stirosorb-514 - TBA - 1M HCl in ethanol as eluent was achieved. It was found that resulting eluates do not contain matrix components which may cause spectral interferences on the stage of NMs determination by ICP-MS. The found scheme of NMs reversible sorption was validated by the analysis of certified reference materials of basic and ultrabasic rocks GPt-5, GPt-6 and SARM-7. Good agreement between the measured NMs concentrations and the certified values was demonstrated. The achieved limits of detection for Ru, Pd, Pt and Au vary within 10(-8)-10(-7)wt% range. PMID:27130114

  4. Determination of plasma frequency, damping constant, and size distribution from the complex dielectric function of noble metal nanoparticles

    SciTech Connect

    Mendoza Herrera, Luis J.; Arboleda, David Muñetón; Schinca, Daniel C.; Scaffardi, Lucía B.

    2014-12-21

    This paper develops a novel method for simultaneously determining the plasma frequency ω{sub P}   and the damping constant γ{sub free} in the bulk damped oscillator Drude model, based on experimentally measured real and imaginary parts of the metal refractive index in the IR wavelength range, lifting the usual approximation that restricts frequency values to the UV-deep UV region. Our method was applied to gold, silver, and copper, improving the relative uncertainties in the final values for ω{sub p} (0.5%–1.6%) and for γ{sub free} (3%–8%), which are smaller than those reported in the literature. These small uncertainties in ω{sub p} and γ{sub free} determination yield a much better fit of the experimental complex dielectric function. For the case of nanoparticles (Nps), a series expansion of the Drude expression (which includes ω{sub p} and γ{sub free} determined using our method) enables size-dependent dielectric function to be written as the sum of three terms: the experimental bulk dielectric function plus two size corrective terms, one for free electron, and the other for bound-electron contributions. Finally, size distribution of nanometric and subnanometric gold Nps in colloidal suspension was determined through fitting its experimental optical extinction spectrum using Mie theory based on the previously determined dielectric function. Results are compared with size histogram obtained from Transmission Electron Microscopy (TEM)

  5. Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting.

    PubMed

    Wang, Haotian; Lee, Hyun-Wook; Deng, Yong; Lu, Zhiyi; Hsu, Po-Chun; Liu, Yayuan; Lin, Dingchang; Cui, Yi

    2015-01-01

    Developing earth-abundant, active and stable electrocatalysts which operate in the same electrolyte for water splitting, including oxygen evolution reaction and hydrogen evolution reaction, is important for many renewable energy conversion processes. Here we demonstrate the improvement of catalytic activity when transition metal oxide (iron, cobalt, nickel oxides and their mixed oxides) nanoparticles (∼20 nm) are electrochemically transformed into ultra-small diameter (2-5 nm) nanoparticles through lithium-induced conversion reactions. Different from most traditional chemical syntheses, this method maintains excellent electrical interconnection among nanoparticles and results in large surface areas and many catalytically active sites. We demonstrate that lithium-induced ultra-small NiFeOx nanoparticles are active bifunctional catalysts exhibiting high activity and stability for overall water splitting in base. We achieve 10 mA cm(-2) water-splitting current at only 1.51 V for over 200 h without degradation in a two-electrode configuration and 1 M KOH, better than the combination of iridium and platinum as benchmark catalysts. PMID:26099250

  6. Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting

    NASA Astrophysics Data System (ADS)

    Wang, Haotian; Lee, Hyun-Wook; Deng, Yong; Lu, Zhiyi; Hsu, Po-Chun; Liu, Yayuan; Lin, Dingchang; Cui, Yi

    2015-06-01

    Developing earth-abundant, active and stable electrocatalysts which operate in the same electrolyte for water splitting, including oxygen evolution reaction and hydrogen evolution reaction, is important for many renewable energy conversion processes. Here we demonstrate the improvement of catalytic activity when transition metal oxide (iron, cobalt, nickel oxides and their mixed oxides) nanoparticles (~20 nm) are electrochemically transformed into ultra-small diameter (2-5 nm) nanoparticles through lithium-induced conversion reactions. Different from most traditional chemical syntheses, this method maintains excellent electrical interconnection among nanoparticles and results in large surface areas and many catalytically active sites. We demonstrate that lithium-induced ultra-small NiFeOx nanoparticles are active bifunctional catalysts exhibiting high activity and stability for overall water splitting in base. We achieve 10 mA cm-2 water-splitting current at only 1.51 V for over 200 h without degradation in a two-electrode configuration and 1 M KOH, better than the combination of iridium and platinum as benchmark catalysts.

  7. Laser-assisted solar cell metallization processing

    NASA Technical Reports Server (NTRS)

    Dutta, S.

    1984-01-01

    Laser assisted processing techniques utilized to produce the fine line, thin metal grid structures that are required to fabricate high efficiency solar cells are investigated. The tasks comprising these investigations are summarized. Metal deposition experiments are carried out utilizing laser assisted pyrolysis of a variety of metal bearing polymer films and metalloorganic inks spun onto silicon substrates. Laser decomposition of spun on silver neodecanoate ink yields very promising results. Solar cell comb metallization patterns are written using this technique.

  8. 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...

  9. Three-Electrode Metal Oxide Reduction Cell

    DOEpatents

    Dees, Dennis W.; Ackerman, John P.

    2005-06-28

    A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

  10. Three-electrode metal oxide reduction cell

    DOEpatents

    Dees, Dennis W.; Ackerman, John P.

    2008-08-12

    A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

  11. Colloidal nickel/gallium nanoalloys obtained from organometallic precursors in conventional organic solvents and in ionic liquids: noble-metal-free alkyne semihydrogenation catalysts

    NASA Astrophysics Data System (ADS)

    Schütte, Kai; Doddi, Adinarayana; Kroll, Clarissa; Meyer, Hajo; Wiktor, Christian; Gemel, Christian; van Tendeloo, Gustaaf; Fischer, Roland A.; Janiak, Christoph

    2014-04-01

    Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)2] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)3] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)4]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively

  12. Planetary noble gases

    NASA Technical Reports Server (NTRS)

    Zahnle, Kevin

    1993-01-01

    An overview of the history and current status of research on planetary noble gases is presented. The discovery that neon and argon are vastly more abundant on Venus than on earth points to the solar wind rather than condensation as the fundamental process for placing noble gases in the atmospheres of the terrestrial planets; however, solar wind implantation may not be able to fully reproduce the observed gradient, nor does it obviously account for similar planetary Ne/Ar ratios and dissimilar planetary Ar/Kr ratios. More recent studies have emphasized escape rather than accretion. Hydrodynamic escape, which is fractionating, readily accounts for the difference between atmospheric neon and isotopically light mantle neon. Atmospheric cratering, which is nearly nonfractionating, can account for the extreme scarcity of nonradiogenic noble gases (and other volatiles) on Mars.

  13. Mechanisms of kidney cell injury from metals.

    PubMed

    Fowler, B A

    1993-04-01

    The most environmentally abundant toxic metals/metalloids (arsenic, cadmium, lead, and mercury) are each known to produce cell injury in the kidney but the molecular mechanisms underlying these events are now being elucidated. It is clear that the nephrotoxicity of these agents is due, in part, to the fact that urinary elimination is a major route of excretion from the body. The role(s) of molecular factors such as metal-binding proteins, inclusion bodies, and cell-specific receptorlike proteins that appear to influence renal tubule cell expression, have attracted increased interest as determinants that modulate cell populations as special risk for toxicity and renal cancer. The future of mechanistic toxicology studies with regard to how and why only certain renal cell populations become targets for toxicity from these metals/metalloids and other less common inorganic nephrotoxicants must focus on the molecular handling of these agents by target cell populations.

  14. The Noble Savage.

    ERIC Educational Resources Information Center

    Greer, Sandy

    1993-01-01

    Traces the history of the "noble savage" concept, from the romantic view of the fifteenth through eighteenth centuries of American Indians as holdovers from the "golden age," to current media images of the medicine man or the Indian princess. Discusses how this patronizing stereotype continues to undermine Indian identity. (SV)

  15. Several new catalysts for reduction of oxygen in fuel cells

    NASA Technical Reports Server (NTRS)

    Cattabriga, R. A.; Cohn, E. M.; Giner, J. D.; Makrides, A. C.; Swette, L. L.

    1970-01-01

    Test results prove nickel carbide or nitride, nickel-cobalt carbide, titanium carbide or nitride, and intermetallic compounds of the transition or noble metals to be efficient electrocatalysts for oxygen reduction in alkaline electrolytes in low temperature fuel cells.

  16. Laser-assisted solar cell metallization processing

    NASA Technical Reports Server (NTRS)

    Dutta, S.

    1984-01-01

    Laser-assisted processing techniques utilized to produce the fine line, thin metal grid structures that are required to fabricate high efficiency solar cells are examined. Two basic techniques for metal deposition are investigated; (1) photochemical decomposition of liquid or gas phase organometallic compounds utilizing either a focused, CW ultraviolet laser (System 1) or a mask and ultraviolet flood illumination, such as that provided by a repetitively pulsed, defocused excimer laser (System 2), for pattern definition, and (2) thermal deposition of metals from organometallic solutions or vapors utilizing a focused, CW laser beam as a local heat source to draw the metallization pattern.

  17. Transition metals activate TFEB in overexpressing cells.

    PubMed

    Peña, Karina A; Kiselyov, Kirill

    2015-08-15

    Transition metal toxicity is an important factor in the pathogenesis of numerous human disorders, including neurodegenerative diseases. Lysosomes have emerged as important factors in transition metal toxicity because they handle transition metals via endocytosis, autophagy, absorption from the cytoplasm and exocytosis. Transcription factor EB (TFEB) regulates lysosomal biogenesis and the expression of lysosomal proteins in response to lysosomal and/or metabolic stresses. Since transition metals cause lysosomal dysfunction, we proposed that TFEB may be activated to drive gene expression in response to transition metal exposure and that such activation may influence transition metal toxicity. We found that transition metals copper (Cu) and iron (Fe) activate recombinant TFEB and stimulate the expression of TFEB-dependent genes in TFEB-overexpressing cells. In cells that show robust lysosomal exocytosis, TFEB was cytoprotective at moderate levels of Cu exposure, decreasing oxidative stress as reported by the expression of heme oxygenase-1 (HMOX1) gene. However, at high levels of Cu exposure, particularly in cells with low levels of lysosomal exocytosis, activation of overexpressed TFEB was toxic, increasing oxidative stress and mitochondrial damage. Based on these data, we conclude that TFEB-driven gene network is a component of the cellular response to transition metals. These data suggest limitations and disadvantages of TFEB overexpression as a therapeutic approach. PMID:26251447

  18. Transition metals activate TFEB in overexpressing cells

    PubMed Central

    Peña, Karina A.; Kiselyov, Kirill

    2015-01-01

    Transition metal toxicity is an important factor in the pathogenesis of numerous human disorders, including neurodegenerative diseases. Lysosomes have emerged as important factors in transition metal toxicity because they handle transition metals via endocytosis, autophagy, absorption from the cytoplasm and exocytosis. Transcription factor EB (TFEB) regulates lysosomal biogenesis and the expression of lysosomal proteins in response to lysosomal and/or metabolic stresses. Since transition metals cause lysosomal dysfunction, we proposed that TFEB may be activated to drive gene expression in response to transition metal exposure and that such activation may influence transition metal toxicity. We found that transition metals copper (Cu) and iron (Fe) activate recombinant TFEB and stimulate the expression of TFEB-dependent genes in TFEB-overexpressing cells. In cells that show robust lysosomal exocytosis, TFEB was cytoprotective at moderate levels of Cu exposure, decreasing oxidative stress as reported by the expression of heme oxygenase-1 (HMOX1) gene. However, at high levels of Cu exposure, particularly in cells with low levels of lysosomal exocytosis, activation of overexpressed TFEB was toxic, increasing oxidative stress and mitochondrial damage. Based on these data, we conclude that TFEB-driven gene network is a component of the cellular response to transition metals. These data suggest limitations and disadvantages of TFEB overexpression as a therapeutic approach. PMID:26251447

  19. Electrocatalyst for alcohol oxidation at fuel cell anodes

    DOEpatents

    Adzic, Radoslav; Kowal, Andrzej

    2011-11-02

    In some embodiments a ternary electrocatalyst is provided. The electrocatalyst can be used in an anode for oxidizing alcohol in a fuel cell. In some embodiments, the ternary electrocatalyst may include a noble metal particle having a surface decorated with clusters of SnO.sub.2 and Rh. The noble metal particles may include platinum, palladium, ruthenium, iridium, gold, and combinations thereof. In some embodiments, the ternary electrocatalyst includes SnO.sub.2 particles having a surface decorated with clusters of a noble metal and Rh. Some ternary electrocatalysts include noble metal particles with clusters of SnO.sub.2 and Rh at their surfaces. In some embodiments the electrocatalyst particle cores are nanoparticles. Some embodiments of the invention provide a fuel cell including an anode incorporating the ternary electrocatalyst. In some aspects a method of using ternary electrocatalysts of Pt, Rh, and SnO.sub.2 to oxidize an alcohol in a fuel cell is described.

  20. Cosmogenic noble gas paleothermometry

    NASA Astrophysics Data System (ADS)

    Tremblay, Marissa M.; Shuster, David L.; Balco, Greg

    2014-08-01

    We present a theoretical basis for reconstructing paleotemperatures from the open-system behavior of cosmogenic noble gases produced in minerals at Earth's surface. Experimentally-determined diffusion kinetics predicts diffusive loss of cosmogenic 3He and 21Ne from common minerals like quartz and feldspars at ambient temperatures; incomplete retention has also been observed empirically in field studies. We show that the theory of simultaneous production and diffusion that applies to radiogenic noble gases in minerals-the basis of thermochronology-can also be applied to cosmogenic noble gases to reconstruct past surface temperatures on Earth. We use published diffusion kinetics and production rates for 3He in quartz and 21Ne in orthoclase to demonstrate the resolving power of cosmogenic noble gas paleothermometry with respect to exposure duration, temperature, and diffusion domain size. Calculations indicate that, when paired with a quantitatively retained cosmogenic nuclide such as 21Ne or 10Be, observations of cosmogenic 3He in quartz can constrain temperatures during surface exposure in polar and high altitude environments. Likewise, 21Ne retention in feldspars is sensitive to temperatures at lower latitudes and elevations, expanding the potential geographic applicability of this technique to most latitudes. As an example, we present paired measurements of 3He and 10Be in quartz from a suite of Antarctic sandstone erratics to test whether the abundances of cosmogenic 3He agree with what is predicted from first principles and laboratory-determined diffusion kinetics. We find that the amounts of cosmogenic 3He present in these samples are consistent with the known mean annual temperature (MAT) for this region of Antarctica between -25 and -30 °C. These results demonstrate the method's ability to record paleotemperatures through geologic time.

  1. Fuel cells and the theory of metals.

    NASA Technical Reports Server (NTRS)

    Bocciarelli, C. V.

    1972-01-01

    Metal theory is used to study the role of metal catalysts in electrocatalysis, with particular reference to alkaline hydrogen-oxygen fuel cells. Use is made of a simple model, analogous to that used to interpret field emission in vacuum. Theoretical values for all the quantities in the Tafel equation are obtained in terms of bulk properties of the metal catalysts (such as free electron densities and Fermi level). The reasons why some processes are reversible (H-electrodes) and some irreversible (O-electrodes) are identified. Selection rules for desirable properties of catalytic materials are established.

  2. Development of nickel-metal hydride cell

    NASA Technical Reports Server (NTRS)

    Kuwajima, Saburo; Kamimori, Nolimits; Nakatani, Kensuke; Yano, Yoshiaki

    1993-01-01

    National Space Development Agency of Japan (NASDA) has conducted the research and development (R&D) of battery cells for space use. A new R&D program about a Nickel-Metal Hydride (Ni-MH) cell for space use from this year, based on good results in evaluations of commercial Ni-MH cells in Tsukuba Space Center (TKSC), was started. The results of those commercial Ni-MH cell's evaluations and recent status about the development of Ni-MH cells for space use are described.

  3. Metal containing polymers as fuel cell catalysts

    NASA Astrophysics Data System (ADS)

    Reed, James L.

    1987-06-01

    Several aspects of the fuel cell problem were addressed in this investigation. The objective of this work was the development of a fuel cell electrode-catalyst for use in a carbon monoxide fuel cell, which would utilize polymer bound metal complexes as the catalytic species. Several commercially available polymers were examined to be used as backbones in the development of an electrode-catalyst. Polystyrene was chosen for more extensive study. The polymer was activated by complete or partial monochloromethylation of the pendant phenyls. Several schemes for binding cyclic tetradentate and bidentate ligands to the activated polymers were not obtained. The transition metals cobalt and nickel were incorporated into the polymers, and these new materials were examined. In addition, the electrochemical behavior of several metal complexes which hold potential as catalytic species was examined.

  4. Solar cell having improved front surface metallization

    SciTech Connect

    Lillington, D.R.; Mardesich, N.; Dill, H.G.; Garlick, G.F.J.

    1987-09-15

    This patent describes a solar cell comprising: a first layer of gallium arsenide semiconductor material of an N+ conductivity; a second layer of gallium arsenide semiconductor material of an N conductivity overlying the first layer; a third layer of gallium arsenide semiconductor material of a P conductivity overlying the N conductivity layer and forming a P-N junction therebetween. A layer of aluminium gallium arsenide semiconductor material of a p conductivity overlying the front major surface of the P conductivity third layer and having an exposed surface essentially parallel to the front major surface and at least one edge; a plurality of metallic contact lines made of a first metal alloy composition and being spaced apart by a first predetermined distance traversing the exposed surface and extending through the aluminium gallium arsenide layer to the front major surface and making electrical contact to the third layer; a plurality of longitudinally disposed metallic grid lines made of a second metal alloy composition and being spaced apart by a second predetermined distance located on the exposed surface of the aluminium gallium arsenide layer and which cross the metallic contact lines and make electrical contact to the metallic lines; a flat metallic strip disposed on the aluminium gallium arsenide layer exposed surface near the edge, the strip electrically coupling the metallic grid lines to one another; and a back contact located on the back major surface.

  5. Trapped noble gases in meteorites

    NASA Technical Reports Server (NTRS)

    Swindle, Timothy D.

    1988-01-01

    The trapped noble gases in meteorites come in two main varieties, usually referred to as solar and planetary. The solar noble gases are implanted solar-wind or solar-flare materials, and thus their relative elemental abundances provide a good estimate of those of the sun. The planetary noble gases have relative elemental abundances similar to those in the terrestrial atmosphere, but there are also important distinctions. At least one other elemental pattern (subsolar) and several isotopic patterns have also been identified.

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

    DOEpatents

    Gorer, Alexander

    2002-01-01

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

  7. PD/MG BIMETALLIC CORROSION CELLS FOR DECHLORINATING PCBS

    EPA Science Inventory

    Two dissimilar metals immersed in a conducting solution develop different corrosion potentials forming a bimetallic corrosion cell. Enhanced corrosion of an active metal like Mg combined with catalytic hydrogenation properties of a noble metal like Pd in such bimetallic cells can...

  8. Apparatus for the electrolytic production of metals

    DOEpatents

    Sadoway, Donald R.

    1993-01-01

    Improved electrolytic cells for producing metals by the electrolytic reduction of a compound dissolved in a molten electrolyte are disclosed. In the improved cells, at least one electrode includes a protective layer comprising an oxide of the cell product metal formed upon an alloy of the cell product metal and a more noble metal. In the case of an aluminum reduction cell, the electrode can comprise an alloy of aluminum with copper, nickel, iron, or combinations thereof, upon which is formed an aluminum oxide protective layer.

  9. Static impedance behavior of programmable metallization cells

    NASA Astrophysics Data System (ADS)

    Rajabi, S.; Saremi, M.; Barnaby, H. J.; Edwards, A.; Kozicki, M. N.; Mitkova, M.; Mahalanabis, D.; Gonzalez-Velo, Y.; Mahmud, A.

    2015-04-01

    Programmable metallization cell (PMC) devices work by growing and dissolving a conducting metallic bridge across a chalcogenide glass (ChG) solid electrolyte, which changes the resistance of the cell. PMC operation relies on the incorporation of metal ions in the ChG films via photo-doping to lower the off-state resistance and stabilize resistive switching, and subsequent transport of these ions by electric fields induced from an externally applied bias. In this paper, the static on- and off-state resistance of a PMC device composed of a layered (Ag-rich/Ag-poor) Ge30Se70 ChG film with active Ag and inert Ni electrodes is characterized and modeled using three dimensional simulation code. Calibrating the model to experimental data enables the extraction of device parameters such as material bandgaps, workfunctions, density of states, carrier mobilities, dielectric constants, and affinities.

  10. Polarized noble gas MRI

    SciTech Connect

    Brookeman, James R.; Mugler, John P. III; Lange, Eduard E. de; Knight-Scott, Jack; Maier, Therese; Bogorad, Paul; Driehuys, Bastiaan; Cates, Gordon; Happer, William; Daniel, Thomas M.; Truwit, Jonathon D.

    1998-01-20

    The development of convenient methods to polarize liter quantities of the noble gases helium-3 and xenon-129 has provided the opportunity for a new MRI method to visualize the internal air spaces of the human lung. These spaces are usually poorly seen with hydrogen-based MRI, because of the limited water content of the lung and the low thermal polarization of the water protons achieved in conventional magnets. In addition, xenon, which has a relatively high solubility and a sufficiently persistent polarization level in blood and biological tissue, offers the prospect of providing perfusion images of the lung, brain and other organs.

  11. Metal electrode for amorphous silicon solar cells

    DOEpatents

    Williams, Richard

    1983-01-01

    An amorphous silicon solar cell having an N-type region wherein the contact to the N-type region is composed of a material having a work function of about 3.7 electron volts or less. Suitable materials include strontium, barium and magnesium and rare earth metals such as gadolinium and yttrium.

  12. 77 FR 70159 - Marble River, LLC v. Noble Clinton Windpark I, LLC, Noble Ellenburg Windpark, LLC, Noble...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-11-23

    ... Energy Regulatory Commission Marble River, LLC v. Noble Clinton Windpark I, LLC, Noble Ellenburg Windpark..., Marble River, LLC (Marble River or Complainant) filed a formal complaint against Noble Clinton Windpark I... pay Marble River for headroom created by common system upgrade facilities that benefit Noble and...

  13. A noble and single source precursor for the synthesis of metal-rich sulphides embedded in an N-doped carbon framework for highly active OER electrocatalysts.

    PubMed

    Barman, Barun Kumar; Nanda, Karuna Kar

    2016-04-21

    Here, we demonstrate a green and environment-friendly pyrolysis route for the synthesis of metal-rich sulphide embedded in an N-doped carbon (NC) framework in the absence of sulphide ions (S(2-)). The metal-chelate complex (tris(ethylenediamine) metal(ii) sulfate) serves as a new and single source precursor for the synthesis of earth abundant and non-precious hybrid structures such as metal-rich sulphides Co9S8@NC and Ni3S2@NC when M(II) = Co(2+) and Ni(2+) and counter sulphate (SO4(2-)) ions are the source of S. Both the hybrids show superior OER activity as compared to commercial RuO2.

  14. Formation of a quasi-solid structure by intercalated noble gas atoms in pores of Cu(I)-MFU-4l metal-organic framework.

    PubMed

    Magdysyuk, Oxana V; Denysenko, Dmytro; Weinrauch, Ingrid; Volkmer, Dirk; Hirscher, Michael; Dinnebier, Robert E

    2015-01-14

    The primary adsorption sites for Kr and Xe within the large-pore metal-organic framework Cu(I)-MFU-4l have been investigated by high-resolution synchrotron powder diffraction, revealing an enormous number of adsorption sites: in total, 10 crystallographically different positions for Xe and 8 positions for Kr were localized, the first five of which are located near metal atoms and the organic linker, and the remaining sites form a second adsorption layer in the pores.

  15. Formation of a quasi-solid structure by intercalated noble gas atoms in pores of Cu(I)-MFU-4l metal-organic framework.

    PubMed

    Magdysyuk, Oxana V; Denysenko, Dmytro; Weinrauch, Ingrid; Volkmer, Dirk; Hirscher, Michael; Dinnebier, Robert E

    2015-01-14

    The primary adsorption sites for Kr and Xe within the large-pore metal-organic framework Cu(I)-MFU-4l have been investigated by high-resolution synchrotron powder diffraction, revealing an enormous number of adsorption sites: in total, 10 crystallographically different positions for Xe and 8 positions for Kr were localized, the first five of which are located near metal atoms and the organic linker, and the remaining sites form a second adsorption layer in the pores. PMID:25418446

  16. Iodide-mediated control of rhodium epitaxial growth on well-defined noble metal nanocrystals: synthesis, characterization, and structure-dependent catalytic properties.

    PubMed

    Sneed, Brian T; Kuo, Chun-Hong; Brodsky, Casey N; Tsung, Chia-Kuang

    2012-11-01

    Metal nanocrystals (NCs) comprising rhodium are heterogeneous catalysts for CO oxidation, NO reduction, hydrogenations, electro-oxidations, and hydroformylation reactions. It has been demonstrated that control of structure at the nanoscale can enhance the performance of a heterogeneous metal catalyst, such as Rh, but molecular-level control of NCs comprising this metal is less studied compared to gold, silver, platinum, and palladium. We report an iodide-mediated epitaxial overgrowth of Rh by using the surfaces of well-defined foreign metal crystals as substrates to direct the Rh surface structures. The epigrowth can be accomplished on different sizes, morphologies, and identities of metal substrates. The surface structures of the resulting bimetallic NCs were studied using electron microscopy, and their distinct catalytic behaviors were examined in CO stripping and the electro-oxidation of formic acid. Iodide was found to play a crucial role in the overgrowth mechanism. With the addition of iodide, the Rh epigrowth can even be achieved on gold substrates despite the rather large lattice mismatch of ~7%. Hollow Rh nanostructures have also been generated by selective etching of the core substrates. The new role of iodide in the overgrowth and the high level of control for Rh could hold the key to future nanoscale control of this important metal's architecture for use in heterogeneous catalysis.

  17. Noble gases in the moon

    NASA Technical Reports Server (NTRS)

    Manuel, O. K.; Srinivasan, B.; Hennecke, E. W.; Sinclair, D. E.

    1972-01-01

    The abundance and isotopic composition of helium, neon, argon, krypton, and xenon which were released by stepwise heating of lunar fines (15601.64) and (15271.65) were measured spectrometrically. The results of a composition of noble gases released from the lunar fines with noble gases in meteorites and in the earth are presented along with the isotopic composition of noble gases in lunar fines, in meteorites, and in the atmosphere. A study of two isotopically distinct components of trapped xenon in carbonaceous chondrites is also included.

  18. Towards a Noble Gas Oscillator

    NASA Astrophysics Data System (ADS)

    Korver, Anna; Walker, Thad

    2014-05-01

    Noble gas NMR detected by alkali co-magnetometers has the potential for measurement of precession frequencies at the pHz level. This is done by eliminating the dominant known sources of systematic errors: alkali frequency shifts and quadrupole shifts. We present results of successful synchronous pumping of noble gas nuclei and measurements of alkali co-magnetometer sensitivity levels that project a 131-Xe noise level of 100 nHz /√{ Hz} . Future dual noble-gas co-magnetometry promises to improve the noise level by a factor of 10 or more. This research is supported by the NSF and Northrop-Grumman Corp.

  19. Carbonates-based noble metal-free lean NOx trap catalysts MOx-K2CO3/K2Ti8O17 (M = Ce, Fe, Cu, Co) with superior catalytic performance

    NASA Astrophysics Data System (ADS)

    Zhang, Yuxia; You, Rui; Liu, Dongsheng; Liu, Cheng; Li, Xingang; Tian, Ye; Jiang, Zheng; Zhang, Shuo; Huang, Yuying; Zha, Yuqing; Meng, Ming

    2015-12-01

    A series of base metal-based lean NOx trap (LNT) catalysts MOx-K2CO3/K2Ti8O17 (M = Ce, Fe, Cu, Co) were synthesized by successive impregnations and employed for the storage and reduction of NOx in the emissions of lean-burn engines at 350 °C. The XRD and XANES/EXAFS results reveal that the active phases in the corresponding catalysts exist as CeO2, Fe2O3, CuO and Co3O4, respectively. Among all the catalysts, CoOx-K2CO3/K2Ti8O17 exhibits the best performance, which cannot only trap the NOx quickly and completely at lean condition, giving the highest storage capacity (3.32 mmol/g) reported so far, but also reduce the NOx at rich condition, showing a NOx reduction percentage as high as 99.0%. Meanwhile, this catalyst displays an ultralow NOx to N2O selectivity (0.3%) during NOx reduction. The excellent performance of CoOx-K2CO3/K2Ti8O17 results from its largest amount of surface active oxygen species as revealed by XPS, O2-TPD and NO-TPD. HRTEM, FT-IR and CO2-TPD results illustrate that several kinds of K species such as sbnd OK groups, K2O, surface carbonates and bulk or bulk-like carbonates coexist in the catalysts. Based upon the in situ DRIFTS results, the participation of K2CO3 in NOx storage is confirmed, and the predominant NOx storage species is revealed as bidentate nitrites formed via multiple kinetic pathways. The low cost and high catalytic performance of the CoOx-based LNT catalyst make it most promising for the substitution of noble metal-based LNT catalysts.

  20. Process for recycling components of a PEM fuel cell membrane electrode assembly

    DOEpatents

    Shore, Lawrence

    2012-02-28

    The membrane electrode assembly (MEA) of a PEM fuel cell can be recycled by contacting the MEA with a lower alkyl alcohol solvent which separates the membrane from the anode and cathode layers of the assembly. The resulting solution containing both the polymer membrane and supported noble metal catalysts can be heated under mild conditions to disperse the polymer membrane as particles and the supported noble metal catalysts and polymer membrane particles separated by known filtration means.

  1. Switching kinetics of electrochemical metallization memory cells.

    PubMed

    Menzel, Stephan; Tappertzhofen, Stefan; Waser, Rainer; Valov, Ilia

    2013-05-14

    The strongly nonlinear switching kinetics of electrochemical metallization memory (ECM) cells are investigated using an advanced 1D simulation model. It is based on the electrochemical growth and dissolution of a Ag or Cu filament within a solid thin film and accounts for nucleation effects, charge transfer, and cation drift. The model predictions are consistent with experimental switching results of a time range of 12 orders of magnitude obtained from silver iodide (AgI) based ECM cells. By analyzing the simulation results the electrochemical processes limiting the switching kinetics are revealed. This study provides new insights into the understanding of the limiting electrochemical processes determining the switching kinetics of ECM cells. PMID:23549450

  2. Density functional theoretical study of pentacene/noble metal interfaces with van der Waals corrections: Vacuum level shifts and electronic structures

    NASA Astrophysics Data System (ADS)

    Toyoda, Kenji; Hamada, Ikutaro; Lee, Kyuho; Yanagisawa, Susumu; Morikawa, Yoshitada

    2010-04-01

    In order to clarify factors determining the interface dipole, we have studied the electronic structures of pentacene adsorbed on Cu(111), Ag(111), and Au(111) by using first-principles density functional theoretical calculations. In the structural optimization, a semiempirical van der Waals (vdW) approach [S. Grimme, J. Comput. Chem. 27, 1787 (2006)] is employed to include long-range vdW interactions and is shown to reproduce pentacene-metal distances quite accurately. The pentacene-metal distances for Cu, Ag, and Au are evaluated to be 0.24, 0.29, and 0.32 nm, respectively, and work function changes calculated by using the theoretically optimized adsorption geometries are in good agreement with the experimental values, indicating the validity of the present approach in the prediction of the interface dipole at metal/organic interfaces. We examined systematically how the geometric factors, especially the pentacene-substrate distance ( Z C ) , and the electronic properties of the metal substrates contribute to the interface dipole. We found that at Z C ≥ 0.35 nm , the work function changes ( Δ ϕ 's) do not depend on the substrate work function ( ϕ m ) , indicating that the interface level alignment is nearly in the Schottky limit, whereas at Z C ≤ 0.25 nm , Δ ϕ 's vary nearly linearly with ϕ m , and the interface level alignment is in the Bardeen limit. Our results indicate the importance of both the geometric and the electronic factors in predicting the interface dipoles. The calculated electronic structure shows that on Au, the long-range vdW interaction dominates the pentacene-substrate interaction, whereas on Cu and Ag, the chemical hybridization contributes to the interaction.

  3. Understanding the adsorption of CuPc and ZnPc on noble metal surfaces by combining quantum-mechanical modelling and photoelectron spectroscopy.

    PubMed

    Huang, Yu Li; Wruss, Elisabeth; Egger, David A; Kera, Satoshi; Ueno, Nobuo; Saidi, Wissam A; Bucko, Tomas; Wee, Andrew T S; Zojer, Egbert

    2014-03-07

    Phthalocyanines are an important class of organic semiconductors and, thus, their interfaces with metals are both of fundamental and practical relevance. In the present contribution we provide a combined theoretical and experimental study, in which we show that state-of-the-art quantum-mechanical simulations are nowadays capable of treating most properties of such interfaces in a quantitatively reliable manner. This is shown for Cu-phthalocyanine (CuPc) and Zn-phthalocyanine (ZnPc) on Au(111) and Ag(111) surfaces. Using a recently developed approach for efficiently treating van der Waals (vdW) interactions at metal/organic interfaces, we calculate adsorption geometries in excellent agreement with experiments. With these geometries available, we are then able to accurately describe the interfacial electronic structure arising from molecular adsorption. We find that bonding is dominated by vdW forces for all studied interfaces. Concomitantly, charge rearrangements on Au(111) are exclusively due to Pauli pushback. On Ag(111), we additionally observe charge transfer from the metal to one of the spin-channels associated with the lowest unoccupied π-states of the molecules. Comparing the interfacial density of states with our ultraviolet photoelectron spectroscopy (UPS) experiments, we find that the use of a hybrid functionals is necessary to obtain the correct order of the electronic states.

  4. Understanding the adsorption of CuPc and ZnPc on noble metal surfaces by combining quantum-mechanical modelling and photoelectron spectroscopy.

    PubMed

    Huang, Yu Li; Wruss, Elisabeth; Egger, David A; Kera, Satoshi; Ueno, Nobuo; Saidi, Wissam A; Bucko, Tomas; Wee, Andrew T S; Zojer, Egbert

    2014-01-01

    Phthalocyanines are an important class of organic semiconductors and, thus, their interfaces with metals are both of fundamental and practical relevance. In the present contribution we provide a combined theoretical and experimental study, in which we show that state-of-the-art quantum-mechanical simulations are nowadays capable of treating most properties of such interfaces in a quantitatively reliable manner. This is shown for Cu-phthalocyanine (CuPc) and Zn-phthalocyanine (ZnPc) on Au(111) and Ag(111) surfaces. Using a recently developed approach for efficiently treating van der Waals (vdW) interactions at metal/organic interfaces, we calculate adsorption geometries in excellent agreement with experiments. With these geometries available, we are then able to accurately describe the interfacial electronic structure arising from molecular adsorption. We find that bonding is dominated by vdW forces for all studied interfaces. Concomitantly, charge rearrangements on Au(111) are exclusively due to Pauli pushback. On Ag(111), we additionally observe charge transfer from the metal to one of the spin-channels associated with the lowest unoccupied π-states of the molecules. Comparing the interfacial density of states with our ultraviolet photoelectron spectroscopy (UPS) experiments, we find that the use of a hybrid functionals is necessary to obtain the correct order of the electronic states. PMID:24609018

  5. Laser-assisted solar cell metallization processing

    NASA Technical Reports Server (NTRS)

    Meier, D. L.

    1986-01-01

    The status of the laser-assisted solar cell metallization processing is described. Metallo-organic silver films were spun-on by argon ion laser beam pyrolysis. The metallo-organic decomposition (MOD) film was spun-on an evaporated Ti/Pd film to produce tood adhesion. In a maskless process, the argon ion laser writes the contact pattern. The film is then built up to obtain the required conductivity using conventional silverplating process. The Ti/Pd film in the field is chemically etched using the plated silver film as the mask. The width of the contact pattern is determined by the power of the laser. Widths as thin as 20 microns were obtained using 0.66 W of laser power. Cells fabricated with the 50 micron line widths of 4 ohm-cm floating zone (Fz) silicon-produced efficiencies of 16.6% (no passivation) which were equivalent to the best cells using conventional metallization/lithography and no passivation.

  6. Spectroscopic enhancement from noble mettalic nanoparticles

    NASA Astrophysics Data System (ADS)

    Tsai, Shu-Ju

    2011-12-01

    Resonant coupling of localized surface plasmon resonances (LSPRs) in noble metallic nanostructures to incident radiation and the related subject of localized behavior of electromagnetic waves are currently of great interest due to their potential application to sensors, biochemical assays, optical transmission, and photovoltaic devices. My thesis research is made up of two related parts. In part one I examined enhanced fluorescence in dye molecules in proximity to Ag nanostructures. In part two I studied the effect of Au nanostructure arrays on the performance of poly(3-hexylthiophene-2,5-diyl) : [6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) bulk heterojunction (BHJ) organic solar cells (OSCs). Nanostructures were fabricated by two different methods: e-beam lithography (top down) and spray pyrolysis (bottom up). Using e-beam lithography, we produced arrays of nanostructures with well defined shapes, sizes, and spacings. By systematically varying these topographical parameters, we measured their effect on nanometer-sized metallic structure-enhanced fluorescence (nMEF) and on absorption and external quantum efficiency (EQE) in OSC devices as a function of optical wavelength. In analyzing experimental results, we carried out numerical simulations of the local electric field under incident light, across plasmonic resonances. The comparison between the calculated local field squared and measured fluorescence/EQE provides physical insight on the configuration-dependence of these two processes. Our results indicate that local field enhancement near nanostructures is dominant in nMEF, and that the local field is strongly affected by the substrate and device architectures. For the OSCs, both measurements and calculations show that absorbance within the active layer is enhanced only in a narrow band of wavelengths (˜640-720 nm) where the active layer is not very absorbing for our prototype nanopillar-patterned devices. The peak enhancement for 180 nm wide Au

  7. Precious Metal Recovery from Fuel Cell MEA's

    SciTech Connect

    Lawrence Shore

    2004-04-25

    In 2003, Engelhard Corporation received a DOE award to develop a cost-effective, environmentally friendly approach to recover Pt from fuel cell membrane electrode assemblies (MEA’s). The most important precious metal used in fuel cells is platinum, but ruthenium is also added to the anode electrocatalyst if CO is present in the hydrogen stream. As part of the project, a large number of measurements of Pt and Ru need to be made. A low-cost approach to measuring Pt is using the industry standard spectrophotometric measurement of Pt complexed with stannous chloride. The interference of Ru can be eliminated by reading the Pt absorbance at 450 nm. Spectrophotometric methods for measuring Ru, while reported in the literature, are not as robust. This paper will discuss the options for measuring Pt and Ru using the method of UV-VIS spectrophotometry

  8. Metal-gas cell with electrolyte reservoir

    SciTech Connect

    Miller, L.E.; Carr, D.D.

    1984-10-16

    A metal-gas electrochemical cell is disclosed wherein electrolyte is progressively supplied from a reservoir into the electrode or cell stack as needed, so as to maintain each stack component with adequate electrolyte, as the plates ''grow'' and absorb electrolyte with repeated cycling. The reservoir preferably is a compressible bladder positioned between on end of the plate stack and a retaining plate. As the plate stack ''grows'' with repeated cycling, the bladder is slowly compressed, forcing electrolyte from the bladder through an electrolyte distribution tube located within the plate stack. One end of the electrolyte distribution tube is fixed to an end plate of the plate stack and the second end of the distribution tube may be connected to a Belleville washer or other spring which acts through the distribution tube to compress the plate stack. The elasticity of the spring permits the stack to expand as the electrodes grow.

  9. The AMOS cell - An improved metal-semiconductor solar cell. [Antireflection coated Metal Oxide Semiconductor

    NASA Technical Reports Server (NTRS)

    Stirn, R. J.; Yeh, Y.-C. M.

    1975-01-01

    A new fabrication process is being developed which significantly improves the efficiency of metal-semiconductor solar cells. The resultant effect, a marked increase in the open-circuit voltage, is produced by the addition of an interfacial layer oxide on the semiconductor. Cells using gold on n-type gallium arsenide have been made in small areas (0.17 sq cm) with conversion efficiencies of 15% in terrestrial sunlight.

  10. Reducing the Cost and Preserving the Reactivity in Noble-Metal-Based Catalysts: Oxidation of CO by Pt and Al-Pt Alloy Clusters Supported on Graphene.

    PubMed

    Koizumi, Kenichi; Nobusada, Katsuyuki; Boero, Mauro

    2016-04-01

    The oxidation mechanisms of CO to CO2 on graphene-supported Pt and Pt-Al alloy clusters are elucidated by reactive dynamical simulations. The general mechanism evidenced is a Langmuir-Hinshelwood (LH) pathway in which O2 is adsorbed on the cluster prior to the CO oxidation. The adsorbed O2 dissociates into two atomic oxygen atoms thus promoting the CO oxidation. Auxiliary simulations on alloy clusters in which other metals (Al, Co, Cr, Cu, Fe, Ni) replace a Pt atom have pointed to the aluminum doped cluster as a special case. In the nanoalloy, the reaction mechanism for CO oxidation is still a LH pathway with an activation barrier sufficiently low to be overcome at room temperature, thus preserving the catalyst efficiency. This provides a generalizable strategy for the design of efficient, yet sustainable, Pt-based catalysts at reduced cost. PMID:26878836

  11. The light-matter interaction of a single semiconducting AlGaN nanowire and noble metal Au nanoparticles in the sub-diffraction limit.

    PubMed

    Sivadasan, A K; Madapu, Kishore K; Dhara, Sandip

    2016-08-24

    Near field scanning optical microscopy (NSOM) is not only a tool for imaging of sub-diffraction limited objects but also a prominent characteristic tool for understanding the intrinsic properties of nanostructures. In order to understand light-matter interactions in the near field regime using a NSOM technique with an excitation of 532 nm (2.33 eV), we selected an isolated single semiconducting AlGaN nanowire (NW) of diameter ∼120 nm grown via a vapor liquid solid (VLS) mechanism along with a metallic Au nanoparticle (NP) catalyst. The role of electronic transitions from different native defect related energy states of AlGaN is discussed in understanding the NSOM images for the semiconducting NW. The effect of strong surface plasmon resonance absorption of an excitation laser on the NSOM images for Au NPs, involved in the VLS growth mechanism of NWs, is also observed. PMID:27511614

  12. The light-matter interaction of a single semiconducting AlGaN nanowire and noble metal Au nanoparticles in the sub-diffraction limit.

    PubMed

    Sivadasan, A K; Madapu, Kishore K; Dhara, Sandip

    2016-08-24

    Near field scanning optical microscopy (NSOM) is not only a tool for imaging of sub-diffraction limited objects but also a prominent characteristic tool for understanding the intrinsic properties of nanostructures. In order to understand light-matter interactions in the near field regime using a NSOM technique with an excitation of 532 nm (2.33 eV), we selected an isolated single semiconducting AlGaN nanowire (NW) of diameter ∼120 nm grown via a vapor liquid solid (VLS) mechanism along with a metallic Au nanoparticle (NP) catalyst. The role of electronic transitions from different native defect related energy states of AlGaN is discussed in understanding the NSOM images for the semiconducting NW. The effect of strong surface plasmon resonance absorption of an excitation laser on the NSOM images for Au NPs, involved in the VLS growth mechanism of NWs, is also observed.

  13. On the mechanisms of cation injection in conducting bridge memories: The case of HfO2 in contact with noble metal anodes (Au, Cu, Ag)

    NASA Astrophysics Data System (ADS)

    Saadi, M.; Gonon, P.; Vallée, C.; Mannequin, C.; Grampeix, H.; Jalaguier, E.; Jomni, F.; Bsiesy, A.

    2016-03-01

    Resistance switching is studied in HfO2 as a function of the anode metal (Au, Cu, and Ag) in view of its application to resistive memories (resistive random access memories, RRAM). Current-voltage (I-V) and current-time (I-t) characteristics are presented. For Au anodes, resistance transition is controlled by oxygen vacancies (oxygen-based resistive random access memory, OxRRAM). For Ag anodes, resistance switching is governed by cation injection (Conducting Bridge random access memory, CBRAM). Cu anodes lead to an intermediate case. I-t experiments are shown to be a valuable tool to distinguish between OxRRAM and CBRAM behaviors. A model is proposed to explain the high-to-low resistance transition in CBRAMs. The model is based on the theory of low-temperature oxidation of metals (Cabrera-Mott theory). Upon electron injection, oxygen vacancies and oxygen ions are generated in the oxide. Oxygen ions are drifted to the anode, and an interfacial oxide is formed at the HfO2/anode interface. If oxygen ion mobility is low in the interfacial oxide, a negative space charge builds-up at the HfO2/oxide interface. This negative space charge is the source of a strong electric field across the interfacial oxide thickness, which pulls out cations from the anode (CBRAM case). Inversely, if oxygen ions migration through the interfacial oxide is important (or if the anode does not oxidize such as Au), bulk oxygen vacancies govern resistance transition (OxRRAM case).

  14. Optimized metallization patterns for large-area silicon solar cells

    NASA Technical Reports Server (NTRS)

    Matzen, W. T.; Chiang, S. Y.; Carbajal, B. G.

    1976-01-01

    Design criteria is presented for optimizing the front-surface metallization pattern of large-area silicon solar cells. A computer program calculates the spacing of metal fingers which minimizes resistive and shadowing losses. Finger spacing and efficiency for the optimum design are presented as a function of finger width and cell size. It is shown that quantitative evaluation of metallization pattern options can be made without cell fabrication.

  15. Testing Metal Chlorides For Use In Sodium-Cell Cathodes

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar V.; Attia, Alan I.; Halpert, Gerald

    1992-01-01

    Cyclic voltammetric curves of transition-metal wires in molten NaAlCl4 electrolyte used to eliminate suitability of transition metals as cathodes in sodium cells. Cyclic voltammetry used in conjunction with measurement of galvanostatic polarization curves determines whether given metal chloride suitable as cathode material in such cell. Cells useful in such high-energy-density and high-power-density applications as leveling loads on electric-power plants, supplying power to electric ground vehicles, and aerospace applications.

  16. Modeling the Noble Metal/TiO2 (110) Interface with Hybrid DFT Functionals: A Periodic Electrostatic Embedded Cluster Model Study

    SciTech Connect

    Ammal, Salai Cheettu; Heyden, Andreas

    2010-10-26

    The interaction of Aun and Ptn (n=2,3) clusters with the stoichiometric and partially reduced rutile TiO2 (110) surfaces has been investigated using periodic slab and periodic electrostatic embedded cluster models. Compared to Au clusters, Pt clusters interact strongly with both stoichiometric and reduced TiO2 (110) surfaces and are able to enhance the reducibility of the TiO2 (110) surface, i.e., reduce the oxygen vacancy formation energy. The focus of this study is the effect of Hartree–Fock exchange on the description of the strength of chemical bonds at the interface of Au/Pt clusters and the TiO2 (110) surface. Hartree–Fock exchange helps describing the changes in the electronic structures due to metal cluster adsorption as well as their effect on the reducibility of the TiO2 surface. Finally, the performance of periodic embedded cluster models has been assessed by calculating the Pt adsorption and oxygen vacancy formation energies. Cluster models, together with hybrid PBE0 functional, are able to efficiently compute reasonable electronic structures of the reduced TiO2 surface and predict charge localization at surface oxygen vacancies, in agreement with the experimental data, that significantly affect computed adsorption and reaction energies.

  17. Comparing Ullmann Coupling on Noble Metal Surfaces: On-Surface Polymerization of 1,3,6,8-Tetrabromopyrene on Cu(111) and Au(111).

    PubMed

    Pham, Tuan Anh; Song, Fei; Nguyen, Manh-Thuong; Li, Zheshen; Studener, Florian; Stöhr, Meike

    2016-04-18

    The on-surface polymerization of 1,3,6,8-tetrabromopyrene (Br4 Py) on Cu(111) and Au(111) surfaces under ultrahigh vacuum conditions was investigated by a combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. Deposition of Br4 Py on Cu(111) held at 300 K resulted in a spontaneous debromination reaction, generating the formation of a branched coordination polymer network stabilized by C-Cu-C bonds. After annealing at 473 K, the C-Cu-C bonds were converted to covalent C-C bonds, leading to the formation of a covalently linked molecular network of short oligomers. In contrast, highly ordered self-assembled two-dimensional (2D) patterns stabilized by both Br-Br halogen and Br-H hydrogen bonds were observed upon deposition of Br4 Py on Au(111) held at 300 K. Subsequent annealing of the sample at 473 K led to a dissociation of the C-Br bonds and the formation of disordered metal-coordinated molecular networks. Further annealing at 573 K resulted in the formation of covalently linked disordered networks. Importantly, we found that the chosen substrate not only plays an important role as catalyst for the Ullmann reaction, but also influences the formation of different types of intermolecular bonds and thus, determines the final polymer network morphology. DFT calculations further support our experimental findings obtained by STM and XPS and add complementary information on the reaction pathway of Br4 Py on the different substrates.

  18. Metal decoration of exfoliated graphite nanoplatelets (xGnP) for fuel cell application

    NASA Astrophysics Data System (ADS)

    Do, In-Hwan

    The synthesis and characterization of metal particles at nanometer length scale has been the object of much research in modern nanotechnology due to their great impact on new nanoscale scientific and technological applications. Nanoscale metal particles possess unique optical, thermal, electronic, magnetic properties and chemical reactivity since the size of the resulting materials is on the same order as the fundamental interaction distances that give rise to physical properties and thus shows the quantum size effect which is not observed in their bulky status. Therefore, an effective synthetic method is required to obtain uniform small metal powders with controlled size and a narrow size distribution and also to produce nanocomposites consisting of either metals or metal oxides supported on carbons or metals dispersed on metal oxides for a variety of applications in chemical industries, automobiles, energy and power generating devices, hydrogen economy as well as for sensors. On the other hand, although their excellent mechanical, thermal and electrical conductivity, excellent corrosion and oxidation resistance, and low impurity levels which are required as a breakthrough material to increase performance of next generation energy devices, exfoliated graphite nanoplatelet (xGnP) has not been studied as deeply as recent new nano structured carbon materials such as single wall carbon nanotubes (SWNT), multi-wall carbon nanotubes (MWNT), carbon nanohorn (CNH), graphite nanofiber (GNF), and fullerenes. In addition, xGnP is much cost-effective compared to other carbon nanostructures. Hence, it is interesting to evaluate the applicability of xGnP as a support material for fuel cell which is one of promising energy devices for the future. In this research, a new simple, efficient and economic way is presented for the synthesis of noble metal nanoparticles such as Pt, Ru, Pd, etc and their deposition on various carbon supports and metal oxides via microwave heating in the

  19. The Fundamental Role of Nano-Scale Oxide Films in the Oxidation of Hydrogen and the Reduction of Oxygen on Noble Metal Electrocatalysts

    SciTech Connect

    Digby Macdonald

    2005-04-15

    The derivation of successful fuel cell technologies requires the development of more effective, cheaper, and poison-resistant electrocatalysts for both the anode (H{sub 2} oxidation in the presence of small amounts of CO from the reforming of carbonaceous fuels) and the cathode (reduction of oxygen in the presence of carried-over fuel). The proposed work is tightly focused on one specific aspect of electrocatalysis; the fundamental role(s) played by nanoscale (1-2 nm thick) oxide (''passive'') films that form on the electrocatalyst surfaces above substrate-dependent, critical potentials, on charge transfer reactions, particularly at elevated temperatures (25 C < T < 200 C). Once the role(s) of these films is (are) adequately understood, we will then use this information to specify, at the molecular level, optimal properties of the passive layer for the efficient electrocatalysis of the oxygen reduction reaction.

  20. Opacity and conductivity measurements in noble gases at conditions of planetary and stellar interiors.

    PubMed

    McWilliams, R Stewart; Dalton, D Allen; Konôpková, Zuzana; Mahmood, Mohammad F; Goncharov, Alexander F

    2015-06-30

    The noble gases are elements of broad importance across science and technology and are primary constituents of planetary and stellar atmospheres, where they segregate into droplets or layers that affect the thermal, chemical, and structural evolution of their host body. We have measured the optical properties of noble gases at relevant high pressures and temperatures in the laser-heated diamond anvil cell, observing insulator-to-conductor transformations in dense helium, neon, argon, and xenon at 4,000-15,000 K and pressures of 15-52 GPa. The thermal activation and frequency dependence of conduction reveal an optical character dominated by electrons of low mobility, as in an amorphous semiconductor or poor metal, rather than free electrons as is often assumed for such wide band gap insulators at high temperatures. White dwarf stars having helium outer atmospheres cool slower and may have different color than if atmospheric opacity were controlled by free electrons. Helium rain in Jupiter and Saturn becomes conducting at conditions well correlated with its increased solubility in metallic hydrogen, whereas a deep layer of insulating neon may inhibit core erosion in Saturn. PMID:26080401

  1. Opacity and conductivity measurements in noble gases at conditions of planetary and stellar interiors

    PubMed Central

    McWilliams, R. Stewart; Dalton, D. Allen; Konôpková, Zuzana; Mahmood, Mohammad F.; Goncharov, Alexander F.

    2015-01-01

    The noble gases are elements of broad importance across science and technology and are primary constituents of planetary and stellar atmospheres, where they segregate into droplets or layers that affect the thermal, chemical, and structural evolution of their host body. We have measured the optical properties of noble gases at relevant high pressures and temperatures in the laser-heated diamond anvil cell, observing insulator-to-conductor transformations in dense helium, neon, argon, and xenon at 4,000–15,000 K and pressures of 15–52 GPa. The thermal activation and frequency dependence of conduction reveal an optical character dominated by electrons of low mobility, as in an amorphous semiconductor or poor metal, rather than free electrons as is often assumed for such wide band gap insulators at high temperatures. White dwarf stars having helium outer atmospheres cool slower and may have different color than if atmospheric opacity were controlled by free electrons. Helium rain in Jupiter and Saturn becomes conducting at conditions well correlated with its increased solubility in metallic hydrogen, whereas a deep layer of insulating neon may inhibit core erosion in Saturn. PMID:26080401

  2. Opacity and conductivity measurements in noble gases at conditions of planetary and stellar interiors.

    PubMed

    McWilliams, R Stewart; Dalton, D Allen; Konôpková, Zuzana; Mahmood, Mohammad F; Goncharov, Alexander F

    2015-06-30

    The noble gases are elements of broad importance across science and technology and are primary constituents of planetary and stellar atmospheres, where they segregate into droplets or layers that affect the thermal, chemical, and structural evolution of their host body. We have measured the optical properties of noble gases at relevant high pressures and temperatures in the laser-heated diamond anvil cell, observing insulator-to-conductor transformations in dense helium, neon, argon, and xenon at 4,000-15,000 K and pressures of 15-52 GPa. The thermal activation and frequency dependence of conduction reveal an optical character dominated by electrons of low mobility, as in an amorphous semiconductor or poor metal, rather than free electrons as is often assumed for such wide band gap insulators at high temperatures. White dwarf stars having helium outer atmospheres cool slower and may have different color than if atmospheric opacity were controlled by free electrons. Helium rain in Jupiter and Saturn becomes conducting at conditions well correlated with its increased solubility in metallic hydrogen, whereas a deep layer of insulating neon may inhibit core erosion in Saturn.

  3. Electrochemical cell utilizing molten alkali metal electrode-reactant

    DOEpatents

    Virkar, Anil V.; Miller, Gerald R.

    1983-11-04

    An improved electrochemical cell comprising an additive-modified molten alkali metal electrode-reactant and/or electrolyte is disclosed. Various electrochemical cells employing a molten alkali metal, e.g., sodium, electrode in contact with a cationically conductive ceramic membrane experience a lower resistance and a lower temperature coefficient of resistance whenever small amounts of selenium are present at the interface of the electrolyte and the molten alkali metal. Further, cells having small amounts of selenium present at the electrolyte-molten metal interface exhibit less degradation of the electrolyte under long term cycling conditions.

  4. Self-discharge in bimetallic cells containing alkali metal

    NASA Technical Reports Server (NTRS)

    Foster, M. S.; Hesson, J. C.; Shimotake, H.

    1969-01-01

    Theoretical analysis of thermally regenerative bimetallic cells with alkali metal anodes shows a relation between the current drawn and the rate of discharge under open-circuit conditions. The self-discharge rate of the cell is due to the dissolution and ionization of alkali metal atoms in the fused-salt electrolyte

  5. Cell Surface-based Sensing with Metallic Nanoparticles

    PubMed Central

    Jiang, Ziwen; Rotello, Vincent M.

    2015-01-01

    Metallic nanoparticles provide versatile scaffolds for biosensing applications. In this review, we focus on the use of metallic nanoparticles for cell surface sensings. Examples of the use of both specific recognition and array-based “chemical nose” approaches to cell surface sensing will be discussed. PMID:25853985

  6. A new method of metallization for silicon solar cells

    NASA Technical Reports Server (NTRS)

    Macha, M.

    1979-01-01

    The new metallization process based on Mo-Sn system was studied. The reaction mechanism of MoO3 and its mixture with Sn was examined. The basic ink composition was modified in order to obtain a low ohmic contact to the cell. The electrical characteristics of the cells were comparable with the existing metallization processes. However, in comparison with the standard processes using silver as the contacting metal, the saving obtained by the use of the new process was substantial.

  7. Noble gas trapping by laboratory carbon condensates

    NASA Technical Reports Server (NTRS)

    Niemeyer, S.; Marti, K.

    1982-01-01

    Trapping of noble gases by carbon-rich matter was investigated by synthesizing carbon condensates in a noble gas atmosphere. Laser evaporation of a solid carbon target yielded submicron grains which proved to be efficient noble gas trappers (Xe distribution coefficients up to 13 cu cm STP/g-atm). The carbon condensates are better noble gas trappers than previously reported synthetic samples, except one, but coefficients inferred for meteoritic acid-residues are still orders of magnitude higher. The trapped noble gases are loosely bound and elementally strongly fractionated, but isotopic fractionations were not detected. Although this experiment does not simulate nebular conditions, the results support the evidence that carbon-rich phases in meteorites may be carriers of noble gases from early solar system reservoirs. The trapped elemental noble gas fractionations are remarkably similar to both those inferred for meteorites and those of planetary atmospheres for earth, Mars and Venus.

  8. A novel microstructured metal-supported solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Fernández-González, R.; Hernández, E.; Savvin, S.; Núñez, P.; Makradi, A.; Sabaté, N.; Esquivel, J. P.; Ruiz-Morales, J. C.

    2014-12-01

    An innovative design, alternative to the conventional metal supported fuel cells (MSC) is proposed. This new design of Solid Oxide Fuel Cell (SOFC), comprises a 200 μm layer of a honeycomb-metallic framework with hexagonal cells which supports a 250 μm layer of electrolyte. Each hexagonal cell is further functionalized with a thin 5-10 μm of Ni-YSZ anode. This new design allows a reduction of ∼65% of the metallic supporting material, rendering performances over 300 mW cm-2 under pure hydrogen at 850 °C, with an OCV of ∼1.1 V.

  9. Molybdenum-tin as a solar cell metallization system

    NASA Technical Reports Server (NTRS)

    Boyd, D. W.; Radics, C.

    1981-01-01

    The operations of solar cell manufacture are briefly examined. The formation of reliable, ohmic, low-loss, and low-cost metal contacts on solar cells is a critical process step in cell manufacturing. In a commonly used process, low-cost metallization is achieved by screen printing a metal powder-glass frit ink on the surface of the Si surface and the conductive metal powder. A technique utilizing a molybdenum-tin alloy for the metal contacts appears to lower the cost of materials and to reduce process complexity. The ink used in this system is formulated from MoO3 with Sn powder and a trace amount of titanium resonate. Resistive losses of the resulting contacts are low because the ink contains no frit. The MoO3 is finally melted and reduced in forming gas (N2+H2) to Mo metal. The resulting Mo is highly reactive which facilitates the Mo-Si bonding.

  10. Cell surface engineering of microorganisms towards adsorption of heavy metals.

    PubMed

    Li, Peng-Song; Tao, Hu-Chun

    2015-06-01

    Heavy metal contamination has become a worldwide environmental concern due to its toxicity, non-degradability and food-chain bioaccumulation. Conventional physical and chemical treatment methods for heavy metal removal have disadvantages such as cost-intensiveness, incomplete removal, secondary pollution and the lack of metal specificity. Microbial biomass-based biosorption is one of the approaches gaining increasing attention because it is effective, cheap, and environmental friendly and can work well at low concentrations. To enhance the adsorption properties of microbial cells to heavy metal ions, the cell surface display of various metal-binding proteins/peptides have been performed using a cell surface engineering approach. The surface engineering of Gram-negative bacteria, Gram-positive bacteria and yeast towards the adsorption of heavy metals are reviewed in this article. The problems and future perspectives of this technology are discussed.

  11. Low-field MRI of laser polarized noble gas

    NASA Technical Reports Server (NTRS)

    Tseng, C. H.; Wong, G. P.; Pomeroy, V. R.; Mair, R. W.; Hinton, D. P.; Hoffmann, D.; Stoner, R. E.; Hersman, F. W.; Cory, D. G.; Walsworth, R. L.

    1998-01-01

    NMR images of laser polarized 3He gas were obtained at 21 G using a simple, homebuilt instrument. At such low fields magnetic resonance imaging (MRI) of thermally polarized samples (e.g., water) is not practical. Low-field noble gas MRI has novel scientific, engineering, and medical applications. Examples include portable systems for diagnosis of lung disease, as well as imaging of voids in porous media and within metallic systems.

  12. Low-field MRI of laser polarized noble gas.

    PubMed

    Tseng, C H; Wong, G P; Pomeroy, V R; Mair, R W; Hinton, D P; Hoffmann, D; Stoner, R E; Hersman, F W; Cory, D G; Walsworth, R L

    1998-10-26

    NMR images of laser polarized 3He gas were obtained at 21 G using a simple, homebuilt instrument. At such low fields magnetic resonance imaging (MRI) of thermally polarized samples (e.g., water) is not practical. Low-field noble gas MRI has novel scientific, engineering, and medical applications. Examples include portable systems for diagnosis of lung disease, as well as imaging of voids in porous media and within metallic systems. PMID:11543589

  13. Development of an all-metal thick film cost affective metallization system for solar cells

    NASA Technical Reports Server (NTRS)

    Ross, B.

    1981-01-01

    An economical thick film solar cell contact for high volume production of low cost silicon solar array modules was investigated. All metal screenable pastes using base metals were studied. Solar cells with junction depths varying by a factor of 3.3, with and without a deposited oxide coating were used. Cells were screened and fired by a two step firing process. Adhesion and metallurgical results are unsatisfactory. No electrical information is obtained due to inadequate contact adhesion.

  14. PROCESS FOR REMOVING NOBLE METALS FROM URANIUM

    DOEpatents

    Knighton, J.B.

    1961-01-31

    A pyrometallurgical method is given for purifying uranium containing ruthenium and palladium. The uranium is disintegrated and oxidized by exposure to air and then the ruthenium and palladium are extracted from the uranium with molten zinc.

  15. Seal tab for a metal-air electrochemical cell

    SciTech Connect

    Oltman, J.E.; Dopp, R.B.; Carpenter, D.D.

    1987-03-10

    This patent describes an only slightly permeable, removable seal tab, having high initial tack, used to cover the air entry ports of a metal-air electrochemical cell between the time the cell is manufactured and the time the cell is used as a source of electrical power. The tab comprises a face stock of biaxially-oriented three-ply polypropylene paper interposed between an acrylic adhesive and a plastic film. A metal-air electrochemical cell is also described wherein a seal tab according to the aforementioned has been mechanically affixed to the cell in such a manner as to cover the air entry port or ports of the cell.

  16. A base-metal conductor system for silicon solar cells

    NASA Technical Reports Server (NTRS)

    Coleman, M. G.; Pryor, R. A.; Sparks, T. G.

    1980-01-01

    Solder, copper, and silver are evaluated as conductor layer metals for silicon solar cell metallization on the basis of metal price stability and reliability under operating conditions. Due to its properties and cost, copper becomes an attractive candidate for the conductor layer. It is shown that nickel operates as an excellent diffusion barrier between copper and silicon while simultaneously serving as an electrical contact and mechanical contact to silicon. The nickel-copper system may be applied to the silicon by plating techniques utilizing a variety of plating bath compositions. Solar cells having excellent current-voltage characteristics are fabricated to demonstrate the nickel-copper metallization system.

  17. Determination of Natural In Vivo Noble-Gas Concentrations in Human Blood

    PubMed Central

    Tomonaga, Yama; Brennwald, Matthias S.; Livingstone, David M.; Tomonaga, Geneviève; Kipfer, Rolf

    2014-01-01

    Although the naturally occurring atmospheric noble gases He, Ne, Ar, Kr, and Xe possess great potential as tracers for studying gas exchange in living beings, no direct analytical technique exists for simultaneously determining the absolute concentrations of these noble gases in body fluids in vivo. In this study, using human blood as an example, the absolute concentrations of all stable atmospheric noble gases were measured simultaneously by combining and adapting two analytical methods recently developed for geochemical research purposes. The partition coefficients determined between blood and air, and between blood plasma and red blood cells, agree with values from the literature. While the noble-gas concentrations in the plasma agree rather well with the expected solubility equilibrium concentrations for air-saturated water, the red blood cells are characterized by a distinct supersaturation pattern, in which the gas excess increases in proportion to the atomic mass of the noble-gas species, indicating adsorption on to the red blood cells. This study shows that the absolute concentrations of noble gases in body fluids can be easily measured using geochemical techniques that rely only on standard materials and equipment, and for which the underlying concepts are already well established in the field of noble-gas geochemistry. PMID:24811123

  18. Fuel cell with metal screen flow-field

    DOEpatents

    Wilson, M.S.; Zawodzinski, C.

    1998-08-25

    A polymer electrolyte membrane (PEM) fuel cell is provided with electrodes supplied with a reactant on each side of a catalyzed membrane assembly (CMA). The fuel cell includes a metal mesh defining a rectangular flow-field pattern having an inlet at a first corner and an outlet at a second corner located on a diagonal from the first corner, wherein all flow paths from the inlet to the outlet through the square flow field pattern are equivalent to uniformly distribute the reactant over the CMA. In a preferred form of metal mesh, a square weave screen forms the flow-field pattern. In a particular characterization of the present invention, a bipolar plate electrically connects adjacent fuel cells, where the bipolar plate includes a thin metal foil having an anode side and a cathode side; a first metal mesh on the anode side of the thin metal foil; and a second metal mesh on the cathode side of the thin metal foil. In another characterization of the present invention, a cooling plate assembly cools adjacent fuel cells, where the cooling plate assembly includes an anode electrode and a cathode electrode formed of thin conducting foils; and a metal mesh flow field there between for distributing cooling water flow over the electrodes to remove heat generated by the fuel cells. 11 figs.

  19. Fuel cell with metal screen flow-field

    DOEpatents

    Wilson, Mahlon S.; Zawodzinski, Christine

    2001-01-01

    A polymer electrolyte membrane (PEM) fuel cell is provided with electrodes supplied with a reactant on each side of a catalyzed membrane assembly (CMA). The fuel cell includes a metal mesh defining a rectangular flow-field pattern having an inlet at a first corner and an outlet at a second corner located on a diagonal from the first corner, wherein all flow paths from the inlet to the outlet through the square flow field pattern are equivalent to uniformly distribute the reactant over the CMA. In a preferred form of metal mesh, a square weave screen forms the flow-field pattern. In a particular characterization of the present invention, a bipolar plate electrically connects adjacent fuel cells, where the bipolar plate includes a thin metal foil having an anode side and a cathode side; a first metal mesh on the anode side of the thin metal foil; and a second metal mesh on the cathode side of the thin metal foil. In another characterization of the present invention, a cooling plate assembly cools adjacent fuel cells, where the cooling plate assembly includes an anode electrode and a cathode electrode formed of thin conducting foils; and a metal mesh flow field therebetween for distributing cooling water flow over the electrodes to remove heat generated by the fuel cells.

  20. Fuel cell with metal screen flow-field

    DOEpatents

    Wilson, Mahlon S.; Zawodzinski, Christine

    1998-01-01

    A polymer electrolyte membrane (PEM) fuel cell is provided with electrodes supplied with a reactant on each side of a catalyzed membrane assembly (CMA). The fuel cell includes a metal mesh defining a rectangular flow-field pattern having an inlet at a first corner and an outlet at a second corner located on a diagonal from the first corner, wherein all flow paths from the inlet to the outlet through the square flow field pattern are equivalent to uniformly distribute the reactant over the CMA. In a preferred form of metal mesh, a square weave screen forms the flow-field pattern. In a particular characterization of the present invention, a bipolar plate electrically connects adjacent fuel cells, where the bipolar plate includes a thin metal foil having an anode side and a cathode side; a first metal mesh on the anode side of the thin metal foil; and a second metal mesh on the cathode side of the thin metal foil. In another characterization of the present invention, a cooling plate assembly cools adjacent fuel cells, where the cooling plate assembly includes an anode electrode and a cathode electrode formed of thin conducting foils; and a metal mesh flow field therebetween for distributing cooling water flow over the electrodes to remove heat generated by the fuel cells.

  1. A metal-organic framework-derived bifunctional oxygen electrocatalyst

    NASA Astrophysics Data System (ADS)

    Xia, Bao Yu; Yan, Ya; Li, Nan; Wu, Hao Bin; Lou, Xiong Wen (David); Wang, Xin

    2016-01-01

    Oxygen electrocatalysis is of great importance for many energy storage and conversion technologies, including fuel cells, metal-air batteries and water electrolysis. Replacing noble metal-based electrocatalysts with highly efficient and inexpensive non-noble metal-based oxygen electrocatalysts is critical for the practical applications of these technologies. Here we report a general approach for the synthesis of hollow frameworks of nitrogen-doped carbon nanotubes derived from metal-organic frameworks, which exhibit higher electrocatalytic activity and stability for oxygen reduction and evolution than commercial Pt/C electrocatalysts. The remarkable electrochemical properties are mainly attributed to the synergistic effect from chemical compositions and the robust hollow structure composed of interconnected crystalline nitrogen-doped carbon nanotubes. The presented strategy for controlled design and synthesis of metal-organic framework-derived functional nanomaterials offers prospects in developing highly active electrocatalysts in electrochemical energy devices.

  2. Development of an all-metal thick film cost effective metallization system for solar cells

    NASA Technical Reports Server (NTRS)

    Ross, B.; Parker, J.

    1983-01-01

    Improved thick film solar cell contacts for the high volume production of low cost silicon solar arrays are needed. All metal screenable pastes made from economical base metals and suitable for application to low to high conductivity silicon were examined. Silver fluoride containing copper pastes and fluorocarbon containing copper pastes were discussed. The effect of hydrogen on the adhesion of metals to silicon was investigated. A cost analysis of various paste materials is provided.

  3. Iron-copper metallization for flexible solar/cell arrays

    NASA Technical Reports Server (NTRS)

    Lavendel, H. W.

    1983-01-01

    The feasibility of a copper-base metallization for shallow-junction cells applied in flexible solar arrays in space is discussed. This type of metallization will reduce usage of precious metals (such as silver), increase case of bonding (by welding or by soldering) and eliminate heavy high Z interconnects (such as molybdenum). The main points of concern are stability against thermally induced diffusion of copper into silicon which causes degradation of shallow cell junctions, and low series resistance of the contact with semiconductor which promotes cell efficiency.

  4. Electrocatalyst advances for hydrogen oxidation in phosphoric acid fuel cells

    NASA Technical Reports Server (NTRS)

    Stonehart, P.

    1984-01-01

    The important considerations that presently exist for achieving commercial acceptance of fuel cells are centered on cost (which translates to efficiency) and lifetime. This paper addresses the questions of electrocatalyst utilization within porous electrode structures and the preparation of low-cost noble metal electrocatalyst combinations with extreme dispersions of the metal. Now that electrocatalyst particles can be prepared with dimensions of 10 A, either singly or in alloy combinations, a very large percentage of the noble metal atoms in a crystallite are available for reaction. The cost savings for such electrocatalysts in the present commercially driven environment are considerable.

  5. Novel fuel cell stack with coupled metal hydride containers

    NASA Astrophysics Data System (ADS)

    Liu, Zhixiang; Li, Yan; Bu, Qingyuan; Guzy, Christopher J.; Li, Qi; Chen, Weirong; Wang, Cheng

    2016-10-01

    Air-cooled, self-humidifying hydrogen fuel cells are often used for backup and portable power sources, with a metal hydride used as the hydrogen storage material. To provide a stable hydrogen flow to the fuel cell stack, heat must be provided to the metal hydride. Conventionally, the heat released from the exothermic reaction of hydrogen and oxygen in the fuel cell stack to the exhaust air is used to heat a separate metal hydride container. In this case, the heat is only partially used instead of being more closely coupled because of the heat transfer resistances in the system. To achieve better heat integration, a novel scheme is proposed whereby hydrogen storage and single fuel cells are more closely coupled. Based on this idea, metal hydride containers in the form of cooling plates were assembled between each pair of cells in the stack so that the heat could be directly transferred to a metal hydride container of much larger surface-to-volume ratio than conventional separate containers. A heat coupled fuel cell portable power source with 10 cells and 11 metal hydride containers was constructed and the experimental results show that this scheme is beneficial for the heat management of fuel cell stack.

  6. Back contact to film silicon on metal for photovoltaic cells

    DOEpatents

    Branz, Howard M.; Teplin, Charles; Stradins, Pauls

    2013-06-18

    A crystal oriented metal back contact for solar cells is disclosed herein. In one embodiment, a photovoltaic device and methods for making the photovoltaic device are disclosed. The photovoltaic device includes a metal substrate with a crystalline orientation and a heteroepitaxial crystal silicon layer having the same crystal orientation of the metal substrate. A heteroepitaxial buffer layer having the crystal orientation of the metal substrate is positioned between the substrate and the crystal silicon layer to reduce diffusion of metal from the metal foil into the crystal silicon layer and provide chemical compatibility with the heteroepitaxial crystal silicon layer. Additionally, the buffer layer includes one or more electrically conductive pathways to electrically couple the crystal silicon layer and the metal substrate.

  7. Stabilizing metal components in electrodes of electrochemical cells

    DOEpatents

    Spengler, Charles J.; Ruka, Roswell J.

    1989-01-01

    Disclosed is a method of reducing the removal or transfer into a gas phase of a current carrying metal in an apparatus, such as an electrochemical cell 2 having a porous fuel electrode 6 containing metal particles 11, where the metal is subject to removal or transfer into a gaseous phase, the method characterized in that (1) a metal organic compound that decomposes to form an electronically conducting oxide coating when heated is applied to the metal and porous electrode, and (2) the compound on the metal is then heated to a temperature sufficient to decompose the compound into an oxide coating 13 by increasing the temperature at a rate that is longer than 1 hour between room temperature and 600.degree. C., resulting in at least one continuous layer 13, 14 of the oxide coating on the metal.

  8. FIB/SEM cell sectioning for intracellular metal granules characterization

    NASA Astrophysics Data System (ADS)

    Milani, Marziale; Brundu, Claudia; Santisi, Grazia; Savoia, Claudio; Tatti, Francesco

    2009-05-01

    Focused Ion Beams (FIBs) provide a cross-sectioning tool for submicron dissection of cells and subcellular structures. In combination with Scanning Electron Microscope (SEM), FIB provides complementary morphological information, that can be further completed by EDX (Energy Dispersive X-ray Spectroscopy). This study focus onto intracellular microstructures, particularly onto metal granules (typically Zn, Cu and Fe) and on the possibility of sectioning digestive gland cells of the terrestrial isopod P. scaber making the granules available for a compositional analysis with EDX. Qualitative and quantitative analysis of metal granules size, amount and distribution are performed. Information is made available of the cellular storing pattern and, indirectly, metal metabolism. The extension to human level is of utmost interest since some pathologies of relevance are metal related. Apart from the common metal-overload-diseases (hereditary hemochromatosis, Wilson's and Menkes disease) it has been demonstrated that metal in excess can influence carcinogenesis in liver, kidney and breast. Therefore protocols will be established for the observation of mammal cells to improve our knowledge about the intracellular metal amount and distribution both in healthy cells and in those affected by primary or secondary metal overload or depletion.

  9. Environmental tests of metallization systems for terrestrial photovoltaic cells

    NASA Technical Reports Server (NTRS)

    Alexander, P., Jr.

    1985-01-01

    Seven different solar cell metallization systems were subjected to temperature cycling tests and humidity tests. Temperature cycling excursions were -50 deg C to 150 deg C per cycle. Humidity conditions were 70 deg C at 98% relative humidity. The seven metallization systems were: Ti/Ag, Ti/Pd/Ag, Ti/Pd/Cu, Ni/Cu, Pd/Ni/Solder, Cr/Pd/Ag, and thick film Ag. All metallization systems showed a slight to moderate decrease in cell efficiencies after subjection to 1000 temperature cycles. Six of the seven metallization systems also evidenced slight increases in cell efficiencies after moderate numbers of cycles, generally less than 100 cycles. The copper based systems showed the largest decrease in cell efficiencies after temperature cycling. All metallization systems showed moderate to large decreases in cell efficiencies after 123 days of humidity exposure. The copper based systems again showed the largest decrease in cell efficiencies after humidity exposure. Graphs of the environmental exposures versus cell efficiencies are presented for each metallization system, as well as environmental exposures versus fill factors or series resistance.

  10. Positive-electrode current collector for liquid-metal cells

    DOEpatents

    Shimotake, H.; Bartholme, L.G.

    1982-09-27

    A current collector for the positive electrode of an electrochemical cell with a positive electrode including a sulfide. The cell also has a negative electrode and a molten salt electrolyte including halides of a metal selected from the alkali metals and the alkaline earth metals in contact with both the positive and negative electrodes. The current collector has a base metal of copper, silver, gold, aluminum or alloys thereof with a coating thereon of iron, nickel, chromium or alloys thereof. The current collector when subjected to cell voltage forms a sulfur-containing compound on the surface thereby substantially protecting the current collector from further attack by sulfur ions during cell operation. Both electroless and electrolytic processes may be used to deposit coatings.

  11. Positive electrode current collector for liquid metal cells

    DOEpatents

    Shimotake, Hiroshi; Bartholme, Louis G.

    1984-01-01

    A current collector for the positive electrode of an electrochemical cell with a positive electrode including a sulfide. The cell also has a negative electrode and a molten salt electrolyte including halides of a metal selected from the alkali metals and the alkaline earth metals in contact with both the positive and negative electrodes. The current collector has a base metal of copper, silver, gold, aluminum or alloys thereof with a coating thereon of iron, nickel, chromium or alloys thereof. The current collector when subjected to cell voltage forms a sulfur-containing compound on the surface thereby substantially protecting the current collector from further attack by sulfur ions during cell operation. Both electroless and electrolytic processes may be used to deposit coatings.

  12. Highly Dispersed Metal Catalyst for Fuel Cell Electrodes

    SciTech Connect

    2009-03-01

    This factsheet describes a study that will bring industrial catalyst experience to fuel cell research. Specifically, industrial catalysts, such as those used in platforming, utilize precious metal platinum as an active component in a finely dispersed form.

  13. Metal-air cell with ion exchange material

    SciTech Connect

    Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

    2015-08-25

    Embodiments of the invention are related to anion exchange membranes used in electrochemical metal-air cells in which the membranes function as the electrolyte material, or are used in conjunction with electrolytes such as ionic liquid electrolytes.

  14. Effects of metal ions on fibroblasts and spiral ganglion cells.

    PubMed

    Paasche, G; Ceschi, P; Löbler, M; Rösl, C; Gomes, P; Hahn, A; Rohm, H W; Sternberg, K; Lenarz, T; Schmitz, K-P; Barcikowski, S; Stöver, T

    2011-04-01

    Degeneration of spiral ganglion cells (SGC) after deafness and fibrous tissue growth around the electrode carrier after cochlear implantation are two of the major challenges in current cochlear implant research. Metal ions are known to possess antimicrobial and antiproliferative potential. The use of metal ions could therefore provide a way to reduce tissue growth around the electrode array after cochlear implantation. Here, we report on in vitro experiments with different concentrations of metal salts with antiproliferative and toxic effects on fibroblasts, PC-12 cells, and freshly isolated spiral ganglion cells, the target cells for electrical stimulation by a cochlear implant. Standard cell lines (NIH/3T3 and L-929 fibroblasts and PC-12 cells) and freshly isolated SGC were incubated with concentrations of metal ions between 0.3 μmol/liter and 10 mmol/liter for 48 hr. Cell survival was investigated by neutral red uptake, CellQuantiBlue assay, or counting of stained surviving neurons. Silver ions exhibited distinct thresholds for proliferating and confluent cells. For zinc ions, the effective concentration was lower for fibroblasts than for PC-12 cells. SGC showed comparable thresholds for reduced cell survival not only for silver and zinc ions but also for copper(II) ions, indicating that these ions might be promising for reducing tissue growth on the surface of CI electrode arrays. These effects were also observed when combinations of two of these ions were investigated. PMID:21312225

  15. Electrochemical cell having an alkali-metal-nitrate electrode

    DOEpatents

    Roche, M.F.; Preto, S.K.

    1982-06-04

    A power-producing secondary electrochemical cell includes a molten alkali metal as the negative-electrode material and a molten-nitrate salt as the positive-electrode material. The molten material in the respective electrodes are separated by a solid barrier of alkali-metal-ion conducting material. A typical cell includes active materials of molten sodium separated from molten sodium nitrate and other nitrates in mixture by a layer of sodium ..beta..'' alumina.

  16. New perspectives for noble gases in oceanography

    NASA Astrophysics Data System (ADS)

    Aeschbach, Werner

    2016-08-01

    Conditions prevailing in regions of deep water formation imprint their signature in the concentrations of dissolved noble gases, which are conserved in the deep ocean. Such "recharge conditions" including temperature, salinity, and interactions with sea ice are important in view of ocean-atmosphere CO2 partitioning. Noble gases, especially the temperature sensitive Kr and Xe, are well-established tracers to reconstruct groundwater recharge conditions. In contrast, tracer oceanography has traditionally focused on He isotopes and the light noble gases Ne and Ar, which could be analyzed at the required high precision. Recent developments of analytical and data interpretation methods now provide fresh perspectives for noble gases in oceanography.

  17. Electrocatalyst for alcohol oxidation in fuel cells

    DOEpatents

    Adzic, Radoslav R.; Marinkovic, Nebojsa S.

    2001-01-01

    Binary and ternary electrocatalysts are provided for oxidizing alcohol in a fuel cell. The binary electrocatalyst includes 1) a substrate selected from the group consisting of NiWO.sub.4 or CoWO.sub.4 or a combination thereof, and 2) Group VIII noble metal catalyst supported on the substrate. The ternary electrocatalyst includes 1) a substrate as described above, and 2) a catalyst comprising Group VIII noble metal, and ruthenium oxide or molybdenum oxide or a combination thereof, said catalyst being supported on said substrate.

  18. Heavy metals in the cell nucleus - role in pathogenesis.

    PubMed

    Sas-Nowosielska, Hanna; Pawlas, Natalia

    2015-01-01

    People are exposed to heavy metals both in an occupational and natural environment. The most pronounced effects of heavy metals result from their interaction with cellular genetic material packed in form of chromatin. Heavy metals influence chromatin, mimicking and substituting natural microelements in various processes taking place in the cell, or interacting chemically with nuclear components: nucleic acids, proteins and lipids. This paper is a review of current knowledge on the effects of heavy metals on chromatin, exerted at the level of various nuclear components.

  19. Absence of Structural Impact of Noble Nanoparticles on P3HT:PCBM Blends for Plasmon-Enhanced Bulk-Heterojunction Organic Solar Cells Probed by Synchrotron GI-XRD

    PubMed Central

    Lilliu, Samuele; Alsari, Mejd; Bikondoa, Oier; Emyr Macdonald, J.; Dahlem, Marcus S.

    2015-01-01

    The incorporation of noble metal nanoparticles, displaying localized surface plasmon resonance, in the active area of donor-acceptor bulk-heterojunction organic photovoltaic devices is an industrially compatible light trapping strategy, able to guarantee better absorption of the incident photons and give an efficiency improvement between 12% and 38%. In the present work, we investigate the effect of Au and Ag nanoparticles blended with P3HT: PCBM on the P3HT crystallization dynamics by synchrotron grazing incidence X-ray diffraction. We conclude that the presence of (1) 80 nm Au, (2) mix of 5 nm, 50 nm, 80 nm Au, (3) 40 nm Ag, and (4) 10 nm, 40 nm, 60 nm Ag colloidal nanoparticles, at different concentrations below 0.3 wt% for Au and below 0.1% for Ag in P3HT: PCBM blends, does not affect the behaviour of the blends themselves. PMID:26030351

  20. Metal catalyst technique for texturing silicon solar cells

    DOEpatents

    Ruby, Douglas S.; Zaidi, Saleem H.

    2001-01-01

    Textured silicon solar cells and techniques for their manufacture utilizing metal sources to catalyze formation of randomly distributed surface features such as nanoscale pyramidal and columnar structures. These structures include dimensions smaller than the wavelength of incident light, thereby resulting in a highly effective anti-reflective surface. According to the invention, metal sources present in a reactive ion etching chamber permit impurities (e.g. metal particles) to be introduced into a reactive ion etch plasma resulting in deposition of micro-masks on the surface of a substrate to be etched. Separate embodiments are disclosed including one in which the metal source includes one or more metal-coated substrates strategically positioned relative to the surface to be textured, and another in which the walls of the reaction chamber are pre-conditioned with a thin coating of metal catalyst material.

  1. 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.

  2. Recycled Cell Phones - A Treasure Trove of Valuable Metals

    USGS Publications Warehouse

    Sullivan, Daniel E.

    2006-01-01

    This U.S. Geological Survey (USGS) Fact Sheet examines the potential value of recycling the metals found in obsolete cell phones. Cell phones seem ubiquitous in the United States and commonplace throughout most of the world. There were approximately 1 billion cell phones in use worldwide in 2002. In the United States, the number of cell phone subscribers increased from 340,000 in 1985 to 180 million in 2004. Worldwide, cell phone sales have increased from slightly more than 100 million units per year in 1997 to an estimated 779 million units per year in 2005. Cell phone sales are projected to exceed 1 billion units per year in 2009, with an estimated 2.6 billion cell phones in use by the end of that year. The U.S. Environmental Protection Agency estimated that, by 2005, as many as 130 million cell phones would be retired annually in the United States. The nonprofit organization INFORM, Inc., anticipated that, by 2005, a total of 500 million obsolete cell phones would have accumulated in consumers' desk drawers, store rooms, or other storage, awaiting disposal. Typically, cell phones are used for only 1 1/2 years before being replaced. Less than 1 percent of the millions of cell phones retired and discarded annually are recycled. When large numbers of cell phones become obsolete, large quantities of valuable metals end up either in storage or in landfills. The amount of metals potentially recoverable would make a significant addition to total metals recovered from recycling in the United States and would supplement virgin metals derived from mining.

  3. Nobel metal alloyed thin-films with optical properties on demand

    NASA Astrophysics Data System (ADS)

    Gong, Chen; Leite, Marina S.

    Metallic materials with tunable optical responses can enable the unprecedented control of optoelectronic and nanophotonic devices with enhanced performance, such as thin-film solar cells, metamaterials and metasurfaces for tunable absorbers and optical filters, among others. Here we present the alloying of noble metals, Ag, Au and Cu, to develop a novel class of material with optical response not achieved by pure metals. We fabricate binary mixtures with controlled chemical composition by co-sputtering. Ellipsometry and surface plasmon polariton coupling angle measurements are in excellent agreement when determining the real part of the dielectric function (ɛ1). Surprisingly, in some cases, a mixture provides a material with higher surface plasmon polariton quality factor than the corresponding pure metals. Our approach paves the way to implement metallic nanostructures with tunable absorption/transmission, overcoming the current limitation of the dielectric function of noble metals.

  4. Whole-Cell Bioreporters for the Detection of Bioavailable Metals

    NASA Astrophysics Data System (ADS)

    Hynninen, Anu; Virta, Marko

    Whole-cell bioreporters are living microorganisms that produce a specific, quantifiable output in response to target chemicals. Typically, whole-cell bioreporters combine a sensor element for the substance of interest and a reporter element coding for an easily detectable protein. The sensor element is responsible for recognizing the presence of an analyte. In the case of metal bioreporters, the sensor element consists of a DNA promoter region for a metal-binding transcription factor fused to a promoterless reporter gene that encodes a signal-producing protein. In this review, we provide an overview of specific whole-cell bioreporters for heavy metals. Because the sensing of metals by bioreporter microorganisms is usually based on heavy metal resistance/homeostasis mechanisms, the basis of these mechanisms will also be discussed. The goal here is not to present a comprehensive summary of individual metal-specific bioreporters that have been constructed, but rather to express views on the theory and applications of metal-specific bioreporters and identify some directions for future research and development.

  5. Noble Gas Temperature Proxy for Climate Change

    EPA Science Inventory

    Noble gases in groundwater appear to offer a practical approach for quantitatively determining past surface air temperatures over recharge areas for any watershed. The noble gas temperature (NGT) proxy should then permit a paleothermometry of a region over time. This terrestria...

  6. Carbon-Based Metal-Free Catalysts for Electrocatalysis beyond the ORR.

    PubMed

    Hu, Chuangang; Dai, Liming

    2016-09-19

    Besides their use in fuel cells for energy conversion through the oxygen reduction reaction (ORR), carbon-based metal-free catalysts have also been demonstrated to be promising alternatives to noble-metal/metal oxide catalysts for the oxygen evolution reaction (OER) in metal-air batteries for energy storage and for the splitting of water to produce hydrogen fuels through the hydrogen evolution reaction (HER). This Review focuses on recent progress in the development of carbon-based metal-free catalysts for the OER and HER, along with challenges and perspectives in the emerging field of metal-free electrocatalysis. PMID:27460826

  7. Carbon-Based Metal-Free Catalysts for Electrocatalysis beyond the ORR.

    PubMed

    Hu, Chuangang; Dai, Liming

    2016-09-19

    Besides their use in fuel cells for energy conversion through the oxygen reduction reaction (ORR), carbon-based metal-free catalysts have also been demonstrated to be promising alternatives to noble-metal/metal oxide catalysts for the oxygen evolution reaction (OER) in metal-air batteries for energy storage and for the splitting of water to produce hydrogen fuels through the hydrogen evolution reaction (HER). This Review focuses on recent progress in the development of carbon-based metal-free catalysts for the OER and HER, along with challenges and perspectives in the emerging field of metal-free electrocatalysis.

  8. Nanodisperse transition metal electrodes (NTME) for electrochemical cells

    DOEpatents

    Striebel, Kathryn A.; Wen, Shi-Jie

    2000-01-01

    Disclosed are transition metal electrodes for electrochemical cells using gel-state and solid-state polymers. The electrodes are suitable for use in primary and secondary cells. The electrodes (either negative electrode or positive electrode) are characterized by uniform dispersion of the transition metal at the nanoscale in the polymer. The transition metal moiety is structurally amorphous, so no capacity fade should occur due to lattice expansion/contraction mechanisms. The small grain size, amorphous structure and homogeneous distribution provide improved charge/discharge cycling performance, and a higher initial discharge rate capability. The cells can be cycled at high current densities, limited only by the electrolyte conductivity. A method of making the electrodes (positive and negative), and their usage in electrochemical cells are disclosed.

  9. Metal-Insulator-Semiconductor Nanowire Network Solar Cells.

    PubMed

    Oener, Sebastian Z; van de Groep, Jorik; Macco, Bart; Bronsveld, Paula C P; Kessels, W M M; Polman, Albert; Garnett, Erik C

    2016-06-01

    Metal-insulator-semiconductor (MIS) junctions provide the charge separating properties of Schottky junctions while circumventing the direct and detrimental contact of the metal with the semiconductor. A passivating and tunnel dielectric is used as a separation layer to reduce carrier recombination and remove Fermi level pinning. When applied to solar cells, these junctions result in two main advantages over traditional p-n-junction solar cells: a highly simplified fabrication process and excellent passivation properties and hence high open-circuit voltages. However, one major drawback of metal-insulator-semiconductor solar cells is that a continuous metal layer is needed to form a junction at the surface of the silicon, which decreases the optical transmittance and hence short-circuit current density. The decrease of transmittance with increasing metal coverage, however, can be overcome by nanoscale structures. Nanowire networks exhibit precisely the properties that are required for MIS solar cells: closely spaced and conductive metal wires to induce an inversion layer for homogeneous charge carrier extraction and simultaneously a high optical transparency. We experimentally demonstrate the nanowire MIS concept by using it to make silicon solar cells with a measured energy conversion efficiency of 7% (∼11% after correction), an effective open-circuit voltage (Voc) of 560 mV and estimated short-circuit current density (Jsc) of 33 mA/cm(2). Furthermore, we show that the metal nanowire network can serve additionally as an etch mask to pattern inverted nanopyramids, decreasing the reflectivity substantially from 36% to ∼4%. Our extensive analysis points out a path toward nanowire based MIS solar cells that exhibit both high Voc and Jsc values. PMID:27172429

  10. Metal-Insulator-Semiconductor Nanowire Network Solar Cells.

    PubMed

    Oener, Sebastian Z; van de Groep, Jorik; Macco, Bart; Bronsveld, Paula C P; Kessels, W M M; Polman, Albert; Garnett, Erik C

    2016-06-01

    Metal-insulator-semiconductor (MIS) junctions provide the charge separating properties of Schottky junctions while circumventing the direct and detrimental contact of the metal with the semiconductor. A passivating and tunnel dielectric is used as a separation layer to reduce carrier recombination and remove Fermi level pinning. When applied to solar cells, these junctions result in two main advantages over traditional p-n-junction solar cells: a highly simplified fabrication process and excellent passivation properties and hence high open-circuit voltages. However, one major drawback of metal-insulator-semiconductor solar cells is that a continuous metal layer is needed to form a junction at the surface of the silicon, which decreases the optical transmittance and hence short-circuit current density. The decrease of transmittance with increasing metal coverage, however, can be overcome by nanoscale structures. Nanowire networks exhibit precisely the properties that are required for MIS solar cells: closely spaced and conductive metal wires to induce an inversion layer for homogeneous charge carrier extraction and simultaneously a high optical transparency. We experimentally demonstrate the nanowire MIS concept by using it to make silicon solar cells with a measured energy conversion efficiency of 7% (∼11% after correction), an effective open-circuit voltage (Voc) of 560 mV and estimated short-circuit current density (Jsc) of 33 mA/cm(2). Furthermore, we show that the metal nanowire network can serve additionally as an etch mask to pattern inverted nanopyramids, decreasing the reflectivity substantially from 36% to ∼4%. Our extensive analysis points out a path toward nanowire based MIS solar cells that exhibit both high Voc and Jsc values.

  11. Nitrogen-doped carbon onions encapsulating metal alloys as efficient and stable catalysts for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Zhu, Chongyang; Xu, Feng; Chen, Jing; Min, Huihua; Dong, Hui; Tong, Ling; Qasim, Khan; Li, Shengli; Sun, Litao

    2016-01-01

    Designing a new class of non-noble metal catalysts with triiodide reduction activity and stability comparable to those of conventional Pt is extremely significant for the application of dye-sensitized solar cells (DSSCs). Here, we demonstrate newly designed counter electrode (CE) materials of onion-like nitrogen-doped carbon encapsulating metal alloys (ONC@MAs) such as FeNi3 (ONC@FeNi3) or FeCo (ONC@FeCo), by a facile and scalable pyrolysis method. The resulting composite catalysts show superior catalytic activities towards the triiodide reduction and exhibit low charge transfer resistance between the electrode surfaces and electrolytes. As a result, the DSSCs based on ONC@FeCo and ONC@FeNi3 achieve outstanding power conversion efficiencies (PCEs) of 8.26% and 8.87%, respectively, which can rival the 8.28% of Pt-based DSSC. Moreover, the excellent electrochemical stabilities for both the two catalysts also have been corroborated by electrochemical impendence spectra and cyclic voltammetry (CV). Noticeably, TEM investigation further reveals that the N-doped graphitic carbon onions exhibit the high structural stability in iodine-containing medium even subject to hundreds of CV scanning. These results make ONC@MAs the promising candidates to supersede costly Pt as efficient and stable CEs for DSSCs.

  12. Metal binding proteins, recombinant host cells and methods

    DOEpatents

    Summers, Anne O.; Caguiat, Jonathan J.

    2004-06-15

    The present disclosure provides artificial heavy metal binding proteins termed chelons by the inventors. These chelons bind cadmium and/or mercuric ions with relatively high affinity. Also disclosed are coding sequences, recombinant DNA molecules and recombinant host cells comprising those recombinant DNA molecules for expression of the chelon proteins. In the recombinant host cells or transgenic plants, the chelons can be used to bind heavy metals taken up from contaminated soil, groundwater or irrigation water and to concentrate and sequester those ions. Recombinant enteric bacteria can be used within the gastrointestinal tracts of animals or humans exposed to toxic metal ions such as mercury and/or cadmium, where the chelon recombinantly expressed in chosen in accordance with the ion to be rededicated. Alternatively, the chelons can be immobilized to solid supports to bind and concentrate heavy metals from a contaminated aqueous medium including biological fluids.

  13. Parasitic corrosion-resistant anode for use in metal/air or metal/O/sub 2/ cells

    DOEpatents

    Joy, R.W.; Smith, D.F.

    1982-09-20

    A consumable metal anode is described which is used in refuelable electrochemical cells and wherein at least a peripheral edge portion of the anode is protected against a corrosive alkaline environment of the cell by the application of a thin metal coating, the coating being formed of metals such as nickel, silver, and gold.

  14. Parasitic corrosion resistant anode for use in metal/air or metal/O.sub.2 cells

    DOEpatents

    Joy, Richard W.; Smith, David F.

    1983-01-01

    A consumable metal anode which is used in refuelable electrochemical cells and wherein at least a peripheral edge portion of the anode is protected against a corrosive alkaline environment of the cell by the application of a thin metal coating, the coating being formed of metals such as nickel, silver, and gold.

  15. Combined toxicity of heavy metal mixtures in liver cells.

    PubMed

    Lin, Xialu; Gu, Yuanliang; Zhou, Qi; Mao, Guochuan; Zou, Baobo; Zhao, Jinshun

    2016-09-01

    With rapid industrialization, China is now facing great challenges in heavy metal contamination in the environment. Human exposure to heavy metals through air, water and food commonly involves a mixture consisting of multiple heavy metals. In this study, eight common heavy metals (Pb, Cd, Hg, Cu, Zn, Mn, Cr, Ni) that cause environmental contamination were selected to investigate the combined toxicity of different heavy metal mixtures in HL7702 cells. Toxicity (24 h LC50 ) of each individual metal on the cells ranked Hg > Cr = Cd > Cu > Zn > Ni > Mn > Pb; toxicity of the different mixtures ranked: M5 > M3PbHgCd > M5+Mn > M5+Cu > M2CdNi > M4A > M8-Mn > M8 > M5+Zn > M4B > M8-Cr > M8-Zn > M8-Cu > M8-Pb > M8-Cd > M8-Hg > M8-Ni > M3PbHgNi > M3CuZnMn. The cytotoxicity data of individual metals were successfully used to build the additive models of two- to eight-component metal mixtures. The comparison between additive model and combination model or partly additive model was useful to evaluate the combined effects in mixture. Synergistic, antagonistic or additive effects of the toxicity were observed in different mixtures. These results suggest that the combined effects should be considered in the risk assessment of heavy metal co-exposure, and more comprehensive investigations on the combined effects of different heavy metal mixtures are needed in the future. Copyright © 2016 John Wiley & Sons, Ltd.

  16. 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.

  17. Generating a Metal-responsive Transcriptional Regulator to Test What Confers Metal Sensing in Cells*

    PubMed Central

    Osman, Deenah; Piergentili, Cecilia; Chen, Junjun; Chakrabarti, Buddhapriya; Foster, Andrew W.; Lurie-Luke, Elena; Huggins, Thomas G.; Robinson, Nigel J.

    2015-01-01

    FrmR from Salmonella enterica serovar typhimurium (a CsoR/RcnR-like transcriptional de-repressor) is shown to repress the frmRA operator-promoter, and repression is alleviated by formaldehyde but not manganese, iron, cobalt, nickel, copper, or Zn(II) within cells. In contrast, repression by a mutant FrmRE64H (which gains an RcnR metal ligand) is alleviated by cobalt and Zn(II). Unexpectedly, FrmR was found to already bind Co(II), Zn(II), and Cu(I), and moreover metals, as well as formaldehyde, trigger an allosteric response that weakens DNA affinity. However, the sensory metal sites of the cells' endogenous metal sensors (RcnR, ZntR, Zur, and CueR) are all tighter than FrmR for their cognate metals. Furthermore, the endogenous metal sensors are shown to out-compete FrmR. The metal-sensing FrmRE64H mutant has tighter metal affinities than FrmR by approximately 1 order of magnitude. Gain of cobalt sensing by FrmRE64H remains enigmatic because the cobalt affinity of FrmRE64H is substantially weaker than that of the endogenous cobalt sensor. Cobalt sensing requires glutathione, which may assist cobalt access, conferring a kinetic advantage. For Zn(II), the metal affinity of FrmRE64H approaches the metal affinities of cognate Zn(II) sensors. Counter-intuitively, the allosteric coupling free energy for Zn(II) is smaller in metal-sensing FrmRE64H compared with nonsensing FrmR. By determining the copies of FrmR and FrmRE64H tetramers per cell, then estimating promoter occupancy as a function of intracellular Zn(II) concentration, we show how a modest tightening of Zn(II) affinity, plus weakened DNA affinity of the apoprotein, conspires to make the relative properties of FrmRE64H (compared with ZntR and Zur) sufficient to sense Zn(II) inside cells. PMID:26109070

  18. Admit One: How Essential and Nonessential Metals Gain Entrance into the Cell

    PubMed Central

    Martinez-Finley, Ebany J.; Chakraborty, Sudipta; Fretham, Stephanie; Aschner, Michael

    2016-01-01

    Metals can have a number of detrimental or beneficial effects in the cell, but first they must get in. Organisms have evolved transport mechanisms to get metals that are required, or essential into the cell. Nonessential metals often enter the cell through use of the machinery provided for essential metals. Much work has been done to advance our understanding of how these metals are transported across the plasma and organelle membranes. This review provides an overview of these metal transport processes. PMID:22337135

  19. Low Cost PEM Fuel Cell Metal Bipolar Plates

    SciTech Connect

    Wang, Conghua

    2013-05-30

    Bipolar plate is an important component in fuel cell stacks and accounts for more than 75% of stack weight and volume. The technology development of metal bipolar plates can effectively reduce the fuel cells stack weight and volume over 50%. The challenge is the metal plate corrosion protection at low cost for the broad commercial applications. This project is aimed to develop innovative technological solutions to overcome the corrosion barrier of low cost metal plates. The feasibility of has been demonstrated and patented (US Patent 7,309,540). The plan is to further reduce the cost, and scale up the technology. The project is built on three pillars: 1) robust experimental evidence demonstrating the feasibility of our technology, 2) a team that consists of industrial leaders in fuel cell stack application, design, and manufactures; 3) a low-risk, significant-milestone driven program that proves the feasibility of meeting program objectives The implementation of this project will reduce the fuel cell stack metal bipolar separator plate cost which accounts 15-21% of the overall stack cost. It will contribute to the market adoption of fuel cell technologies. In addition, this corrosion protection technology can be used similar energy devices, such as batteries and electrolyzers. Therefore, the success of the project will be benefit in broad markets.

  20. Effect of Noble Gases on Sonoluminescence Temperatures during Multibubble Cavitation

    SciTech Connect

    Didenko, Yuri T.; McNamara, William B. III; Suslick, Kenneth S.

    2000-01-24

    Sonoluminescence spectra were collected from Cr(CO){sub 6} solutions in octanol and dodecane saturated with various noble gases. The emission from excited-state metal atoms serves as an internal thermometer of cavitation. The intensity and temperature of sonoluminescence increases from He to Xe. The intensity of the underlying continuum, however, grows faster with increasing temperature than the line emission. Dissociation of solvent molecules within the bubble consumes a significant fraction of the energy generated by the collapsing bubble, which can limit the final temperature inside the bubble. (c) 2000 The American Physical Society.