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Sample records for metales nobles pd

  1. Noble metal ionic catalysts.

    Science.gov (United States)

    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

  2. Phase formation study of noble metal (Au, Ag and Pd) doped lanthanum perovskites synthesized by hydrothermal method

    Energy Technology Data Exchange (ETDEWEB)

    Nikam, Shrikant K. [Department of Chemistry, Savitribai Phule Pune University, Pune 411007 (India); Anantrao Thopte College, Bhor, Pune 412206 (India); Athawale, Anjali A., E-mail: agbed@chem.unipune.ac.in [Department of Chemistry, Savitribai Phule Pune University, Pune 411007 (India)

    2015-04-01

    Noble metal (Au, Ag and Pd) doped Lanthanum perovskites (LaMnO{sub 3}, LaCrO{sub 3} and LaFeO{sub 3}) have been synthesized by hydrothermal method. The effect of dopant and their concentration on the phase purity, crystallite size, morphology and magnetic character of the synthesized perovskites were systematically studied by FTIR spectroscopy, XRD, TGA, SEM, ICP-AES and VSM. The results show that phase pure products were obtained only after calcining the hydrothermally synthesized products above 760 °C for a minimum of 6 h. Nature and concentration of the dopant plays an important role in determining the phase formation temperature, morphology and magnetic character. The dopant ion preferentially occupies A-site and homogeneous phase of product is obtained upto a dopant concentration of 4%, higher concentration results in phase separation. The products exhibit spherical morphology. Lanthanum ferrite shows ferromagnetic nature, while the doped samples show weak magnetic properties. - Highlights: • Hydrothermal synthesis of noble metal doped lanthanum perovskites. • Site preference of noble metal (Au, Ag and Pd) doping in LaBO{sub 3} (B = Mn, Cr and Fe). • Dopant ions affect the phase formation temperature and morphology the perovskites. • 4% appears to be the maximum limit of doping at A-site.

  3. Recovery and use of fission product noble metals

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, G.A.; Rohmann, C.A.; Perrigo, L.D.

    1980-06-01

    Noble metals in fission products are of strategic value. Market prices for noble metals are rising more rapidly than recovery costs. A promising concept has been developed for recovery of noble metals from fission product waste. Although the assessment was made only for the three noble metal fission products (Rh, Pd, Ru), there are other fission products and actinides which have potential value. (DLC)

  4. Recovery and use of fission product noble metals

    International Nuclear Information System (INIS)

    Jensen, G.A.; Rohmann, C.A.; Perrigo, L.D.

    1980-06-01

    Noble metals in fission products are of strategic value. Market prices for noble metals are rising more rapidly than recovery costs. A promising concept has been developed for recovery of noble metals from fission product waste. Although the assessment was made only for the three noble metal fission products (Rh, Pd, Ru), there are other fission products and actinides which have potential value

  5. Structural, electronic, elastic and superconducting properties of noble metal nitrides MN{sub 2} (M = Ru, Rh, Pd)

    Energy Technology Data Exchange (ETDEWEB)

    Puvaneswari, S. [Department of Physics, E.M.G. Yadava Women' s College, Madurai, Tamilnadu 625 014 (India); Rajeswarapalanichamy, R., E-mail: rrpcaspd2003@gmail.com [Department of Physics, N.M.S.S. Vellaichamy Nadar College, Madurai, Tamilnadu 625019 (India); Sudha Priyanga, G. [Department of Physics, N.M.S.S. Vellaichamy Nadar College, Madurai, Tamilnadu 625019 (India)

    2015-02-01

    The structural stability, electronic structure, elastic and superconducting properties of noble metal nitrides MN{sub 2} (M = Ru, Rh, Pd) are investigated in tetragonal (P4/mbm), fluorite (Fm3m), orthorhombic (Pnnm), pyrite (Pa-3) and hexagonal (P6/mmm) phases using first principles calculations. The calculated lattice parameters are in good agreement with other theoretical results. Among the considered structures, RhN{sub 2} and PdN{sub 2} are found to be most stable in tetragonal structure, whereas RuN{sub 2} is stable in fluorite structure. A sequence of structural phase transition is predicted under high pressure in these metal nitrides. The electronic structure reveals that these nitrides are metallic. These metal nitrides are found to be covalent, ionic and metallic in the stable phase. The observations show that these metal nitrides are mechanically stable at ambient condition. The superconducting transition temperatures for RuN{sub 2}, RhN{sub 2} and PdN{sub 2} are found to be 1.65 K, 5.01 K and 8.7 K respectively. - Highlights: • Electronic, structural and elastic properties of RuN{sub 2}, RhN{sub 2} and PdN{sub 2} are studied. • A pressure induced structural phase transition is predicted. • Electronic structure reveals that these materials exhibit metallic behavior. • High bulk modulus indicates that RuN{sub 2}, RhN{sub 2} and PdN{sub 2} are superhard materials. • Superconducting temperature values are reported.

  6. Noble-Metal Chalcogenide Nanotubes

    Directory of Open Access Journals (Sweden)

    Nourdine Zibouche

    2014-10-01

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

  7. A first-principles study on the interaction of biogas with noble metal (Rh, Pt, Pd) decorated nitrogen doped graphene as a gas sensor: A DFT study

    Science.gov (United States)

    Zhao, Chunjiang; Wu, Huarui

    2018-03-01

    Density functional theory calculations are carried out to investigate the adsorption characteristics of methane (CH4), carbon dioxide (CO2), hydrogen (H2), hydrogen sulfide (H2S), nitrogen (N2), and oxygen (O2) on the surface of pyridine-like nitrogen doped graphene (PNG) as well as noble metal (Rh, Pt, Pd) decorated PNG to elaborate their potentials as gas sensors. The adsorption intensities of biogas on noble metal (Rh, Pt, Pd) decorated PNG are in the order of O2> H2S> N2> CH4> CO2> H2, which are corresponded to the order of their sensitivity on surface. Compared with biogas adsorption on pristine PNG, there exist higher adsorption ability, higher charge transfer and higher orbital hybridization upon adsorption on noble metal (Rh, Pt, Pd) decorated PNG. Consequently, the noble metal (Rh, Pt, Pd) decorated PNG can transform the existence of CH4, CO2, H2, H2S, N2, and O2 molecules into electrical signal and they could potentially be used as ideal sensors for detection of biogas in ambient situation.

  8. Photochemical synthesis of noble metal (Ag, Pd, Au, Pt) on graphene/ZnO multihybrid nanoarchitectures as electrocatalysis for H2O2 reduction.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2014-05-01

    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).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

  10. Disruption, segregation, and passivation for Pd and noble-metal overlayers on YBa2Cu3O/sub 6.9/

    International Nuclear Information System (INIS)

    Wagener, T.J.; Gao, Y.; Vitomirov, I.M.; Aldao, C.M.; Joyce, J.J.; Capasso, C.; Weaver, J.H.; Capone II, D.W.

    1988-01-01

    We have investigated interfaces formed when Pd and the noble metals Cu, Ag, and Au are deposited onto polycrystalline samples of YBa 2 Cu 3 O/sub 6.9/ fractured in ultrahigh vacuum. Synchrotron-radiation photoemission results show that Cu and Pd overlayers leach oxygen from the underlying YBa 2 Cu 3 O/sub 6.9/ substrate, disrupt the superconductor, and destroy electronic states near the Fermi level. Interface reactions become kinetically limited at room temperature after the deposition of ∼4 A of Cu or Pd, significantly sooner than for the reactive metals Fe, Al, Ti, and In. The presence of Ba near the surface after the deposition of more than 100 A of Cu and Pd reflects substrate disruption and subsequent surface segregation. In contrast, overlayers of Ag and Au do not disrupt the superconductor substrate, no segregation is observed, but the overlayers are nonuniform and the quality of passivation is in question for coverages <100 A

  11. Development of casting investment preventing blackening of noble metal alloys part 1. Application of developed investment for Ag-Pd-Cu-Au alloy.

    Science.gov (United States)

    Kakuta, Kiyoshi; Nakai, Akira; Goto, Shin-ichi; Wakamatsu, Yasushi; Yara, Atushi; Miyagawa, Yukio; Ogura, Hideo

    2003-03-01

    The objective of this study is to develop a casting investment that prevents the blackening of the cast surface of noble metal alloys. The experimental investments were prepared using a gypsum-bonded investment in which the metallic powders such as boron (B), silicon (Si), aluminum (Al) and titanium (Ti) were added as oxidizing agents. An Ag-Pd-Cu-Au alloy was cast into the mold made of the prepared investment. The effect of the addition of each metal powder was evaluated from the color difference between the as-cast surface and the polished surface of the cast specimen. The color of the as-cast surface approached that of the polished surface with increasing B and Al content. A lower mean value in the color difference was obtained at 0.25-1.00 mass% B content. B and Al are useful as an additive in a gypsum-bonded investment to prevent the blackening of an Ag-Pd-Cu-Au alloy. The effects of Si and Ti powder addition could not be found.

  12. Enantioselection on Heterogeneous Noble Metal Catalyst: Proline-Induced Asymmetry in the Hydrogenation of Isophorone on Pd Catalyst.

    Science.gov (United States)

    Rodríguez-García, Laura; Hungerbühler, Konrad; Baiker, Alfons; Meemken, Fabian

    2015-09-23

    In the (S)-proline-mediated asymmetric hydrogenation of isophorone (IP) on supported Pd catalyst, excellent enantioselectivity is achieved, with an enantiomeric excess of up to 99%. The role of the heterogeneous catalyst has been the subject of a controversial debate, and the current mechanistic understanding cannot explain the observed enantioselectivity of this catalytic system. The lack of in situ information about the role of the heterogeneous catalyst has prompted us to investigate the surface processes occurring at the methanol-Pd catalyst interface using attenuated total reflection infrared spectroscopy. Time-resolved monitoring of the homogeneous solution and of the catalytic solid-liquid interface coupled with catalytic data provides crucial information on the catalytically relevant enantiodifferentiating processes. While the condensation of IP and the corresponding chiral product 3,3,5-trimethylcyclohexanone with the chiral amine is connected to the enantiodifferentiation, it was found that the crucial enantioselectivity-controlling steps take place on the metal surface, and the reaction has to be classified as heterogeneous asymmetric hydrogenation. The presented spectroscopic and catalytic results provide strong evidence for the existence of two competing enantioselective processes leading to opposing enantioselection. Depending on surface coverage of the Pd catalyst, the reaction is controlled either by kinetic resolution ((S)-pathway) or by chiral catalysis ((R)-pathway). Steering the hydrogenation on the (R)-reaction pathway requires sufficient concentration of IP-(S)-proline condensate, as this chiral reactive intermediate becomes the most abundant surface species, inhibiting the competing kinetic resolution. The unraveled (R)-reaction pathway emphasizes an intriguing strategy for inducing chirality in heterogeneous asymmetric catalysis.

  13. A general approach to mesoporous metal oxide microspheres loaded with noble metal nanoparticles

    KAUST Repository

    Jin, Zhao

    2012-04-26

    Catalytic microspheres: A general approach is demonstrated for the facile preparation of mesoporous metal oxide microspheres loaded with noble metal nanoparticles (see TEM image in the picture). Among 18 oxide/noble metal catalysts, TiO 2/0.1 mol Pd microspheres showed the highest turnover frequency in NaBH 4 reduction of 4-nitrophenol (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Electrocatalysis of chemically synthesized noble metal nanoparticles on carbon electrodes

    DEFF Research Database (Denmark)

    Zhang, Ling; Ulstrup, Jens; Zhang, Jingdong

    Noble metal nanoparticles (NPs), such as platinum (Pt) and palladium (Pd) NPs are promising catalysts for dioxygen reduction and oxidation of molecules such as formic acid and ethanol in fuel cells. Carbon nanomaterials are ideal supporting materials for electrochemical catalysts due to their good...... on their interfacial interaction with the supporting electrodes. In this work we aim at chemical production of size and shape controlled, specifically 22 nm cubic Pd NPs, and further understanding of the Pd NPs as electrocatalysts at the nanometer scale using both scanning tunneling microscopy (STM) and atomic force...

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

    Science.gov (United States)

    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.

  16. 21 CFR 872.3060 - Noble metal alloy.

    Science.gov (United States)

    2010-04-01

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

  17. Polymer-noble metal nanocomposites: Review

    CSIR Research Space (South Africa)

    Folarin, OM

    2011-09-01

    Full Text Available Polymer-noble metal nanocomposites have been extensively investigated due to their potential ability to provide materials with novel mechanical, electronic or chemical behaviour for technological applications. Many preparative procedures have been...

  18. Noble metal superparticles and methods of preparation thereof

    Science.gov (United States)

    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.

  19. Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

    Directory of Open Access Journals (Sweden)

    Zhenghua Tang

    2018-02-01

    Full Text Available Highly-efficient catalysts for the oxygen reduction reaction (ORR have been extensively investigated for the development of proton exchange membrane fuel cells (PEMFCs. The state-of-the-art Pt/C catalysts suffer from high price, limited accessibility of Pt, sluggish reaction kinetics, as well as undesirable long-term durability. Engineering ultra-small noble metal clusters with high surface-to-volume ratios and robust stabilities for ORR represents a new avenue. After a simple introduction regarding the significance of ORR and the recent development of noble metal clusters, the general ORR mechanism in both acidic and basic media is firstly discussed. Subsequently, we will summarize the recent efforts employing Pt, Au, Ag, Pd and Ru clusters, as well as the alloyed bi-metallic clusters for acquiring highly efficient catalysts to enhance both the activity and stability of ORR. Molecular noble metal clusters with definitive composition to reveal the relevant ORR mechanism will be particularly highlighted. Finally, the current challenges, the future outlook, as well as the perspectives in this booming field will be proposed, featuring the great opportunities and potentials to engineering noble metal clusters as highly-efficient and durable cathodic catalysts for fuel cell applications.

  20. Noble Metal Nanoparticles for Biosensing Applications

    Science.gov (United States)

    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. Noble metal alloys for metal-ceramic restorations.

    Science.gov (United States)

    Anusavice, K J

    1985-10-01

    A review of the comparative characteristics and properties of noble metal alloys used for metal-ceramic restorations has been presented. Selection of an alloy for one's practice should be based on long-term clinical data, physical properties, esthetic potential, and laboratory data on metal-ceramic bond strength and thermal compatibility with commercial dental porcelains. Although gold-based alloys, such as the Au-Pt-Pd, Au-Pd-Ag, and Au-Pd classes, may appear to be costly compared with the palladium-based alloys, they have clearly established their clinical integrity and acceptability over an extended period of time. Other than the relatively low sag resistance of the high gold-low silver content alloys and the potential thermal incompatibility with some commercial porcelain products, few clinical failures have been observed. The palladium-based alloys are less costly than the gold-based alloys. Palladium-silver alloys require extra precautions to minimize porcelain discoloration. Palladium-copper and palladium-cobalt alloys may also cause porcelain discoloration, as copper and cobalt are used as colorants in glasses. The palladium-cobalt alloys are least susceptible to high-temperature creep compared with all classes of noble metals. Nevertheless, insufficient clinical data exist to advocate the general use of the palladium-copper and palladium-cobalt alloys at the present time. One should base the selection and use of these alloys in part on their ability to meet the requirements of the ADA Acceptance Program. A list of acceptable or provisionally acceptable alloys is available from the American Dental Association and is published annually in the Journal of the American Dental Association. Dentists have the legal and ethical responsibility for selection of alloys used for cast restorations. This responsibility should not be delegated to the dental laboratory technician. It is advisable to discuss the criteria for selection of an alloy with the technician and the

  2. One parameter model potential for noble metals

    International Nuclear Information System (INIS)

    Idrees, M.; Khwaja, F.A.; Razmi, M.S.K.

    1981-08-01

    A phenomenological one parameter model potential which includes s-d hybridization and core-core exchange contributions is proposed for noble metals. A number of interesting properties like liquid metal resistivities, band gaps, thermoelectric powers and ion-ion interaction potentials are calculated for Cu, Ag and Au. The results obtained are in better agreement with experiment than the ones predicted by the other model potentials in the literature. (author)

  3. Noble metal ionic sites for catalytic hydrogen combustion: spectroscopic insights.

    Science.gov (United States)

    Deshpande, Parag A; Madras, Giridhar

    2011-01-14

    A catalytic hydrogen combustion reaction was carried out over noble metal catalysts substituted in ZrO(2) and TiO(2) in ionic form. The catalysts were synthesized by the solution combustion technique. The compounds showed high activity and CO tolerance for the reaction. The activity of Pd and Pt ion substituted TiO(2) was comparable and was higher than Pd and Pt ion substituted ZrO(2). The mechanisms of the reaction over the two supports were proposed by making use of the X-ray photoelectron spectroscopy and FT infrared spectroscopic observations. The reaction over ZrO(2) supported catalysts was proposed to take place by the utilization of the surface hydroxyl groups while the reaction over TiO(2) supported catalysts was hypothesized to be a hybrid mechanism utilizing surface hydroxyl groups and the lattice oxygen.

  4. PROCESS FOR THE PREPARATION OF ALLOY NANOPARTICLES COMPRISING A NOBLE AND A NON-NOBLE METAL

    DEFF Research Database (Denmark)

    2017-01-01

    The present invention concerns a chemical process for preparing nanoparticles of an alloy comprising both a noble metal, such as platinum, and a non-noble transition or lanthanide metal, such as yttrium, gadolinium or terbium. The process is carried out by reduction with hydrogen and removal...

  5. Influence of the noble metals (Pd, Au, Ag) in the thermoluminescent signal induced by radiation in the ZrO2

    International Nuclear Information System (INIS)

    Villa S, G.

    2006-01-01

    When increasing the use of the ionizing and non ionizing radiations (for example, gamma and ultraviolet radiation) in different areas of the science and technology, there is necessary to apply more accurate safety measures and to avoid over-exposures that could put in risk the life of workers that manipulate radiation sources, patient that are exposed to this under some medical treatment, as well as materials that undergo intentionally to radiation. Also, the UV radiation that arrives to the earth can cause some damages, to the one to weaken the protector layer of ozone the UV radiation increases that arrives to the earth surface being able to affect the alive beings and the materials. By this so much the development of new materials able to take a census of in a more accurate way, fields of gamma and UV radiation is becoming necessary. In this sense, this work presents the obtained results when quantifying radiation fields, through the analysis in the thermoluminescent behavior (TL) induced by the gamma and UV radiation in the zirconium dioxide synthesized by the sol gel method and doped with nanoparticles of Pd, Au and Ag. It is necessary to mention that in reported works in this respect its mention that the zircon has good thermoluminescent sensitivity induced by these radiation types, however it has shown high thermoluminescent instability that is translated in an important lost of the information after the irradiation. For that through the incorporation of the metallic nanoparticles it was intended to stabilize the TL behavior of zircon. The results showed that the doped zircon has a high sensitivity to the gamma and UV radiation. These also show that the ionizing and non ionizing radiation induce a thermoluminescent curve consisting of two TL peaks with maxima located around 65 C and 145 C and that the intensity is increased with the dose, following a lineal behavior in certain interval of dose exposure that is influenced by the presence of the nanoparticles

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

    Science.gov (United States)

    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.

  7. Activity and selectivity control in reductive amination of butyraldehyde over noble metal catalysts.

    NARCIS (Netherlands)

    Bodis, E.; Lefferts, Leonardus; Muller, T.E.; Pestman, R.; Lercher, J.A.

    2005-01-01

    Approaches to control selectivity and activity in the catalytic reductive amination of butyraldehyde with ammonia over carbon supported noble metal catalysts (Ru, Rh, Pd, and Pt) were explored. Detailed analysis of the reaction network shows that the Schiff base N-[butylidene]butan-1-amine is the

  8. Template Synthesis of Noble Metal Nanocrystals with Unusual Crystal Structures and Their Catalytic Applications.

    Science.gov (United States)

    Fan, Zhanxi; Zhang, Hua

    2016-12-20

    crystal structures of noble metal nanocrystals, which might not be easily synthesized by commonly used chemical synthesis. To be specific, by using the epitaxial growth method, a series of noble metal nanocrystals with unusual crystal structures has been obtained, such as hexagonal close-packed Ag, 4H Ag, Pd, Pt, Ir, Rh, Os, and Ru, and face-centered cubic Ru nanostructures. Meanwhile, the galvanic replacement reaction method offers an efficient way to synthesize noble metal alloy nanocrystals with unusual crystal structures, such as 4H PdAg, PtAg, and PtPdAg nanostructures. We then briefly introduce the stability of noble metal nanocrystals with unusual crystal structures. After that, we demonstrate the catalytic applications of the resultant noble metal nanocrystals with unusual crystal structures toward different chemical reactions like hydrogen evolution reaction, hydrogen oxidation reaction and organic reactions. The relationship between crystal structures of noble metal nanocrystals and their catalytic performances is discussed. Finally, we summarize the whole paper, and address the current challenges and future opportunities for the template synthesis of noble metal nanocrystals with unusual crystal structures. We expect that this Account will promote the crystal structure-controlled synthesis of noble metal nanocrystals, which can provide a new way to further improve their advanced functional properties toward their practical applications.

  9. Non-noble metal fuel cell catalysts

    CERN Document Server

    Chen, Zhongwei; Zhang, Jiujun

    2014-01-01

    Written and edited by a group of top scientists and engineers in the field of fuel cell catalysts from both industry and academia, this book provides a complete overview of this hot topic. It covers the synthesis, characterization, activity validation and modeling of different non-noble metal and metalfree electrocatalysts for the reduction of oxygen, as well as their integration into acid or alkaline polymer exchange membrane (PEM) fuel cells and their performance validation, while also discussing those factors that will drive fuel cell commercialization. With its well-structured app

  10. Selective extraction and detection of noble metal based on ionic ...

    Indian Academy of Sciences (India)

    With the dramatic increase in economic growth, noble metals have been extensively utilized for wide range of industries and economic activities. Gold is one of the noble metals, which used in various applications because of its unique properties. However, various reports have mentioned that gold species may cause an ...

  11. Solvent extraction of noble metals by formazans

    International Nuclear Information System (INIS)

    Grote, M.; Hueppe, U.; Kettrup, A.

    1984-01-01

    The extraction properties of ion-pairs composed of quaternary ammonium cations and a sulphonated formazan were compared with those of an unsulphonated formazan, for various solvent media. In dichloromethane the combined system behaves as a 'coloured anion-exchanger', with displacement of the sulphonated formazan, whereas in toluene Pd(II) and Ag(I) are extracted as the metal formazan chelates from aqueous medium. The rates of extraction are remarkably higher than with the simple extractants. Because of the higher stability only the simple chelating extraction systems afford satisfactory separation of Pd(II) from excess of Pt(IV) and of Ag(I) from Cu(II). The extracted metals can be stripped and the extractant regenerated. (author)

  12. Noble Metal Nanoparticles Applications in Cancer

    Directory of Open Access Journals (Sweden)

    João Conde

    2012-01-01

    Full Text Available 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.

  13. Spectrophotometric methods for determining noble metals

    International Nuclear Information System (INIS)

    Gur'eva, R.F.; Savvin, S.B.

    2002-01-01

    The main trends of the development of spectrophotometric methods for determining noble metals (NMs) including ruthenium are considered. One of these trends is the synthesis and study of new, highly sensitive and selective organic reagents for determining NMs in solutions and solid phase. Another trend is the search for and developing of new methodological approaches (techniques) and color reactions, including those that involve modified and immobilized reagents. The third trend includes the improvement of equipment and automation. It is shown that the present-day spectrophotometry can provide the determination of NMs in samples with concentrations from several to 10 -4 % (photometry and differential photometry) and down to 10 -7 % (test and sorption-spectroscopic methods based on photometry and diffuse-reflectance spectroscopy, including the use of chromaticity functions) [ru

  14. Surface treatment of nanoporous silicon with noble metal ions and characterizations

    Energy Technology Data Exchange (ETDEWEB)

    Kanungo, J.; Maji, S. [IC Design and Fabrication Centre, Dept. of Electronics and Tele-comm. Engineering, Jadavpur University, Kolkata 700032 (India); Mandal, A.K.; Sen, S. [Central Glass and Ceramic Research Institute, CSIR, Kolkata (India); Bontempi, E. [INSTM and Laboratorio di Chimica per le Tecnologie, Universita di Brescia, via Branze 38, 25123 Brescia (Italy); Balamurugan, A.K.; Tyagi, A.K. [Materials Science Division, Indira Gandhi Centre for Atomic Research (IGCAR), Kalpakkam 603102 (India); Uvdal, K. [Division of Molecular Surface Physics and Nanoscience, Department of Physics, Chemistry and Biology (IFM), Linkoeping University, SE-581 83 Linkoeping (Sweden); Sinha, S. [Department of Physics, University of New Haven (United States); Saha, H. [IC Design and Fabrication Centre, Dept. of Electronics and Tele-comm. Engineering, Jadavpur University, Kolkata 700032 (India); Basu, S., E-mail: sukumar_basu@yahoo.co.uk [IC Design and Fabrication Centre, Dept. of Electronics and Tele-comm. Engineering, Jadavpur University, Kolkata 700032 (India)

    2010-04-15

    A very large surface to volume ratio of nanoporous silicon (PS) produces a high density of surface states, which are responsible for uncontrolled oxidation of the PS surface. Hence it disturbs the stability of the material and also creates difficulties in the formation of a reliable electrical contact. To passivate the surface states of the nanoporous silicon, noble metals (Pd, Ru, and Pt) were dispersed on the PS surface by an electroless chemical method. GIXRD (glancing incidence X-ray diffraction) proved the crystallinity of PS and the presence of noble metals on its surface. While FESEM (field emission scanning electron microscopy) showed the morphology, the EDX (energy dispersive X-ray) line scans and digital X-ray image mapping indicated the formation of the noble metal islands on the PS surface. Dynamic SIMS (secondary ion mass spectroscopy) further confirmed the presence of noble metals and other impurities near the surface of the modified PS. The variation of the surface roughness after the noble metal modification was exhibited by AFM (atomic force microscopy). The formation of a thin oxide layer on the modified PS surface was verified by XPS (X-ray photoelectron spectroscopy).

  15. Effect of the Noble Metals Addition on the Oxidation Behavior of Ni3Al

    Directory of Open Access Journals (Sweden)

    J. J. Ramos-Hernandez

    2018-01-01

    Full Text Available This paper discusses the effect of the addition of noble metals on the microstructure, mechanism, and oxidation kinetics of the Ni3Al intermetallic alloy. Ni3Al was doped with 1% (atomic percent of Au, Ag, Pd, and Pt. Oxidation behavior of the alloys was evaluated at 900, 1000, and 1100°C in O2 for 24 hours. XRD analysis showed that the addition of noble metals favored the oxide growth on preferential crystallographic planes. In addition, the preferential substitution of the noble metals in the Ni3Al structure modifies the surface composition by increasing the Al/Ni ratio. It was observed that most of the alloys showed a subparabolic behavior, and only the intermetallic base and the alloy doped with Ag show a parabolic behavior at 900°C. The developed oxides were analyzed both superficially and in cross section by scanning electron microscopy (SEM and energy dispersive X-ray analysis (EDXA. It was evident that only the intermetallic base showed the formation of a duplex oxide scale (Al2O3/NiO. The alloys doped with noble metals showed the oxide growth practically of pure Al2O3. This was due to a decrease in the diffusion of the Ni cations because of the presence of the noble metals in the crystalline structure.

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

    Science.gov (United States)

    Davis, Patricia; Miller, Irvin; Upchurch, Billy

    2010-01-01

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

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

    Science.gov (United States)

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

    Science.gov (United States)

    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. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Influence of the noble metals (Pd, Au, Ag) in the thermoluminescent signal induced by radiation in the ZrO{sub 2}; Influencia de los metales nobles (Pd, Au, Ag) en la senal termoluminiscente inducida por la radiacion en la ZrO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Villa S, G

    2006-07-01

    When increasing the use of the ionizing and non ionizing radiations (for example, gamma and ultraviolet radiation) in different areas of the science and technology, there is necessary to apply more accurate safety measures and to avoid over-exposures that could put in risk the life of workers that manipulate radiation sources, patient that are exposed to this under some medical treatment, as well as materials that undergo intentionally to radiation. Also, the UV radiation that arrives to the earth can cause some damages, to the one to weaken the protector layer of ozone the UV radiation increases that arrives to the earth surface being able to affect the alive beings and the materials. By this so much the development of new materials able to take a census of in a more accurate way, fields of gamma and UV radiation is becoming necessary. In this sense, this work presents the obtained results when quantifying radiation fields, through the analysis in the thermoluminescent behavior (TL) induced by the gamma and UV radiation in the zirconium dioxide synthesized by the sol gel method and doped with nanoparticles of Pd, Au and Ag. It is necessary to mention that in reported works in this respect its mention that the zircon has good thermoluminescent sensitivity induced by these radiation types, however it has shown high thermoluminescent instability that is translated in an important lost of the information after the irradiation. For that through the incorporation of the metallic nanoparticles it was intended to stabilize the TL behavior of zircon. The results showed that the doped zircon has a high sensitivity to the gamma and UV radiation. These also show that the ionizing and non ionizing radiation induce a thermoluminescent curve consisting of two TL peaks with maxima located around 65 C and 145 C and that the intensity is increased with the dose, following a lineal behavior in certain interval of dose exposure that is influenced by the presence of the nanoparticles

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

    Science.gov (United States)

    Li, Guodong; Tang, Zhiyong

    2014-04-21

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  2. Structural and plasmonic properties of noble metal doped ZnO nanomaterials

    Science.gov (United States)

    Pathak, Trilok K.; Swart, H. C.; Kroon, R. E.

    2018-04-01

    Noble metal doped ZnO has been synthesized by the combustion method and the effect of different metals (Ag, Au, Pd) on the structural, morphological, optical, photoluminescence and localized surface plasmon resonance (LSPR) properties has been investigated. X-ray diffraction analysis revealed that the ZnO had a hexagonal wurtzite structure and the crystallite sizes were affected by the doping. The formation of noble metal nanoparticles (NPs) was investigated using transmission electron microscopy and diffuse reflectance spectra. The LSPR of the metallic NPs was predicted using Mie theory calculations. The absorption spectra were calculated using the Kubelka-Munk function and the optical bandgap varied from 3.06 to 3.18 eV for the different doping materials. The experimental results suggest that the origin of enhanced emission was due to direct interaction between the laser photons and the noble material NPs which in turn leads to photoemission transfer of electrons from the noble metals NPs to the conduction band of ZnO.

  3. Noble metals in ferromanganese crusts from marginal seas of the Northwest Pacific

    Science.gov (United States)

    Astakhova, N. V.

    2017-07-01

    Based on data on the concentration of noble metals (Au, Ag, Pt, Os, Ir, and Ru) in bulk samples of ferromanganese crusts, the presence of inclusions of micro- and nanosized grains of Ag, Au, Pd, and Pt, often with impurities of other elements, as well as their chaotic distribution, three sources of incorporation of these metals into ore crusts of Far Eastern seas are suggested: seawater, postvolcanic gas-hydrothermal fluids, and hydrothermal plumes. The presence of grains of platinoids and gold in ferromanganese crusts on only some mounts may result from peculiarities in the formation of volcanic rocks on the ancient continental basement.

  4. NOBLE METAL CHEMISTRY AND HYDROGEN GENERATION DURING SIMULATED DWPF MELTER FEED PREPARATION

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D

    2008-06-25

    Simulations of the Defense Waste Processing Facility (DWPF) Chemical Processing Cell vessels were performed with the primary purpose of producing melter feeds for the beaded frit program plus obtaining samples of simulated slurries containing high concentrations of noble metals for off-site analytical studies for the hydrogen program. Eight pairs of 22-L simulations were performed of the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles. These sixteen simulations did not contain mercury. Six pairs were trimmed with a single noble metal (Ag, Pd, Rh, or Ru). One pair had all four noble metals, and one pair had no noble metals. One supporting 4-L simulation was completed with Ru and Hg. Several other 4-L supporting tests with mercury have not yet been performed. This report covers the calculations performed on SRNL analytical and process data related to the noble metals and hydrogen generation. It was originally envisioned as a supporting document for the off-site analytical studies. Significant new findings were made, and many previous hypotheses and findings were given additional support as summarized below. The timing of hydrogen generation events was reproduced very well within each of the eight pairs of runs, e.g. the onset of hydrogen, peak in hydrogen, etc. occurred at nearly identical times. Peak generation rates and total SRAT masses of CO{sub 2} and oxides of nitrogen were reproduced well. Comparable measures for hydrogen were reproduced with more variability, but still reasonably well. The extent of the reproducibility of the results validates the conclusions that were drawn from the data.

  5. Peptide-templated noble metal catalysts: syntheses and applications.

    Science.gov (United States)

    Wang, Wei; Anderson, Caleb F; Wang, Zongyuan; Wu, Wei; Cui, Honggang; Liu, Chang-Jun

    2017-05-01

    Noble metal catalysts have been widely used in many applications because of their high activity and selectivity. However, a controllable preparation of noble metal catalysts still remains as a significant challenge. To overcome this challenge, peptide templates can play a critical role in the controllable syntheses of catalysts owing to their flexible binding with specific metallic surfaces and self-assembly characteristics. By employing peptide templates, the size, shape, facet, structure, and composition of obtained catalysts can all be specifically controlled under the mild synthesis conditions. In addition, catalysts with spherical, nanofiber, and nanofilm structures can all be produced by associating with the self-assembly characteristics of peptide templates. Furthermore, the peptide-templated noble metal catalysts also reveal significantly enhanced catalytic behaviours compared with conventional catalysts because the electron conductivity, metal dispersion, and reactive site exposure can all be improved. In this review, we summarize the research progresses in the syntheses of peptide-templated noble metal catalysts. The applications of the peptide-templated catalysts in organic reactions, photocatalysis, and electrocatalysis are discussed, and the relationship between structure and activity of these catalysts are addressed. Future opportunities, including new catalytic materials designed by using biological principles, are indicated to achieve selective, eco-friendly, and energy neutral synthesis approaches.

  6. Variations of color with alloying elements in Pd-free Au-Pt-based high noble dental alloys

    International Nuclear Information System (INIS)

    Shiraishi, Takanobu; Takuma, Yasuko; Miura, Eri; Fujita, Takeshi; Hisatsune, Kunihiro

    2007-01-01

    The effects of alloying addition of a small amount of base metals (In, Sn, Fe, Zn) on color variations in Pd-free Au-Pt-based high noble dental alloys were investigated in terms of rectilinear and polar color coordinates. The ternary Au-Pt-X (X = In, Sn, Fe, Zn) and quaternary Au-Pt-In-Y (Y = Sn, Fe, Zn) alloys were prepared from high purity component metals. The amount of alloying base metals, X and Y, were restricted up to 2 at.%. The alloying addition of a small amount of Fe, In, Sn, to a binary Au-10 at.% Pt alloy (referred to as AP10) effectively increased chroma, C *. On the other hand, the addition of Zn to the parent alloy AP10 did not change color coordinates greatly. The increase in chroma in the present Au-Pt-based high noble alloys was attributed to the increase in the slope of spectral reflectance curve at its absorption edge near 515 nm. It was found that the addition of a small amount of Fe to the parent alloy AP10 markedly increased lightness, L *, and the addition of Sn gave a very light tint of red to the parent alloy. Although red-green chromaticity index a * contributed to chroma to some extent, contribution of yellow-blue chromaticity index b * was much greater in determining chroma in this Pd-free Au-Pt-based multi-component alloys. The present results are expected to be valuable in case color is to be taken into account in designing Pd-free Au-Pt-based high noble dental alloys

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

    International Nuclear Information System (INIS)

    Hart, R.J.

    1978-01-01

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

  8. Green synthesis of noble nanometals (Au, Pt, Pd) using glycerol under microwave irradiation conditions

    Science.gov (United States)

    A newer application of glycerol in the field of nanomaterials synthesis has been developed from both the economic and environmental points of view. Glycerol can act as a reducing agent for the fabrication of noble nanometals, such as Au, Pt, and Pd, under microwave irradiation. T...

  9. Towards to Extraction of Nanodispersed Noble Metals From Natural Black Graphite Shales

    Directory of Open Access Journals (Sweden)

    Elena A. Mikhailenko

    2012-01-01

    Full Text Available A theoretical approach based on the density functional theory and the pseudopotential method was applied to consider diffusion and accumulation of Au, Pt, and Pd in graphite. It is shown that Pt atoms migrate easily inside graphite. They can stop at structure defects and accumulate there, attracting each other and forming plate clusters. Atoms of gold do not penetrate into graphite but link with edge atoms of broken graphite crystallites, forming three-dimensional metallic particles. Palladium behavior is intermediate between platinum and gold. Addition of silicon into graphite can promote the extraction of noble metals because Si atoms force out Pt, Pd, and Au atoms from their bonded states. Last effect can be used as a mechanism of striking off metals from graphite and their extraction from shales

  10. Classical and quantum effects in noble metal and graphene plasmonics

    DEFF Research Database (Denmark)

    Mortensen, N. Asger

    2015-01-01

    such as nonclassical electrodynamics with a nonlocal response of the plasmons. Nonlocal effects are being explored both theoretically and experimentally in different charge-conducting material systems with examples ranging from sub-10 nanometer noble metal particles to one-atom thin disks of doped graphene....

  11. Noble-Metal Nanocrystals with Controlled Facets for Electrocatalysis.

    Science.gov (United States)

    Hong, Jong Wook; Kim, Yena; Kwon, Yongmin; Han, Sang Woo

    2016-08-19

    Noble-metal nanocrystals (NCs) show excellent catalytic performance for many important electrocatalysis reactions. The crystallographic properties of the facets by which the NCs are bound, closely associated with the shape of the NCs, have a profound influence on the electrocatalytic function of the NCs. To develop an efficient strategy for the synthesis of NCs with controlled facets as well as compositions, understanding of the growth mechanism of the NCs and their interaction with the chemical species involved in NC synthesis is quite important. Furthermore, understanding the facet-dependent catalytic properties of noble-metal NCs and the corresponding mechanisms for various electrocatalysis reactions will allow for the rational design of robust electrocatalysts. In this review, we summarize recently developed synthesis strategies for the preparation of mono- and bimetallic noble-metal NCs by classifying them by the type of facets through which they are enclosed and discuss the electrocatalytic applications of noble-metal NCs with controlled facets, especially for reactions associated with fuel-cell applications, such as the oxygen reduction reaction and fuel (methanol, ethanol, and formic acid) oxidation reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A review of dry (CO2) reforming of methane over noble metal catalysts.

    Science.gov (United States)

    Pakhare, Devendra; Spivey, James

    2014-11-21

    Dry (CO2) reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. This reaction produces syngas that can be used to produce a wide range of products, such as higher alkanes and oxygenates by means of Fischer-Tropsch synthesis. DRM is inevitably accompanied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires operating temperatures of 800-1000 °C to attain high equilibrium conversion of CH4 and CO2 to H2 and CO and to minimize the thermodynamic driving force for carbon deposition. The most widely used catalysts for DRM are based on Ni. However, many of these catalysts undergo severe deactivation due to carbon deposition. Noble metals have also been studied and are typically found to be much more resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved in the activation and conversion of CH4 and CO2. This review will cover DRM literature for catalysts based on Rh, Ru, Pt, and Pd metals. This includes the effect of these noble metals on the kinetics, mechanism and deactivation of these catalysts.

  13. Noble Metal/Ceramic Composites in Flame Processes

    DEFF Research Database (Denmark)

    Schultz, Heiko; Madler, Lutz; Strobel, Reto

    conditions influence the resulting noble metal particles size in those systems [1]. For every specific application the particle size and the metal/metal oxide interaction affect the performance of these nano-composite materials [2]. Recently, aerosol processes have been successfully used to produce platinum...... [3,4], palladium [5], silver [6] and gold [7] crystallites on Al2O3 [3,5], SiO2 [7] and TiO2 [4,6,7] in a single step.. The as-prepared materials exhibited a high external specific surface area (40 – 320 m2 g-1) [3-7] with a high degree of crystallinity and an excellent noble metal distribution [3...... size is mainly dependent on its loading [3,7]. In this study, the role of the supporting metal oxide on the noble metal particle size was systematically investigated for the flame spray pyrolysis process. The materials were produced at fixed process conditions such as resident time of the particles...

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  15. Visible light active TiO 2 films prepared by electron beam deposition of noble metals

    Science.gov (United States)

    Hou, Xing-Gang; Ma, Jun; Liu, An-Dong; Li, De-Jun; Huang, Mei-Dong; Deng, Xiang-Yun

    2010-03-01

    TiO 2 films prepared by sol-gel method were modified by electron beam deposition of noble metals (Pt, Pd, and Ag). Effects of noble metals on the chemical and surface characteristics of the films were studied using XPS, TEM and UV-Vis spectroscopy techniques. Photocatalytic activity of modified TiO 2 films was evaluated by studying the degradation of methyl orange dye solution under visible light UV irradiation. The result of TEM reveals that most of the surface area of TiO 2 is covered by tiny particles of noble metals with diameter less than 1 nm. Broad red shift of UV-Visible absorption band of modified photocatalysts was observed. The catalytic degradation of methyl orange in aqueous solutions under visible light illumination demonstrates a significant enhancement of photocatalytic activity of these films compared with the un-loaded films. The photocatalytic efficiency of modified TiO 2 films by this method is affected by the concentration of impregnating solution.

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

    Science.gov (United States)

    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.

  17. Enriching Silver Nanocrystals with a Second Noble Metal.

    Science.gov (United States)

    Wu, Yiren; Sun, Xiaojun; Yang, Yin; Li, Jumei; Zhang, Yun; Qin, Dong

    2017-07-18

    Noble-metal nanocrystals have received considerable interests owing to their fascinating properties and promising applications in areas including plasmonics, catalysis, sensing, imaging, and medicine. As demonstrated by ample examples, the performance of nanocrystals in these and related applications can be augmented by switching from monometallic to bimetallic systems. The inclusion of a second metal can enhance the properties and greatly expand the application landscape by bringing in new capabilities. Seeded growth offers a powerful route to bimetallic nanocrystals. This approach is built upon the concept that preformed nanocrystals with uniform, well-controlled size, shape, and structure can serve as seeds to template and direct the deposition of metal atoms. Seeded growth is, however, limited by galvanic replacement when the deposited metal is less reactive than the seed. The involvement of galvanic replacement not only makes it difficult to control the outcome of seeded growth but also causes degradation to some properties. We have successfully addressed this issue by reducing the salt precursor(s) into atoms with essentially no galvanic replacement. In the absence of self-nucleation, the atoms are preferentially deposited onto the seeds to generate bimetallic nanocrystals with controlled structures. In this Account, we use Ag nanocubes as an example to demonstrate the fabrication of Ag@M and Ag@Ag-M (M = Au, Pd, or Pt) nanocubes with a core-frame or core-shell structure by controlling the deposition of M atoms. A typical synthesis involves the titration of M n+ (a precursor to M) ions into an aqueous suspension containing Ag nanocubes, ascorbic acid, and poly(vinylpyrrolidone) under ambient conditions. In one approach, aqueous sodium hydroxide is introduced to increase the initial pH of the reaction system. At pH = 11.9, ascorbic acid is dominated by ascorbate monoanion, a much stronger reductant, to suppress the galvanic replacement between M n+ and Ag. In

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

    Science.gov (United States)

    Zou, Xiaoxin; Zhang, Yu

    2015-08-07

    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.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    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, UO 2 fuel dissolved in nitric acid and UO 2 fuel dissolved in ammonium-carbonate and hydrogen-peroxide solution, are compared. - Highlights: • The noble metal phase was chemically extracted from spent nuclear fuel and analyzed non-destructively. • Noble metal phase nuclides and long-lived iodine were identified and quantified using neutron activation analysis. • Activation to shorter-lived radionuclides allowed rapid analysis of long-lived fission products in spent fuel using gamma spectrometry

  20. Liquid state properties of certain noble and transition metals

    International Nuclear Information System (INIS)

    Bhuiyan, G.M.; Rahman, A.; Khaleque, M.A.; Rashid, R.I.M.A.; Mujibur Rahman, S.M.

    1998-07-01

    Certain structural, thermodynamic and atomic transport properties of a number of liquid noble and transition metals are reported. The underlying theory combines together a simple form of the N-body potential and the thermodynamically self-consistent variational modified hypernetted chain (VMHNC) theory of liquid. The static structure factors calculated by using the VMHNC resemble the hard sphere (HS) values. Consequently the HS model is used to calculate the thermodynamic properties viz. specific heat, entropy, isothermal compressibility and atomic transport properties. (author)

  1. Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

    OpenAIRE

    Zhenghua Tang; Wen Wu; Kai Wang

    2018-01-01

    Highly-efficient catalysts for the oxygen reduction reaction (ORR) have been extensively investigated for the development of proton exchange membrane fuel cells (PEMFCs). The state-of-the-art Pt/C catalysts suffer from high price, limited accessibility of Pt, sluggish reaction kinetics, as well as undesirable long-term durability. Engineering ultra-small noble metal clusters with high surface-to-volume ratios and robust stabilities for ORR represents a new avenue. After a simple introduction ...

  2. Near transferable phenomenological n-body potentials for noble metals

    Science.gov (United States)

    Pontikis, Vassilis; Baldinozzi, Gianguido; Luneville, Laurence; Simeone, David

    2017-09-01

    We present a semi-empirical model of cohesion in noble metals with suitable parameters reproducing a selected set of experimental properties of perfect and defective lattices in noble metals. It consists of two short-range, n-body terms accounting respectively for attractive and repulsive interactions, the former deriving from the second moment approximation of the tight-binding scheme and the latter from the gas approximation of the kinetic energy of electrons. The stability of the face centred cubic versus the hexagonal compact stacking is obtained via a long-range, pairwise function of customary use with ionic pseudo-potentials. Lattice dynamics, molecular statics, molecular dynamics and nudged elastic band calculations show that, unlike previous potentials, this cohesion model reproduces and predicts quite accurately thermodynamic properties in noble metals. In particular, computed surface energies, largely underestimated by existing empirical cohesion models, compare favourably with measured values, whereas predicted unstable stacking-fault energy profiles fit almost perfectly ab initio evaluations from the literature. All together the results suggest that this semi-empirical model is nearly transferable.

  3. Discrete Silver(I)-Palladium(II)-Oxo Nanoclusters, {Ag4Pd13} and {Ag5Pd15}, and the Role of Metal-Metal Bonding Induced by Cation Confinement.

    Science.gov (United States)

    Yang, Peng; Xiang, Yixian; Lin, Zhengguo; Lang, Zhongling; Jiménez-Lozano, Pablo; Carbó, Jorge J; Poblet, Josep M; Fan, Linyuan; Hu, Changwen; Kortz, Ulrich

    2016-12-19

    We introduce the class of discrete silver(I)-palladium(II)-oxo nanoclusters with the preparation of {Ag 4 Pd 13 } and {Ag 5 Pd 15 }. Both polyanions represent the first examples of noble metal-capped polyoxo-noble-metalates in a fully inorganic assembly, featuring an unprecedented host-guest mode containing hetero- and homometallic Ag-Pd and Ag-Ag bonding interactions. Comprehensive theoretical calculations suggest that the Ag-Pd metallic bonds originate partially from surface confinement of Ag I guest ions onto the anionic polyoxopalladate host that is induced by strong electrostatic forces. This work opens the field of fully inorganic silver-palladium-oxo nanoclusters, which can be considered as discrete mixed noble metal precursors for the formation of monodisperse core-shell nanoparticles, with high relevance for catalysis. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  6. Fabrication and Performance of Noble Metal Promoted Birnessite Catalysts for Complete Oxidation of Formaldehyde at Low Temperatures.

    Science.gov (United States)

    Liu, Linlin; Tian, Hua; He, Junhui; Wang, Donghui; Ma, Chunyan; Yang, Qiaowen

    2015-04-01

    Noble metal (Au, Ag, Pd and Pt) promoted birnessite (Bir) catalysts were successfully prepared and tested for catalytic oxidation of formaldehyde (HCHO). The catalysts were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), hydrogen temperature programmed reduction (H2-TPR), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and N2 adsorption-desorption. The activities of noble metal (Au, Ag, Pd and Pt) promoted birnessite catalysts follow the order of 1.0Pt/Bir > 1.0Pd/Bir > Bir > 1.0Ag/Bir > 1.0Au/Bir, revealing that the loading of Pd and Pt improves the catalytic activity of birnessite, but the loading of Ag and Au slightly decreases the catalytic activity of birnessite. Effects of the Pt loading amount were also investigated on the activity of Pt/Bir catalysts for HCHO oxidation. Pt/Bir with a Pt loading of 1.5 wt% (1.5 Pt/Bir), which has the best reduction properties, was found to be the most efficient catalyst. Over this catalyst, HCHO could be completely oxidized into CO2 and H2O at 70°. 1.5 Pt/Bir also shows good catalytic stability under the HCHO oxidation atmosphere. The differences in the catalytic activity of these materials are largely attributed to their reducibility as well as the dispersion of metal nanoparticles, but are not directly related to their specific surface areas.

  7. Efficient noble metal nanocatalysts supported on HfC(001 for O2 dissociation

    Directory of Open Access Journals (Sweden)

    Shiyan Wang

    2017-03-01

    Full Text Available The adsorption and dissociation of O2 on the M4 (M=Au, Pd, Pt clusters supported on HfC(001 (Hafnium Carbide are investigated using ab initio density functional theory calculations. The geometric and electronic structures are analyzed in detail. It is found that the dissociation barriers of O2 on Au4/HfC(001 (0.26 eV, Pd4/HfC(001 (0.49 eV and Pt4/HfC(001 (0.09 eV are much smaller than those on the clean surfaces of HfC(001 (1.60 eV, Au(111 (1.37 eV, Pd(111 (1.0 and 0.91 eV and Pt(111 (0.27–0.7 eV, respectively. The low dissociation barriers imply that the Pt4/HfC(001 exhibits the highest catalytic activity for O2 dissociation, and the Au4/HfC(001 and Pd4/HfC(001 may also be possible substitutes with lower cost for the current Pt/C catalyst for O2 dissociation. The present study is conductive to designing new efficient noble metal catalyst using HfC support for efficiently promoting O2 dissociation.

  8. Nanoparticles of noble metals in the supergene zone

    Science.gov (United States)

    Zhmodik, S. M.; Kalinin, Yu. A.; Roslyakov, N. A.; Mironov, A. G.; Mikhlin, Yu. L.; Belyanin, D. K.; Nemirovskaya, N. A.; Spiridonov, A. M.; Nesterenko, G. V.; Airiyants, E. V.; Moroz, T. N.; Bul'bak, T. A.

    2012-04-01

    Formation of noble metal nanoparticles is related to various geological processes in the supergene zone. Dispersed mineral phases appear during weathering of rocks with active participation of microorganisms, formation of soil, in aqueous medium and atmosphere. Invisible gold and other noble metals are incorporated into oxides, hydroxides, and sulfides, as well as in dispersed organic and inorganic carbonic matter. Sulfide minerals that occur in bedrocks and ores unaltered by exogenic processes and in cementation zone are among the main concentrators of noble metal nanoparticles. The ability of gold particles to disaggregate is well-known and creates problems in technological and analytical practice. When Au and PGE nanoparticles and clusters occur, these problems are augmented because of their unusual reactions and physicochemical properties. The studied gold, magnetite, titanomagnetite and pyrite microspherules from cementation zone and clay minerals of laterites in Republic of Guinea widen the knowledge of their abundance and inferred formation conditions, in particular, in the contemporary supergene zone. Morphology and composition of micrometer-sized Au mineral spherules were studied with SEM and laser microprobe. The newly formed segregations of secondary gold on the surface of its residual grains were also an object of investigation. The character of such overgrowths is the most indicative for nanoparticles. The newly formed Au particles provide evidence for redistribution of ultradispersed gold during weathering. There are serious prerequisites to state that microorganisms substantially control unusual nano-sized microspherical morphology of gold particles in the supergene zone. This is supported by experiments indicating active absorption of gold by microorganisms and direct evidence for participation of Ralstonia metallidurans bacteria in the formation of peculiar corroded bacteriomorphic surface of gold grains. In addition, the areas enriched in carbon

  9. Studies on PEM Fuel Cell Noble Metal Catalyst Dissolution

    DEFF Research Database (Denmark)

    Ma, Shuang; Skou, Eivind Morten

    Incredibly vast advance has been achieved in fuel cell technology regarding to catalyst efficiency, improvement of electrolyte conductivity and optimization of cell system. With breathtakingly accelerating progress, Proton Exchange Membrane Fuel Cells (PEMFC) is the most promising and most widely....... Membrane Electrode Assembly (MEA) is commonly considered as the heart of cell system [2]. Degradation of the noble metal catalysts in MEAs especially Three-Phase-Boundary (TPB) is a key factor directly influencing fuel cell durability. In this work, electrochemical degradation of Pt and Pt/Ru alloy were...

  10. Effects of metal primers on the bonding of an adhesive resin cement to noble metal ceramic alloys after thermal cycling.

    Science.gov (United States)

    Minami, Hiroyuki; Murahara, Sadaaki; Suzuki, Shiro; Tanaka, Takuo

    2011-12-01

    Although the effectiveness of primers for resin bonding to noble alloys has been demonstrated, no effective clinical technique for bonding to noble metal ceramic alloys has been established. The purpose of this study was to evaluate the effects of metal primers on the shear bond strength of an adhesive resin to noble metal ceramic alloys after thermal cycling. Sixty-three disk-shaped specimens (10 × 2.5 mm) were cast from high-gold-content alloys (Super Metal W-85: W85 or IFK88 GR: IFK88), a high-palladium-content alloy (Super Metal N-40: N40), and an Ag-Pd-Cu-Au alloy (Castwell M.C.12: MC12). Smaller-sized disk-shaped specimens (8 × 2.5 mm) were fabricated with MC12. Bonding surfaces were finished with 600-grit SiC-paper and airborne-particle abraded with 50-μm alumina. Pairs of disks were primed (V-Primer: VP; ML Primer: ML; or Metaltite: MT) and bonded with an adhesive resin (Super-Bond C&B). The bond strengths were determined before and after 20,000 and 50,000 thermal cycles (n=7). Data were analyzed by using a 3-way ANOVA and the Bonferroni test (α=.05). Failure modes were determined by optical microscope and SEM observation. Bond strengths to high-gold-content alloys with VP and MT significantly decreased after the thermal cycling (Palloys were not degraded up to 50,000 thermal cycles when primed with ML. None of the primers evaluated was effective for high-palladium-content alloy. Copyright © 2011 The Editorial Council of the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights reserved.

  11. Synthesis of Self-assembled Noble Metal Nanoparticle Chains Using Amyloid Fibrils of Lysozyme as Templates

    Directory of Open Access Journals (Sweden)

    Ziming Xu

    2016-01-01

    Full Text Available We reported a facile method for preparing self-assembled noble metal nanoparticle chains by using lysozyme amyloid fibrils as a biotemplate in an aqueous environ‐ ment. The nanoparticle chains of gold (AuNPCs, palladi‐ um (PdNPCs, platinum (PtNPCs and rhodium (RhNPCs, which are lysozyme fibrils coated by gold, palladium, platinum and rhodium nanoparticles, can be fabricated by simply reducing the corresponding metal salt precursors using NaBH4. Under the same molar ratio between salt precursors and fibrils, two types of morphologies of high- yield AuNPCs (thin- and thick- AuNPCs were synthesized as a result of adjusting the fibrosis time and temperature in the final stage. Abundant PdNPCs with a length of several micrometres intertwisted with each other to form PdNPC networks. The growth of RhNPCs started from the inner surface of the fibrils and gradually spread to the whole fibre as superabundant rhodium nanoparticles (RhNPs bound to the fibrils. Finally, PtNPCs at different growing periods were presented. The nanostructures were investigated by transmission electron microscope, UV-visible spectrosco‐ py, fluorescence spectroscopy, energy-dispersive X-ray spectroscopy and atomic force microscope.

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

    Science.gov (United States)

    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.

  13. Automated electrodeposition of bimetallic noble-metal nanoclusters via redox-replacement reactions for electrocatalysis

    CSIR Research Space (South Africa)

    Mkwizu, TS

    2009-01-01

    Full Text Available of Bimetallic Noble-Metal Nanoclusters via Redox- Replacement Reactions for Electrocatalysis T. S. Mkwizua,b, M. K. Matheb, and I. Cukrowskia aDepartment of Chemistry, University of Pretoria, NW-1 Building, Pretoria, 0002, South Africa b... strategies have utilized surface-limited redox-replacement reactions involving spontaneous replacement of less noble, sacrificial elements, such as Cu or Pb, used as templating layers in controlled synthesis of multilayers composed of noble metals...

  14. Optical Properties and Immunoassay Applications of Noble Metal Nanoparticles

    Directory of Open Access Journals (Sweden)

    Shaoli Zhu

    2010-01-01

    Full Text Available Noble metal, especially gold (Au and silver (Ag nanoparticles exhibit unique and tunable optical properties on account of their surface plasmon resonance (SPR. In this paper, we mainly discussed the theory background of the enhanced optical properties of noble metal nanoparticles. Mie theory, transfer matrix method, discrete dipole approximation (DDA method, and finite-difference time domain (FDTD method applied brute-force computational methods for different nanoparticles optical properties. Some important nanostructure fabrication technologies such as nanosphere lithography (NSL and focused ion beam (FIB are also introduced in this paper. Moreover, these fabricated nanostructures are used in the plasmonic sensing fields. The binding signal between the antibody and antigen, amyloid-derived diffusible ligands (ADDLs-potential Alzheimer's disease (AD biomarkers, and staphylococcal enterotixn B (SEB in nano-Moore per liter (nM concentration level are detected by our designed nanobiosensor. They have many potential applications in the biosensor, environment protection, food security, and medicine safety for health, and so forth, fields.

  15. Optical Properties and Immunoassay Applications of Noble Metal Nanoparticles

    International Nuclear Information System (INIS)

    Zhu, S.; Zhou, W.

    2010-01-01

    Noble metal, especially gold (Au) and silver (Ag) nanoparticles exhibit unique and tunable optical properties on account of their surface plasmon resonance (SPR). In this paper, we mainly discussed the theory background of the enhanced optical properties of noble metal nanoparticles. Mie theory, transfer matrix method, discrete dipole approximation (DDA) method, and finite-difference time domain (FDTD) method applied brute-force computational methods for different nanoparticles optical properties. Some important nanostructure fabrication technologies such as nanosphere lithography (NSL) and focused ion beam (FIB) are also introduced in this paper. Moreover, these fabricated nanostructures are used in the plasmonic sensing fields. The binding signal between the antibody and antigen, amyloid-derived diffusible ligands (ADDLs)-potential Alzheimer's disease (AD) biomarkers, and staphylococcal enterotoxin B (SEB) in nano-Moore per liter (nM) concentration level are detected by our designed nanobiosensor. They have many potential applications in the biosensor, environment protection, food security, and medicine safety for health, and so forth, fields.

  16. Modification of titanium electrodes by a noble metal deposit

    Energy Technology Data Exchange (ETDEWEB)

    Devilliers, D.; Mahe, E. [Pierre et Marie Curie Univ., Paris (France). Laboratoire LI2C, UMR CNRS

    2008-07-01

    Titanium is commonly used as a substrate for dimensionally stable anodes (DSAs) because it is corrosion-resistant in acid media and because a passive titanium oxide (TiO2) film can be formed on the surface. This paper reported on a study in which titanium substrates were first covered by anodization with a TiO2 layer. The electrochemical properties of the Ti/TiO2 electrodes were investigated. The modification of the substrates by cathodic electrodeposition of a noble metal was described. The reactivity of the Ti/TiO2/Pt structures were illustrated by impedance spectroscopy experiments. The impedance studies performed with Ti/ TiO2 electrodes in the presence of a redox couple in solution (Fe3+/Fe2+ system in sulphuric acid) showed that the electronic transfer is very slow. It was concluded that the deposition of a noble metal coating on Ti/TiO2 substrates leads to modified titanium electrodes that exhibit electrocatalytic behaviour versus specific electrochemical reactions. 1 ref., 3 figs.

  17. Noble metals decorated hierarchical maghemite magnetic tubes as an efficient recyclable catalyst.

    Science.gov (United States)

    Purbia, Rahul; Paria, Santanu

    2018-02-01

    The noble metal nanocatalysts on high surface area magnetic material supports have huge technological importance in the field of catalysis. The green synthesis of magnetic-noble metal hybrid material has another technological importance. In this study, we report a novel, efficient, and sustainable synthesis methodology for Au nanoparticles (NPs) deposited hierarchical magnetic maghemite (γ-Fe 2 O 3 ) tubes. In this methodology, the green tea extract was used as a reducing agent for both iron oxide and Au NPs synthesis. The natural cotton fibers were used as a sacrificial template to obtain porous and high surface area (90m 2 /g) magnetic γ-Fe 2 O 3 tubes. Further, the Au NPs (7±2nm) were in situ deposited onto the tubes surface after reduction of Au salt by green tea extract. The XPS spectra was confirmed the presence of negatively charged Au on the iron oxide supports due to charge transfer process and strong metal-support material electronic interaction. The Au NPs decorated γ-Fe 2 O 3 tubes were possessed 18emu/g saturation magnetization at room temperature which is large enough for the magnetic separation. The synthesized material was showed very good catalytic activity for the hydrogenation reaction of 4-nitrophenol to aminophenol conversion. As the catalyst has very good magnetic property, the reusability of catalyst was checked after magnetic separation and found only 0.29% reduction in catalytic activity after the sixth cycle. Further, the Ag and Pd NPs decorated γ-Fe 2 O 3 tubes were also synthesized and tested for the same catalytic reaction and found the highest activity for Pd. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Application of ASA supported noble metal catalysts in the deep hydrodesulphurisation of diesel fuel

    Energy Technology Data Exchange (ETDEWEB)

    Reinhoudt, H.R.; Troost, R.; Van Schalkwijk, S.; Van Langeveld, A.D.; Sie, S.T.; Moulijn, J.A. [Delft University of Technology, Delft (Netherlands); Schulz, H. [Universitaet Karlsruhe, Engler Bunte Institut, Karlsruhe (Germany); Chadwick, D. [Imperial College of Science, Technology and Medicine, London (United Kingdom); Cambra, J. [Escuela de Ingenierios, Bilbao (Spain); De Beer, V.H.J.; Van Veen, J.A.R. [Eindhoven University of Technology, Eindhoven (Netherlands); Fierro, J.L.G. [C.S.I.C., Madrid (Spain)

    1997-07-01

    The potential of Amorphous Silica Alumina (ASA) supported Pt and Pd catalysts for deep hydrodesulphurisation (HDS) of diesel fuels was investigated. It appeared that the ASA supported catalysts exhibit an excellent activity for the conversion of 4-Ethyl, 6-Methyl Dibenzothiophene (4-E,6-M DBT) under model conditions as compared to conventional HDS catalysts and {gamma}-Al{sub 2}O{sub 3} supported noble metal catalysts. Pt/ASA was also tested under practical conditions using a diesel fuel feed. The Pt/ASA catalyst showed a comparable activity to the NiW/{gamma}-Al{sub 2}O{sub 3} catalyst which was higher than that of the conventional CoMo/{gamma}-Al{sub 2}O{sub 3} catalyst. The main difference of the catalyst was the better hydroconversion of the 4,6 di-alkylated DBT's. The better performance of Pt/ASA in the testing under model conditions as compared to the diesel fuel HDS can be attributed to poisoning of part of the active phase by basic nitrogen compounds like quinoline. It is concluded that ASA supported noble metal catalysts have a promising potential for deep HDS processing. 5 refs.

  19. Metal-organic frameworks for adsorption and separation of noble gases

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Greathouse, Jeffery A.; Staiger, Chad

    2017-05-30

    A method including exposing a gas mixture comprising a noble gas to a metal organic framework (MOF), including an organic electron donor and an adsorbent bed operable to adsorb a noble gas from a mixture of gases, the adsorbent bed including a metal organic framework (MOF) including an organic electron donor.

  20. Role of noble metal nanoparticles in DNA base damage and catalysis: a radiation chemical investigation

    International Nuclear Information System (INIS)

    Sharma, Geeta K.

    2011-01-01

    In the emerging field of nanoscience and nanotechnology, tremendous focus has been made by researcher to explore the applications of nanomaterials for human welfare by converting the findings into technology. Some of the examples have been the use of nanoparticles in the field of opto-electronic, fuel cells, medicine and catalysis. These wide applications and significance lies in the fact that nanoparticles possess unique physical and chemical properties very different from their bulk precursors. Numerous methods for the synthesis of noble nanoparticles with tunable shape and size have been reported in literature. The goal of our group is to use different methods of synthesis of noble metal nanoparticles (Au, Ag, Pt and Pd) and test their protective/damaging role towards DNA base damage induced by ionizing radiation (Au and Ag) and to test the catalytic activity of nanoparticles (Pt and Pd) in certain known organic synthesis/electron transfer reactions. Using radiation chemical techniques such as pulse radiolysis and steady state radiolysis complemented by the product analysis using HPLC/LC-MS, a detailed mechanism for the formation of transient species, kinetics leading to the formation of stable end products is studied in the DNA base damage induced by ionizing radiation in presence and absence of Au and Ag nanoparticles. Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step towards gaining fundamental insight in catalysis. The catalytic activity of Pt and Pd nanoparticles in electron transfer and Suzuki coupling reactions has been determined. Investigations are currently underway to gain insight into the interaction between catalysts and reactants using time resolved spectroscopic measurements. These studies will be detailed during the presentation. (author)

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

    Science.gov (United States)

    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.

  2. Thermodynamic studies on molybdenum-noble metal alloys

    International Nuclear Information System (INIS)

    Yamawaki, M.; Kanno, M.

    1979-01-01

    Electromotive force cells have been used to determine the activities of molybdenum for Mo-Pd, Mo-Rh and Mo-Ru-Pd alloys over the temperature range 1200-1300K, and thermodynamic functions were derived from the results. Solid ZrO 2 -11 mol-% CaO was used as the electrolyte. In ternary Mo-Rud-Pd alloy the ratio Ru:Pd was fixed to 72,5:27.5 in atomic % in order to simulate the white metallic inclusions in irradiated (U, Pu)O 2 fuel. Activities of molybdenum showed negative deviations from Raoult's law in the composition range where the atomic fraction of molybdenum Nsub(Mo) being less than about 0.3, and then positive deviations in the intermediate Nsub(Mo) range. It was shown that the estimation of activities of molybdenum in the white metallic inclusions based on the regular solution approximation were generally fairly good, but might lead to error in the intermediate and higher Nsub(Mo) ranges. Standard Gibbs energy of formation of Mo-Rh intermetallic epsilon phase was shown to be negatively larger than those of some other Mo intermetallic phases, showing higher thermodynamic stability of this phase. (orig.) [de

  3. An effective hydrothermal route for the synthesis of multiple PDDA-protected noble-metal nanostructures.

    Science.gov (United States)

    Chen, Hongjun; Wang, Yuling; Dong, Shaojun

    2007-12-10

    In this article, we demonstrate an effective hydrothermal route for the synthesis of multiple PDDA-protected (PDDA = poly(diallyl dimethylammonium) chloride) noble-metal (including silver, platinum, palladium, and gold) nanostructures in the absence of any seeds and surfactants, in which PDDA, an ordinary and water-soluble polyelectrolyte, acts as both a reducing and a stabilizing agent. Under optimal experimental conditions, Ag nanocubes, Pt and Pd nanopolyhedrons, and Au nanoplates can be obtained, which were characterized by transmission electron microscopy , scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction. More importantly, the nanostructures synthesized show potential applications in surface-enhanced Raman scattering and electrocatalysis, in which Ag nanocubes and Pt nanopolyhedrons were chosen as the examples, respectively.

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

    Science.gov (United States)

    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

  5. Studies on PEM fuel cell noble metal catalyst dissolution

    DEFF Research Database (Denmark)

    Andersen, S. M.; Grahl-Madsen, L.; Skou, E. M.

    2011-01-01

    A combination of electrochemical, spectroscopic and gravimetric methods was carried out on Proton Exchange Membrane (PEM) fuel cell electrodes with the focus on platinum and ruthenium catalysts dissolution, and the membrane degradation. In cyclic voltammetry (CV) experiments, the noble metals were...... found to dissolve in 1 M sulfuric acid solution and the dissolution increased exponentially with the upper potential limit (UPL) between 0.6 and 1.6 vs. RHE. 2-20% of the Pt (depending on the catalyst type) was found to be dissolved during the experiments. Under the same conditions, 30-100% of the Ru...... (depending on the catalyst type) was found to be dissolved. The faster dissolution of ruthenium compared to platinum in the alloy type catalysts was also confirmed by X-ray diffraction measurements. The dissolution of the carbon supported catalyst was found one order of magnitude higher than the unsupported...

  6. Interaction between Nafion ionomer and noble metal catalyst for PEMFCs

    DEFF Research Database (Denmark)

    Andersen, Shuang Ma

    The implement of polymer impregnation in electrode structure (catalyst layer) decreasing the noble metal catalyst loading by a factor of ten , , is one of the essential mile stones in the evolution of Proton Exchange Membrane Fuel Cells’ development among the application of catalyst support...... and electrode deposition etc. In fuel cell reactions, both electrons and protons are involved. Impregnation of Nafion ionomer in catalyst layer effectively increases the proton-electron contact, enlarge the reaction zone, extend the reaction from the surface to the entire electrode. Therefore, the entire...... catalyst layer conducts both electrons and protons so that catalyst utilization in the layer is improved dramatically. The catalyst layer will in turn generate and sustain a higher current density. One of the generally adapted methods to impregnate Nafion into the catalyst layer is to mix the catalysts...

  7. High-pressure synthesis of noble metal hydrides.

    Science.gov (United States)

    Donnerer, Christian; Scheler, Thomas; Gregoryanz, Eugene

    2013-04-07

    The formation of hydride phases in the noble metals copper, silver, and gold was investigated by in situ x-ray diffraction at high hydrogen pressures. In the case of copper, a novel hexagonal hydride phase, Cu2H, was synthesised at pressures above 18.6 GPa. This compound exhibits an anti-CdI2-type structure, where hydrogen atoms occupy every second layer of octahedral interstitial sites. In contrast to chemically produced CuH, this phase does not show a change in compressibility compared to pure copper. Furthermore, repeated compression (after decomposition of Cu2H) led to the formation of cubic copper hydride at 12.5 GPa, a phenomenon attributed to an alteration of the microstructure during dehydrogenation. No hydrides of silver (up to 87 GPa) or gold (up to 113 GPa) were found at both room and high temperatures.

  8. Synthesis, characterization and photocatalytic activity of noble metal-modified TiO2 nanosheets with exposed {0 0 1} facets

    International Nuclear Information System (INIS)

    Diak, Magdalena; Grabowska, Ewelina; Zaleska, Adriana

    2015-01-01

    Graphical abstract: - Highlights: • TiO 2 nanosheets with exposed {0 0 1} facets were prepared by hydrothermal method. • Pd and Ag NPs-loaded enhanced the photocatalytic activity under visible irradiation. • Photodeposition is an effective method to obtain noble metal NPs on TiO 2 surface. - Abstract: Pt, Pd, Ag and Au nanoparticles were photodeposited on the {0 0 1} crystal facets of the TiO 2 anatase nanosheets. Morphological and surface characterization of the samples as well as photocatalytic activity were studied. The influence of metal precursor concentration used during photodeposition (0.05−0.5%) on size of formed metal nanoparticles together with UV and vis-mediated activity of Pt, Pd, Ag or Au−TiO 2 was investigated. Generally, samples obtained by photodeposition of noble metal nanoparticles using their 0.2% precursor solutions revealed highest activity in phenol degradation reaction under visible light (λ > 420 nm). The photoactivity of the as-prepared samples with respect to the modified metal species was ordered Ag≅Pd > Au > Pt. TEM analysis showed that photodeposited metal nanoparticles appeared only on {0 0 1} facets of TiO 2 . The average degradation rate of phenol in the presence of Pd and Ag−TiO 2 was 0.5 μmol dm −3 min −1 after 60 min of irradiation under visible light, and was five times higher than that of pure TiO 2 nanosheets

  9. On the methodology of radiochemical neutron activation analysis of noble metals

    International Nuclear Information System (INIS)

    Chai, C.F.; Ma, S.L.; Mao, X.Y.; Liao, K.N.; Liu, W.C.

    1986-01-01

    Two different radiochemical procedures were developed: chelate ion resin exchange and amine solvent extraction. Two kinds of new Chinese chelate resins (NANKAI-3926 and BEI-5) and a new long-chain primary amine N 1923 were compared with Srafion NMRR and the tertiary amine N 235 in absorption performance of noble metals, respectively. Influences of various experimental conditions, e.g. sample digestion, acidity, equilibrium time, as well as elution of noble metals, on analytical sensitivity and chemical yield were discussed. Combining with neutron activation, the radiochemical separation procedures developed were used to determine the noble metal contents in the geological samples from Permina/Triassic boundary in South China. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  11. The efficacy of noble metal alloy urinary catheters in reducing catheter-associated urinary tract infection

    Directory of Open Access Journals (Sweden)

    Alanood Ahmed Aljohi

    2016-01-01

    Results: A 90% relative risk reduction in the rate of CAUTI was observed with the noble metal alloy catheter compared to the standard catheter (10 vs. 1 cases, P = 0.006. When considering both catheter-associated asymptomatic bacteriuria and CAUTI, the relative risk reduction was 83% (12 vs. 2 cases, P = 0.005. In addition to CAUTI, the risk of acquiring secondary bacteremia was lower (100% for the patients using noble metal alloy catheters (3 cases in the standard group vs. 0 case in the noble metal alloy catheter group, P = 0.24. No adverse events related to any of the used catheters were recorded. Conclusion: Results from this study revealed that noble metal alloy catheters are safe to use and significantly reduce CAUTI rate in ICU patients after 3 days of use.

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

    NARCIS (Netherlands)

    Krystek, P.W.; Brandsma, S.H.; Leonards, P.E.G.; de Boer, J.

    2016-01-01

    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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  15. Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

    Science.gov (United States)

    Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

    2014-12-01

    Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Influence of noble metals on the performance of Co/SiO{sub 2} catalyst for 1-hexene hydroformylation

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, X.Q.; Tsubaki, N.; Sun, S.L.; Fujimoto, K. [Tsing Hua University, Beijing (China). Dept. of Chemistry, State Key Laboratory of C1 Chemistry of Technology

    2002-08-01

    Effect of small amount of Pt, Pd and Ru promoters on the characteristics and performance of Co/SiO{sub 2} catalyst, which was prepared from the mixture of cobalt nitrate and cobalt acetate, was investigated in the hydroformylation of 1-hexene. It was found that the addition of small amount of a noble metal to the supported cobalt catalyst led into great improvement of catalyst activity for hydroformylation of 1-hexene. The 1-hexene conversion as high as 89.7% and oxygenate products selectivity of 88.9% were obtained after reaction of 2 h over Pd promoted CO/SiO{sub 2} catalyst. The increasing of reduction degree, the minimizing of cobalt particle size and the enhancement of carbonyl and linear CO adsorption were responsible for the improved performance of the catalyst. 19 refs., 3 figs., 3 tabs.

  17. Noble-metal-based catalysts supported on zeolites and macro-mesoporous metal oxide supports for the total oxidation of volatile organic compounds.

    Science.gov (United States)

    Barakat, Tarek; Rooke, Joanna C; Tidahy, Haingomalala Lucette; Hosseini, Mahsa; Cousin, Renaud; Lamonier, Jean-François; Giraudon, Jean-Marc; De Weireld, Guy; Su, Bao-Lian; Siffert, Stéphane

    2011-10-17

    The use of porous materials to eliminate volatile organic compounds (VOCs) has proven very effective towards achieving sustainability and environmental protection goals. The activity of zeolites and macro-mesoporous metal-oxide supports in the total oxidation of VOCs has been investigated, with and without noble-metal deposition, to develop highly active catalyst systems where the formation of by-products was minimal. The first catalysts employed were zeolites, which offered a good activity in the oxidation of VOCs, but were rapidly deactivated by coke deposition. The effects of the acido-basicity and ionic exchange of these zeolites showed that a higher basicity was related to exchanged ions with lower electronegativities, resulting in better catalytic performances in the elimination of VOCs. Following on from this work, noble metals were deposited onto macro-mesoporous metal-oxide supports to form mono and bimetallic catalysts. These were then tested in the oxidation of toluene to study their catalytic performance and their deactivation process. PdAu/TiO(2) and PdAu/TiO(2) -ZrO(2) 80/20 catalysts demonstrated the best activity and life span in the oxidation of toluene and propene and offered the lowest temperatures for a 50 % conversion of VOCs and the lowest coke content after catalytic testing. Different characterization techniques were employed to explain the changes occurring in catalyst structure during the oxidation of toluene and propene. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Wire gauze and cordierite supported noble metal catalysts for passive autocatalytic recombiner

    International Nuclear Information System (INIS)

    Sanap, Kiran K.; Varma, S.; Waghmode, S.B.; Bharadwaj, S.R.

    2015-01-01

    Highlights: • Synthesis by electroless deposition method and chemical reduction route. • Particle size of 0.1–0.5 μm & 3.5–5 nm for Pt–Pd/Wg & Pt–Pd/Cord catalysts. • Active for H 2 and O 2 reaction with initial H 2 concentration of 1.5 to 7% in air. • Active in presence of different contaminants like CO 2 , CH 4 , CO & relative humidity. • Enhanced resistance of Pt–Pd/Cord catalyst towards the poisoning of CO. - Abstract: Hydrogen released in nuclear reactor containment under severe accident scenario poses a threat to containment and hence needs to be regulated by catalytic recombination. Mixed noble metal catalysts with platinum–palladium supported on stainless steel wire gauze and cordierite support have been developed for this purpose. The developed catalysts have been found to be highly efficient for removal of hydrogen concentration in the range of 1.5 to 7.0% v/v in air. Though both the catalysts exhibit similar kinetics for lower hydrogen concentration, cordierite supported catalysts exhibits better kinetic rate at higher hydrogen concentration. The performances of these catalysts in presence of various probable catalytic poison like carbon monoxide and catalytic inhibitors like moisture, carbon dioxide, and hydrocarbons provide data for use of these catalysts under the actual scenario. Compared to stainless steel wire gauze supported catalyst, the cordierite based catalyst are found to exhibit enhanced resistance towards carbon monoxide and limited temperature rise for safer application at higher hydrogen concentrations.

  19. Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media

    International Nuclear Information System (INIS)

    King, R.B.; Bhattacharyya, N.K.; Wiemers, K.D.

    1994-08-01

    Simulants for the Hanford Waste Vitrification Plant (HWVP) feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO 3 2- , NO 3 -, and NO 2 - were used as media to evaluate the stability of formic acid towards hydrogen evolution by the reaction HCO 2 H → H 2 + CO 2 catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Small scale experiments using 40-50 mL of feed simulant in closed glass reactors (250-550 mL total volume) at 80-100 degree C were used to study the effect of nitrite and nitrate ion on the catalytic activities of the noble metals for formic acid decomposition. Reactions were monitored using gas chromatography to analyze the CO 2 , H 2 , NO, and N 2 O in the gas phase as a function of time. Rhodium, which was introduced as soluble RhCl 3 ·3H 2 O, was found to be the most active catalyst for hydrogen generation from formic acid above ∼80 degree C in the presence of nitrite ion in accord with earlier observations. The inherent homogeneous nature of the nitrite-promoted Rh-catalyzed formic acid decomposition is suggested by the approximate pseudo first-order dependence of the hydrogen production rate on Rh concentration. Titration of the typical feed simulants containing carbonate and nitrite with formic acid in the presence of rhodium at the reaction temperature (∼90 degree C) indicates that the nitrite-promoted Rh-catalyzed decomposition of formic acid occurs only after formic acid has reacted with all of the carbonate and nitrite present to form CO 2 and NO/N 2 O, respectively. The catalytic activities of Ru and Pd towards hydrogen generation from formic acid are quite different than those of Rh in that they are inhibited rather than promoted by the presence of nitrite ion

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

    International Nuclear Information System (INIS)

    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 3 production. The noble metals catalyze H 2 and NH 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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  2. Measurement of the composition of noble-metal particles in high-burnup CANDU fuel by wavelength dispersive X-ray microanalysis

    International Nuclear Information System (INIS)

    Hocking, W.H.; Szostak, F.J.

    1999-09-01

    An investigation of the composition of the metallic inclusions in CANDU fuel, which contain Mo, Tc, Ru, Rh and Pd, has been conducted as a function of burnup by wavelength dispersive X-ray (WDX) microanalysis. Quantitative measurements were performed on micrometer sized particles embedded in thin sections of fuel using elemental standards and the ZAF method. Because the fission yields of the noble metals change with burnup, as a consequence of a shift from almost entirely 235 U fission to mainly 239 Pu fission, their inventories were calculated from the fuel power histories using the WIMS-Origin code for comparison with experiment. Contrary to expectations that the oxygen potential would be buffered by progressive Mo oxidation, little evidence was obtained for reduced incorporation of Mo in the noble-metal particles at high burnup. These surprising results are discussed with respect to the oxygen balance in irradiated CANDU fuels and the likely intrinsic and extrinsic sinks for excess oxygen. (author)

  3. Noble metal (NM) behavior during simulated HLLW vitrification in induction melter with cold crucible

    International Nuclear Information System (INIS)

    Demin, A.V.; Matyunin, Y.I.; Fedorova, M.I.

    1995-01-01

    The investigation of noble metal (Ru, Rh, Pd) properties in, glass melts are connected with their specific behaviors during HLLW vitrification. Ruthenium, rhodium and palladium volatilities and heterogeneous platinoid phases forming on melts are investigated in reasonable details conformably to Joule's heating ceramic melters. The vitrification conditions in melters with induction heating of melts are differ from the vitrification ones in ceramic melters on some numbers of parameters (the availability of significant temperature gradients and convection flows in melts, short time of molten mass updating in melter and probability of definite interaction between high-frequency field and melt inhomogeneities). The results of simulated HLLW solidification modelling of the vitrification process in induction melter with cold crucible to produce phosphate and boron-silicate materials are presented. The properties of received glasses and behavior of platinoids are shown to have analogies and distinctions in comparison with compounds, synthesized in ceramic melter. The structures of dispersed particles of NM heterogeneous phases forming in glass melts prepared in induction melter with cold crucible are identified. The results of investigations show, that the marked distinctions between two processes can influence (in definite degree) as on property of synthesized materials, as on behavior of platinoid during vitrifications

  4. Noble metal catalysts in the production of biofuels

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, A.

    2013-11-01

    The energy demand is increasing in the world together with the need to ensure energy security and the desire to decrease greenhouse gas emissions. While several renewable alternatives are available for the production of electricity, e.g. solar energy, wind power, and hydrogen, biomass is the only renewable source that can meet the demand for carbon-based liquid fuels and chemicals. The technology applied in the conversion of biomass depends on the type and complexity of the biomass, and the desired fuel. Hydrogen and hydrogen-rich mixtures (synthesis gas) are promising energy sources as they are more efficient and cleaner than existing fuels, especially when they are used in fuel cells. Hydrotreatment is a catalytic process that can be used in the conversion of biomass or biomass-derived liquids into fuels. In autothermal reforming (ATR), catalysts are used in the production of hydrogen-rich mixtures from conventional fuels or bio-fuels. The different nature of biomass and biomass-derived liquids and mineral oil makes the use of catalysts developed for the petroleum industry challenging. This requires the improvement of available catalysts and the development of new ones. To overcome the limitations of conventional hydrotreatment and ATR catalysts, zirconia-supported mono- and bimetallic rhodium, palladium, and platinum catalysts were developed and tested in the upgrading of model compounds for wood-based pyrolysis oil and in the production of hydrogen, using model compounds for gasoline and diesel. Catalysts were also tested in the ATR of ethanol. For comparative purposes commercial catalysts were tested and the results obtained with model compounds were compared with those obtained with real feedstocks (hydrotreatmet tests with wood-based pyrolysis oil and ATR tests with NExBTL renewable diesel). Noble metal catalysts were active and selective in the hydrotreatment of guaiacol used as the model compound for the lignin fraction of wood-based pyrolysis oil and wood

  5. Bond strength of resin cements to noble and base metal alloys with different surface treatments.

    Directory of Open Access Journals (Sweden)

    Farkhondeh Raeisosadat

    2014-10-01

    Full Text Available 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.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.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.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.

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

    Science.gov (United States)

    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. Copyright © 2015. Published by Elsevier B.V.

  7. Synthesis, characterization and photocatalytic activity of noble metal-modified TiO{sub 2} nanosheets with exposed {0 0 1} facets

    Energy Technology Data Exchange (ETDEWEB)

    Diak, Magdalena; Grabowska, Ewelina, E-mail: ewelina.grabowska@ug.edu.pl; Zaleska, Adriana

    2015-08-30

    Graphical abstract: - Highlights: • TiO{sub 2} nanosheets with exposed {0 0 1} facets were prepared by hydrothermal method. • Pd and Ag NPs-loaded enhanced the photocatalytic activity under visible irradiation. • Photodeposition is an effective method to obtain noble metal NPs on TiO{sub 2} surface. - Abstract: Pt, Pd, Ag and Au nanoparticles were photodeposited on the {0 0 1} crystal facets of the TiO{sub 2} anatase nanosheets. Morphological and surface characterization of the samples as well as photocatalytic activity were studied. The influence of metal precursor concentration used during photodeposition (0.05−0.5%) on size of formed metal nanoparticles together with UV and vis-mediated activity of Pt, Pd, Ag or Au−TiO{sub 2} was investigated. Generally, samples obtained by photodeposition of noble metal nanoparticles using their 0.2% precursor solutions revealed highest activity in phenol degradation reaction under visible light (λ > 420 nm). The photoactivity of the as-prepared samples with respect to the modified metal species was ordered Ag≅Pd > Au > Pt. TEM analysis showed that photodeposited metal nanoparticles appeared only on {0 0 1} facets of TiO{sub 2}. The average degradation rate of phenol in the presence of Pd and Ag−TiO{sub 2} was 0.5 μmol dm{sup −3} min{sup −1} after 60 min of irradiation under visible light, and was five times higher than that of pure TiO{sub 2} nanosheets.

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

    Science.gov (United States)

    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.

  9. Grains of Nonferrous and Noble Metals in Iron-Manganese Formations and Igneous Rocks of Submarine Elevations of the Sea of Japan

    Science.gov (United States)

    Kolesnik, O. N.; Astakhova, N. V.

    2018-01-01

    Iron-manganese formations and igneous rocks of submarine elevations in the Sea of Japan contain overlapping mineral phases (grains) with quite identical morphology, localization, and chemical composition. Most of the grains conform to oxides, intermetallic compounds, native elements, sulfides, and sulfates in terms of the set of nonferrous, noble, and certain other metals (Cu, Zn, Sn, Pb, Ni, Mo, Ag, Pd, and Pt). The main conclusion that postvolcanic hydrothermal fluids are the key sources of metals is based upon a comparison of the data of electron microprobe analysis of iron-manganese formations and igneous rocks dredged at the same submarine elevations in the Sea of Japan.

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

    Directory of Open Access Journals (Sweden)

    Rudolf Herrmann

    2014-12-01

    Full Text Available 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.

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

    Science.gov (United States)

    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.

  12. Polyetheretherketone Overlay Prosthesis over High Noble Ball Attachments to Overcome Base Metal Sensitivity: A Clinical Report.

    Science.gov (United States)

    Zoidis, Panagiotis

    2018-01-11

    A modified polyetheretherketone (PEEK) framework material in combination with heat-polymerized denture base acrylic resin was used for the fabrication of an overlay prosthesis for a patient sensitive to base metals. High noble metal was used for the fabrication of the post/coping/ball attachment assemblies to promote retention and stability. These protruding attachments into the acrylic resin could result in stress concentration; therefore, a framework is often used to strengthen the prosthesis. PEEK frameworks could be a treatment alternative to high noble or Ti frameworks since they combine good mechanical properties with biocompatibility, reduced cost, and common laboratory procedures. © 2018 by the American College of Prosthodontists.

  13. The preparation of primary standard solutions for each of the noble metals

    International Nuclear Information System (INIS)

    Mallett, R.C.; Wall, G.J.; Jones, E.A.; Royal, S.J.

    1977-01-01

    A revised method for the preparation of primary standard solutions for each of the noble metals is described. It is now recommended that standard noble-metal solutions should be made from the pure metals and not from salts as previously described. Metals should have a certified purity of 99,95 per cent or better, and the purity should be confirmed by analysis, the techniques of emission spectography or spark-source mass spectrography being used. After the metals have been dissolved, the solutions are made up to volume and the metal content of the standard solutions is checked. For most instrumental techniques for which the standards are intended, the check analysis should be within 0,3 per cent of the certified value

  14. Autoradiographic techniques to determine noble metal distribution in automotive catalyst substrates

    International Nuclear Information System (INIS)

    Lange, W.H.

    1976-01-01

    The distribution of noble metals in the ceramic substrates of automotive catalytic converter systems is important to the functional characteristics of the systems. A radiotracer technique involving microtomy of bead substrate samples and autoradiography using the resultant thin sections was developed to produce detailed images of the metal distributions. The method is particularly valuable to determine the distribution of one metal in the presence of another to aid in the development of more efficient systems

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

    International Nuclear Information System (INIS)

    Koopman, David C.:Eibling, Russel E

    2005-01-01

    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

  16. Non-noble metal based electro-catalyst compositions for proton exchange membrane based water electrolysis and methods of making

    Energy Technology Data Exchange (ETDEWEB)

    Kumta, Prashant N.; Kadakia, Karan Sandeep; Datta, Moni Kanchan; Velikokhatnyi, Oleg

    2017-02-07

    The invention provides electro-catalyst compositions for an anode electrode of a proton exchange membrane-based water electrolysis system. The compositions include a noble metal component selected from the group consisting of iridium oxide, ruthenium oxide, rhenium oxide and mixtures thereof, and a non-noble metal component selected from the group consisting of tantalum oxide, tin oxide, niobium oxide, titanium oxide, tungsten oxide, molybdenum oxide, yttrium oxide, scandium oxide, cooper oxide, zirconium oxide, nickel oxide and mixtures thereof. Further, the non-noble metal component can include a dopant. The dopant can be at least one element selected from Groups III, V, VI and VII of the Periodic Table. The compositions can be prepared using a surfactant approach or a sol gel approach. Further, the compositions are prepared using noble metal and non-noble metal precursors. Furthermore, a thin film containing the compositions can be deposited onto a substrate to form the anode electrode.

  17. The Behavior and Effects of the Noble Metals in the DWPF Melter System

    Energy Technology Data Exchange (ETDEWEB)

    Smith, M.E. [Westinghouse Savannah River Company, AIKEN, SC (United States); Bickford, D.F.

    1997-11-30

    Governments worldwide have committed to stabilization of high-level nuclear waste (HLW) by vitrification to a durable glass form for permanent disposal. All of these nuclear wastes contain the fission-product noble metals: ruthenium, rhodium, and palladium. SRS wastes also contain natural silver from iodine scrubbers. Closely associated with the noble metals are the fission products selenium and tellurium which are chemical analogs of sulfur and which combine with noble metals to influence their behavior and properties. Experience has shown that these melt insoluble metals and their compounds tend to settle to the floor of Joule-heated ceramic melters. In fact, almost all of the major research and production facilities have experienced some operational problem which can be associated with the presence of dense accumulations of these relatively conductive metals and/or their compounds. In most cases, these deposits have led to a loss of production capability, in some cases, to the point that melter operation could not continue. HLW nuclear waste vitrification facilities in the United States are the Department of Energy`s Defense Waste Processing Facility (DWPF) at the Savannah River Site, the planned Hanford Waste Vitrification Plant (HWVP) at the Hanford Site and the operating West Valley Demonstration Project (WVDP) at West Valley, NY. The Integrated DWPF Melter System (IDMS) is a vitrification test facility at the Savannah River Technology Center (SRTC). It was designed and constructed to provide an engineering-scale representation of the DWPF melter and its associated feed preparation and off-gas treatment systems. An extensive noble metals testing program was begun in 1990. The objectives of this task were to explore the effects of the noble metals on the DWPF melter feed preparation and waste vitrification processes. This report focuses on the vitrification portion of the test program.

  18. Ligand-Assisted Co-Assembly Approach toward Mesoporous Hybrid Catalysts of Transition-Metal Oxides and Noble Metals: Photochemical Water Splitting.

    Science.gov (United States)

    Liu, Ben; Kuo, Chung-Hao; Chen, Jiejie; Luo, Zhu; Thanneeru, Srinivas; Li, Weikun; Song, Wenqiao; Biswas, Sourav; Suib, Steven L; He, Jie

    2015-07-27

    A bottom-up synthetic approach was developed for the preparation of mesoporous transition-metal-oxide/noble-metal hybrid catalysts through ligand-assisted co-assembly of amphiphilic block-copolymer micelles and polymer-tethered noble-metal nanoparticles (NPs). The synthetic approach offers a general and straightforward method to precisely tune the sizes and loadings of noble-metal NPs in metal oxides. This system thus provides a solid platform to clearly understand the role of noble-metal NPs in photochemical water splitting. The presence of trace amounts of metal NPs (≈0.1 wt %) can enhance the photocatalytic activity for water splitting up to a factor of four. The findings can conceivably be applied to other semiconductors/noble-metal catalysts, which may stand out as a new methodology to build highly efficient solar energy conversion systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. First-principles calculations of the vacancy formation energy in transition and noble metals

    DEFF Research Database (Denmark)

    Korzhavyi, P.A.; Abrikosov, Igor A.; Johansson, Börje

    1999-01-01

    Abstract: The vacancy formation energy and the vacancy formation volume of the 3d, 4d, and 5d transition and noble metals have been calculated within the local-density approximation. The calculations employ the order-N locally self-consistent Green's-function method in conjunction with a supercel...

  20. Physical properties of some noble metal compounds from PAW-DFT ...

    African Journals Online (AJOL)

    The heats of formation, shear modulus, fracture toughness, density and melting points of compounds formed between some noble metals and aluminum, scandium, hafnium and zirconium were evaluated by the ab initio quantum mechanical projector augmented wave (PAW) calculation methods, using the Density ...

  1. Comparison Of Different Noble Metal Catalysts For The Low Temperature Catalytic Partial Oxidation Of Methane

    Energy Technology Data Exchange (ETDEWEB)

    Rabe, S.; Truong, T.-B.; Vogel, F.

    2005-03-01

    The generation of synthesis gas at low temperatures can contribute to a more economic production of clean transportation fuels (Fischer-Tropsch liquids) from natural gas. In this report, the performance of different noble metal catalysts in a low temperature catalytic partial oxidation process is presented. (author)

  2. On the calculation of lattice parameters of solid solutions on the basis of noble metals

    International Nuclear Information System (INIS)

    Barsukov, A.D.; Zhuravleva, N.S.; Ageeva, G.N.; Pedos, A.A.

    1996-01-01

    Lattice constants for noble metal solid solutions have been calculated taking into account atomic volumes, number of bonding electrons as well as chemical interaction between the components. Miscount is of the same order as the experimental error. 10 refs.; 2 tabs

  3. Letter Report on the Issue of Noble Metals in the DWPF Melter

    Energy Technology Data Exchange (ETDEWEB)

    Hutson, N.D.

    2001-09-05

    This report presents some historical data from the radioactive operation of the DWPF melter. Some of the data seem to indication that the melter is displaying symptoms that may be linked to accumulation of noble metal or other conductive material on the melter floor. The complex and often competing effects of waste composition, glass pool temperatures, and operating conditions must also be considered.

  4. Characterisation and radiolysis of modified lithium orthosilicate pebbles with noble metal impurities

    DEFF Research Database (Denmark)

    Tamulevičius, Sigitas; Zariņš, A.; Valtenbergs, O.

    2017-01-01

    of the noble metals on the radiolysis was evaluated after irradiation with accelerated electrons (E = 5 MeV), up to 12 MGy absorbed dose at 300–345 K in a dry argon atmosphere. Using electron spin resonance (ESR) spectroscopy, it was determined that the noble metals (up to 300 ppm) do not significantly......Modified lithium orthosilicate (Li4SiO4) pebbles with additions of titanium dioxide (TiO2) are suggested as an alternative tritium breeding ceramic for the European solid breeder test blanket module. The noble metals – platinum (Pt), gold (Au) and rhodium (Rh), can be introduced into the modified...... Li4SiO4 pebbles during the melt-based process, due to the corrosion of Pt-Rh and Pt-Au alloy crucible components. In this study, the surface microstructure, chemical and phase composition of the modified Li4SiO4 pebbles with different contents of the noble metals was analysed. The influence...

  5. 4,6-Dimethyl-dibenzothiophene conversion over Al{sub 2}O{sub 3}-TiO{sub 2}-supported noble metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Nunez, Sara [Departamento de Ingenieria de Procesos e Hidraulica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Vicentina, Iztapalapa, 09340, Mexico, D.F. (Mexico); Escobar, Jose, E-mail: jeaguila@imp.mx [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, 07730, Mexico, D.F. (Mexico); Vazquez, Armando; Reyes, Jose Antonio de los [Departamento de Ingenieria de Procesos e Hidraulica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Vicentina, Iztapalapa, 09340, Mexico, D.F. (Mexico); Hernandez-Barrera, Melissa [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, 07730, Mexico, D.F. (Mexico)

    2011-03-15

    Research highlights: {yields} Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-TiO{sub 2} (molar ratio Al/Ti = 2, AT2) mixed oxides were pore-filling impregnated to obtain Pd, Pt and Pd-Pt catalysts with {approx}1 wt% nominal metal loading. {yields} Reduced catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS). {yields} In Pd-containing materials, TiO{sub 2} incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts. {yields} Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide. {yields} Yield to different products over various catalysts seemed to be strongly influenced by metallic particles dispersion. - Abstract: Al{sub 2}O{sub 3} and Al{sub 2}O{sub 3}-TiO{sub 2} (molar ratio Al/Ti = 2, AT2) mixed oxides were synthesized using a low-temperature sol-gel method and were further pore-filling impregnated to obtain Pd and Pt catalysts with {approx}1 wt% nominal metal loading. Simultaneous impregnation was used to prepare bimetallic materials at Pd:Pt = 80:20. Solids characterization was carried out by N{sub 2}-physisorption, high-resolution transmission electron microscopy (HR-TEM and E-FTEM), X-ray diffraction, temperature-programmed reduction and CO-chemisorption. Reduced (350 deg. C, H{sub 2} flow) catalysts were tested in the 4,6-dimethyl-dibenzothiophene hydrodesulfurization (HDS) (in n-dodecane, at 300 deg. C and 5.5 MPa, batch reactor). In Pd-containing materials, TiO{sub 2} incorporation into the alumina support was favorable to the catalytic activity of noble metal catalysts, where bimetallic Pd-Pt with AT2 carrier had the highest organo-S compound conversion. Enhanced intrinsic activity (per exposed metallic site) was obtained in Pt-containing catalysts supported on the AT2 mixed oxide (as compared to alumina-supported ones). Yield to different products over various catalysts seemed to be strongly influenced by

  6. Synthesis, characterization and photocatalytic activity of noble metal-modified TiO2 nanosheets with exposed {0 0 1} facets

    Science.gov (United States)

    Diak, Magdalena; Grabowska, Ewelina; Zaleska, Adriana

    2015-08-01

    Pt, Pd, Ag and Au nanoparticles were photodeposited on the {0 0 1} crystal facets of the TiO2 anatase nanosheets. Morphological and surface characterization of the samples as well as photocatalytic activity were studied. The influence of metal precursor concentration used during photodeposition (0.05-0.5%) on size of formed metal nanoparticles together with UV and vis-mediated activity of Pt, Pd, Ag or Au-TiO2 was investigated. Generally, samples obtained by photodeposition of noble metal nanoparticles using their 0.2% precursor solutions revealed highest activity in phenol degradation reaction under visible light (λ > 420 nm). The photoactivity of the as-prepared samples with respect to the modified metal species was ordered Ag≅Pd > Au > Pt. TEM analysis showed that photodeposited metal nanoparticles appeared only on {0 0 1} facets of TiO2. The average degradation rate of phenol in the presence of Pd and Ag-TiO2 was 0.5 μmol dm-3 min-1 after 60 min of irradiation under visible light, and was five times higher than that of pure TiO2 nanosheets.

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

    Science.gov (United States)

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

    2017-12-01

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

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

    International Nuclear Information System (INIS)

    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

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

    Science.gov (United States)

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

    2014-11-01

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

  10. Observation of shell effects in nanowires for the noble metals copper, silver and gold

    OpenAIRE

    Mares, A. I.; van Ruitenbeek, J. M.

    2005-01-01

    We extend our previous shell effect observation in gold nanowires at room temperature under ultra high vacuum to the other two noble metals: silver and copper. Similar to gold, silver nanowires present two series of exceptionally stable diameters related to electronic and atomic shell filling. This observation is in concordance to what was previously found for alkali metal nanowires. Copper however presents only electronic shell filling. Remarkably we find that shell structure survives under ...

  11. Dispersion forces and small-angle neutron scattering from liquid noble metals

    International Nuclear Information System (INIS)

    March, N.H.

    1988-01-01

    Maggs and Ashcroft [Phys. Rev. letts., 59,113 (1987)] have re-opened the question of the analogy between the cohesion of a molecular crystal, in which dispersion forces play a major role, and that in a metal crystal with polarizable ion cores. It is pointed out that small-angle neutron scattering from liquid noble metals could be used to test their predictions. (author)

  12. Modeling impurity-assisted chain creation in noble-metal break junctions

    International Nuclear Information System (INIS)

    Di Napoli, S; Thiess, A; Blügel, S; Mokrousov, Y

    2012-01-01

    In this work we present the generalization of the model for chain formation in break junctions, introduced by Thiess et al (2008 Nano Lett. 8 2144), to zigzag transition-metal chains with s and p impurities. We apply this extended model to study the producibility trends for noble-metal chains with impurities, often present in break junction experiments, namely, Cu, Ag and Au chains with H, C, O and N adatoms. Providing the material-specific parameters for our model from systematic full-potential linearized augmented plane-wave first-principles calculations, we find that the presence of such impurities crucially affects the binding properties of the noble-metal chains. We reveal that both the impurity-induced bond strengthening and the formation of zigzag bonds can lead to a significantly enhanced probability for chain formation in break junctions. (paper)

  13. Stability and Activity of Non-Noble-Metal-Based Catalysts Toward the Hydrogen Evolution Reaction.

    Science.gov (United States)

    Ledendecker, Marc; Mondschein, Jared S; Kasian, Olga; Geiger, Simon; Göhl, Daniel; Schalenbach, Max; Zeradjanin, Aleksandar; Cherevko, Serhiy; Schaak, Raymond E; Mayrhofer, Karl

    2017-08-07

    A fundamental understanding of the behavior of non-noble based materials toward the hydrogen evolution reaction is crucial for the successful implementation into practical devices. Through the implementation of a highly sensitive inductively coupled plasma mass spectrometer coupled to a scanning flow cell, the activity and stability of non-noble electrocatalysts is presented. The studied catalysts comprise a range of compositions, including metal carbides (WC), sulfides (MoS 2 ), phosphides (Ni 5 P 4 , Co 2 P), and their base metals (W, Ni, Mo, Co); their activity, stability, and degradation behavior was elaborated and compared to the state-of-the-art catalyst platinum. The non-noble materials are stable at HER potentials but dissolve substantially when no current is flowing. Through pre- and post-characterization of the catalysts, explanations of their stability (thermodynamics and kinetics) are discussed, challenges for the application in real devices are analyzed, and strategies for circumventing dissolution are suggested. The precise correlation of metal dissolution with applied potential/current density allows for narrowing down suitable material choices as replacement for precious group metals as for example, platinum and opens up new ways in finding cost-efficient, active, and stable new-generation electrocatalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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 polyphenol 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.

  17. Analysis of noble metal on automotive exhaust catalysts by radioisotope-induce x-ray fluorescence

    International Nuclear Information System (INIS)

    Elgart, M.F.

    1976-01-01

    A technique was developed for the in-situ analysis of noble metals deposited on monolithic automotive exhaust catalysts. This technique is based on radioisotope-induced x-ray fluorescence, and provides a detailed picture of the distribution of palladium and platinum on catalyst samples. The experimental results for the cross section of a monolithic exhaust catalyst, analyzed in increments of 0.2 cm 3 , are compared with analyses for palladium and platinum obtained by instrumental neutron activation analysis

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

    Science.gov (United States)

    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.

  19. Noble Metal Catalysts Supported on Nanofibrous Polymeric Membranes for Environmental Applications

    Czech Academy of Sciences Publication Activity Database

    Soukup, Karel; Topka, Pavel; Hejtmánek, Vladimír; Petráš, D.; Valeš, V.; Šolcová, Olga

    2014-01-01

    Roč. 236, NOV 1 (2014), s. 3-11 ISSN 0920-5861 R&D Projects: GA ČR GPP106/11/P459; GA ČR GP13-24186P Institutional support: RVO:67985858 Keywords : electrospinning * noble metals * catalytic oxidation * volatile organic compoundas Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 3.893, year: 2014

  20. A facile and general preparation of high-performance noble-metal-based free-standing nanomembranes by a reagentless interfacial self-assembly strategy

    Science.gov (United States)

    Wu, Haoxi; He, Haili; Zhai, Yujuan; Li, Haijuan; Lai, Jianping; Jin, Yongdong

    2012-10-01

    As a simple and flexible 2D platform, the water-air interface is envisioned as an environmentally-friendly approach to prepare ultrathin free-standing nanomembranes (FNMs) of monolayered nanoparticles of interest via interfacial self-assembly. However, attempts so far have been rather rare due to the lack of efficient methods. In this article, we report on a facile and general strategy for fabrication of a family of noble metal-based FNMs by a simple and reagentless interfacial self-assembly tactics to prepare functional (plasmonic or catalytic) FNMs, such as Au, Ag, Pd, Pt-FNMs and their bimetallic hybrids, Ag/Au-FNMs and Pd/Pt-FNMs. The organic solvent-free process, varying somewhat from metal to metal only in precursors, reducing agents and dosage of reagents used, is found to be a general phenomenon and ligand-independent (irrespective of the monolayer quality of the resulting FNMs), allowing the growth of high-quality noble metal-based FNMs with well-defined nanoparticulate and monolayer morphology as large as several square centimeters. Heat treatment (boiling) is performed to accelerate the formation of FNMs within 15 min. More significantly, the as-prepared plasmonic Au-FNMs acting as a SERS substrate show a superior activity; whereas the resulting catalytic Pd-FNMs, except for their excellent ethanol electrooxidation performance, exhibit higher electrocatalytic activity for formic acid oxidation than commercial catalysts.As a simple and flexible 2D platform, the water-air interface is envisioned as an environmentally-friendly approach to prepare ultrathin free-standing nanomembranes (FNMs) of monolayered nanoparticles of interest via interfacial self-assembly. However, attempts so far have been rather rare due to the lack of efficient methods. In this article, we report on a facile and general strategy for fabrication of a family of noble metal-based FNMs by a simple and reagentless interfacial self-assembly tactics to prepare functional (plasmonic or

  1. Deposition and characterization of noble metal onto surfaces of 304l stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Contreras R, A.; Arganis J, C. R.; Aguilar T, J. A.; Medina A, A. L., E-mail: aida.contreras@inin.gob.m [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2010-10-15

    Noble metal chemical addition (NMCA) plus hydrogen water chemistry is an industry-wide accepted approach for potential intergranular stress corrosion cracking mitigation of BWR internals components. NMCA is a method of applying noble metal onto BWR internals surfaces using reactor water as the transport medium that causes the deposition of noble metal from the liquid onto surfaces. In this work different platinum concentration solutions were deposited onto pre-oxidized surfaces of 304l steel at 180 C during 48 hr in an autoclave. In order to simulate the zinc water conditions, deposits of Zn and Pt-Zn were also carried out. The solutions used to obtain the deposits were: sodium hexahydroxyplatinate (IV), zinc nitrate hydrate and zinc oxide. The deposits obtained were characterized by scanning electron microscopy and X-ray diffraction. Finally, the electrochemical corrosion potential of pre-oxidized samples with Pt deposit were obtained and compared with the electrochemical corrosion potential of only pre-oxidized samples. (Author)

  2. BWR containment vessel drywell head bolt de-tensioning during noble metal chemical application

    International Nuclear Information System (INIS)

    Herrera, M.; Mattson, R.

    2001-01-01

    Implementation of Noble Metal Chemical Application (NMCA) in a Boiling Water Reactor (BWR) requires injection of a noble metal compound while the reactor is idle at hot shutdown conditions. In order to minimize outage time, utilities are very pro-actively finding ways to reduce the number of critical path tasks. One of these tasks is to remove some containment vessel drywell head bolts during the NMCA idle time. This, thereby, saves the utilities outage time, or they can perform other tasks as desired. Using design basis conditions and state-of-the-art analytical techniques, detailed finite element stress analyses of the closure region are performed. Two acceptance criteria are evaluated. The first is that contained within Section III of the ASME Code for allowable stresses. The second relates to leak tightness, i.e., with bolt removal the joint must still remain leak tight. This paper describes the activities performed to justify bolt removal during the noble metal compound injection idle time at a particular plant. Drywell joint integrity criteria, design input, and assumptions are defined, and analytical results justifying bolt removal are presented. (author)

  3. Non-Noble Metal-based Carbon Composites in Hydrogen Evolution Reaction: Fundamentals to Applications.

    Science.gov (United States)

    Wang, Jing; Xu, Fan; Jin, Haiyan; Chen, Yiqing; Wang, Yong

    2017-04-01

    Hydrogen has been hailed as a clean and sustainable alternative to finite fossil fuels in many energy systems. Water splitting is an important method for hydrogen production in high purity and large quantities. To accelerate the hydrogen evolution reaction (HER) rate, it is highly necessary to develop high efficiency catalysts and to select a proper electrolyte. Herein, the performances of non-noble metal-based carbon composites under various pH values (acid, alkaline and neutral media) for HER in terms of catalyst synthesis, structure and molecular design are systematically discussed. A detailed analysis of the structure-activity-pH correlations in the HER process gives an insight on the origin of the pH-dependence for HER, and provide guidance for future HER mechanism studies on non-noble metal-based carbon composites. Furthermore, this Review gives a fresh impetus to rational design of high-performance noble-metal-free composites catalysts and guide researchers to employ the established electrocatalysts in proper water electrolysis technologies. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Noble-metal testing results for the West Valley vitrification system

    International Nuclear Information System (INIS)

    Bowan, B.W.; Jain, V.

    1989-01-01

    At the West Valley Demonstration Project (WVDP), the slurry-fed ceramic melter (SFCM) has been in test operation since December 1984 to vitrify simulated waste slurries. Over 4 yr, a moderate range of glass formulations, some containing RuO 2 , have been processed. Since these noble-metal oxides not only have a limited solubility in the melt, and are also electrically conductive, their accumulation in large amounts on the floor of the SFCM poses a potential electrical hazard to the joule-heated SFCM. The design of the WVDP melter cavity and electrode configuration is specifically intended to allow modest noble-metal accumulation without compromise to melter life or performance. In this study, an attempt has been made to estimate the amount of RuO 2 that has accumulated on the floor of the SFCM since initiation of the WVDP vitrification test program. The total amount of RuO 2 that has been processed in the SFCM to date is shown. This preliminary study indicates that the West Valley SFCM displays a good capability for sweeping insoluble noble metals through and for tolerating the remaining fraction on the floor without compromising melter life or performance over the course of the WVDP radioactive vitrification campaign

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

    Science.gov (United States)

    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 (magna or adsorption to particles occurred because only 1-5% of the exposed ENPs remained in the exposure medium. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Oxidation of ethoxylated fatty alcohols to alkylpolyglycol carboxylic acids using noble metals as catalysts

    Directory of Open Access Journals (Sweden)

    Sagredos, Angelos

    2009-09-01

    Full Text Available The conversion of ethoxylated fatty alcohols to the corresponding carboxylic acids through dehydrogenation/ oxidation using noble-metal catalysts has been studied. Ethoxylated primary aliphatic alcohols, ethoxylated random secondary aliphatic alcohols and ethoxylated alkylphenols have been converted to the corresponding acids in the presence of a base. The noble metal catalysts Palladium and Platinum were used without significant degradation of the ethoxyl chain in yields that exceeded 90%. On the other hand, the catalysts Rhodium and Ruthenium gave yields of about 80% and 60% respectively.La conversión de alcoholes grasos etoxilados a los correspondientes ácidos carboxílicos por deshidrogenación/ oxidación con metales nobles como catalizador ha sido estudiada. Alcoholes primarios alifáticos etoxilados, alcoholes alifáticos secundarios etoxilados al azar y alquilfenoles etoxilados han sido convertidos a los correspondientes ácidos en presencia de base. Los catalizadores paladio y platino fueron usados sin degradación significativa de las cadenas etoxiladas con un rendimiento que excedió del 90%. Por otra parte catalizadores de rodio y rutenio produjeron rendimientos del 80 y 60%, respectivamente.

  7. Graphene–Noble Metal Nano-Composites and Applications for Hydrogen Sensors

    Directory of Open Access Journals (Sweden)

    Sukumar Basu

    2017-10-01

    Full Text Available Graphene based nano-composites are relatively new materials with excellent mechanical, electrical, electronic and chemical properties for applications in the fields of electrical and electronic devices, mechanical appliances and chemical gadgets. For all these applications, the structural features associated with chemical bonding that involve other components at the interface need in-depth investigation. Metals, polymers, inorganic fibers and other components improve the properties of graphene when they form a kind of composite structure in the nano-dimensions. Intensive investigations have been carried out globally in this area of research and development. In this article, some salient features of graphene–noble metal interactions and composite formation which improve hydrogen gas sensing properties—like higher and fast response, quick recovery, cross sensitivity, repeatability and long term stability of the sensor devices—are presented. Mostly noble metals are effective for enhancing the sensing performance of the graphene–metal hybrid sensors, due to their superior catalytic activities. The experimental evidence for atomic bonding between metal nano-structures and graphene has been reported in the literature and it is theoretically verified by density functional theory (DFT. Multilayer graphene influences gas sensing performance via intercalation of metal and non-metal atoms through atomic bonding.

  8. Catalytic activity of noble metals promoting hydrogen uptake

    NARCIS (Netherlands)

    Borgschulte, A.; Westerwaal, R.J.; Rector, J.H.; Schreuders, H.; Dam, B.; Griessen, R.P.

    2006-01-01

    The engineering of pure and metal alloy catalysts for hydrogen absorption is needed to improve the kinetics of hydrogen-related devices. We introduce a new route to search for alloys that can yield superior catalytic behavior for hydrogen absorption, using an optical technique to measure the

  9. Development of casting investment preventing blackening of noble metal alloys. Part 4: effect of Mg(OH)2 and Ca(OH)2 as additives.

    Science.gov (United States)

    Nakai, Akira; Ogura, Hideo

    2007-11-01

    The objective of this study was to develop a casting investment that prevents the blackening of the cast surface of noble metal alloys. Experimental investments were prepared using a gypsum-bonded investment in which a hydroxide, namely Mg(OH)2 or Ca(OH)2, was added. An Ag-Pd-Cu-Au alloy was cast into the mold made of the prepared investment. The addition of both hydroxides showed a significant effect on the color of as-cast surfaces, which was improved with increase in additive content. When Mg(OH)2 or Ca(OH)2 was added at more than 4.0 mass% to the investment, it was useful in preventing the blackening of the as-cast surfaces of an Ag-Pd-Cu-Au alloy. As for differences in the effects between Mg(OH)2 and Ca(OH)2, they were not found.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ebbinghaus, Bartley B. [Univ. of California, Berkeley, CA (United States)

    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 CaF2, ThO2, YDT(0.85ThO2-0.15YO1.5), and LDT(0.85ThO2- 0.15LaO1.5) 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

    Energy Technology Data Exchange (ETDEWEB)

    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. Tuning the Morphology of Li2O2by Noble and 3d metals: A Planar Model Electrode Study for Li-O2Battery.

    Science.gov (United States)

    Yang, Yao; Liu, Wei; Wu, Nian; Wang, Xiaochen; Zhang, Tao; Chen, Linfeng; Zeng, Rui; Wang, Yingming; Lu, Juntao; Fu, Lei; Xiao, Li; Zhuang, Lin

    2017-06-14

    In this work, a planar model electrode method has been used to investigate the structure-activity relationship of multiple noble and 3d metal catalysts for the cathode reaction of Li-O 2 battery. The result shows that the battery performance (discharge/charge overpotential) strongly depends not only on the type of catalysts but also on the morphology of the discharge product (Li 2 O 2 ). Specifically, according to electrochemical characterization and scanning electron microscopy (SEM) observation, noble metals (Pd, Pt, Ru, Ir, and Au) show excellent battery performance (smaller discharge/charge overpotential), with wormlike Li 2 O 2 particles with size less than 200 nm on their surfaces. On the other hand, 3d metals (Fe, Co, Ni, and Mn) offered poor battery performance (larger discharge/charge overpotential), with much larger Li 2 O 2 particles (1 μm to a few microns) on their surfaces after discharging. Further research shows that a "volcano plot" is found by correlating the discharging/charging plateau voltage with the adsorption energy of LiO 2 on different metals. The metals with better battery performance and worm-like-shaped Li 2 O 2 are closer to the top of the "volcano", indicating adsorption energy of LiO 2 is one of the key characters for the catalyst to reach a good performance for the oxygen electrode of Li-O 2 battery, and it has a strong influence on the morphology of the discharge product on the electrode surface.

  13. Noble Metal Immersion Spectroscopy of Silica Alcogels and Aerogels

    Science.gov (United States)

    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. Composite nanomaterials of semiconductors and noble metals as plasmonic photocatalysts

    DEFF Research Database (Denmark)

    Engelbrekt, Christian; Law, Matt; Zhang, Jingdong

    Harnessing sunlight and storing the energy in chemical bonds is an important element in the transition towards green and sustainable technologies. Solar fuel production requires photocatalysts that (1) absorb large parts of the solar spectrum, (2) generate charges with significant lifetimes...... and appropriate energies, (3) catalyze relevant chemical transformations from abundant, low - energy starting materials, and (4) are stable under operating conditions. A new avenue within solar fuels involve plasmonic metal nanoparticles (PNPs). These materials have tunable optical properties, exciting catalytic...

  15. The secondary electron yield of noble metal surfaces

    Science.gov (United States)

    Gonzalez, L. A.; Angelucci, M.; Larciprete, R.; Cimino, R.

    2017-11-01

    Secondary electron yield (SEY) curves in the 0-1000 eV range were measured on polycrystalline Ag, Au and Cu samples. The metals were examined as introduced in the ultra-high vacuum chamber and after having been cleaned by Ar+ ion sputtering. The comparison between the curves measured on the clean samples and in the presence of contaminants, due to the permanence in atmosphere, confirmed that the SEY behavior is strongly influenced by the chemical state of the metal surface. We show that when using very slow primary electrons the sample work function can be determined with high accuracy from the SEY curves. Moreover we prove that SEY is highly sensitive to the presence of adsorbates even at submonolayer coverage. Results showing the effect of small quantities of CO adsorbed on copper are presented. Our findings demonstrate that SEY, besides being an indispensable mean to qualify technical materials in many technological fields, can be also used as a flexible and advantageous diagnostics to probe surfaces and interfaces.

  16. The secondary electron yield of noble metal surfaces

    Directory of Open Access Journals (Sweden)

    L. A. Gonzalez

    2017-11-01

    Full Text Available Secondary electron yield (SEY curves in the 0-1000 eV range were measured on polycrystalline Ag, Au and Cu samples. The metals were examined as introduced in the ultra-high vacuum chamber and after having been cleaned by Ar+ ion sputtering. The comparison between the curves measured on the clean samples and in the presence of contaminants, due to the permanence in atmosphere, confirmed that the SEY behavior is strongly influenced by the chemical state of the metal surface. We show that when using very slow primary electrons the sample work function can be determined with high accuracy from the SEY curves. Moreover we prove that SEY is highly sensitive to the presence of adsorbates even at submonolayer coverage. Results showing the effect of small quantities of CO adsorbed on copper are presented. Our findings demonstrate that SEY, besides being an indispensable mean to qualify technical materials in many technological fields, can be also used as a flexible and advantageous diagnostics to probe surfaces and interfaces.

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Air- and Water-Resistant Noble Metal Coated Ferromagnetic Cobalt Nanorods

    Energy Technology Data Exchange (ETDEWEB)

    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; Tendeloo, Gustaaf Van; 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 tore 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.

  19. Air- and Water-Resistant Noble Metal Coated Ferromagnetic Cobalt Nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Lentijo-Mozo, Sergio [Laboratoire de Physique et Chimie des Nano-objets (LPCNO), Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, 31077 Toulouse, France; Tan, Reasmey P. [Laboratoire de Physique et Chimie des Nano-objets (LPCNO), Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, 31077 Toulouse, France; Garcia-Marcelot, Cécile [Laboratoire de Physique et Chimie des Nano-objets (LPCNO), Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, 31077 Toulouse, France; Centre d’Elaboration de Matériaux et d’Etudes Structurales (CEMES-CNRS), 29 rue Jeanne Marvig, B.P. 94347, 31055 Toulouse, France; Altantzis, Thomas [Electron Microscopy for Materials Research (EMAT), University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium; Fazzini, Pier-Francesco [Laboratoire de Physique et Chimie des Nano-objets (LPCNO), Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, 31077 Toulouse, France; Hungria, Teresa [Laboratoire de Physique et Chimie des Nano-objets (LPCNO), Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, 31077 Toulouse, France; Cormary, Benoit [Laboratoire de Physique et Chimie des Nano-objets (LPCNO), Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, 31077 Toulouse, France; Gallagher, James R. [Chemical Science and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Argonne, Illinois 60439, United States; Miller, Jeffrey T. [Chemical Science and Engineering Division, Argonne National Laboratory, 9700 S Cass Avenue, Argonne, Illinois 60439, United States; Martinez, Herve [IPREM-ECP CNRS UMR 5254, Université de Pau, Hélioparc Pau Pyrénées, 2 av. Pierre Angot, 64053 Pau Cedex 9, France; Schrittwieser, Stefan [Molecular Diagnostics, AIT Austrian Institute of Technology, Vienna, Donau City Strasse 1, 1220 Vienna, Austria; Schotter, Joerg [Molecular Diagnostics, AIT Austrian Institute of Technology, Vienna, Donau City Strasse 1, 1220 Vienna, Austria; Respaud, Marc [Laboratoire de Physique et Chimie des Nano-objets (LPCNO), Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, 31077 Toulouse, France; Bals, Sara [Electron Microscopy for Materials Research (EMAT), University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium; Tendeloo, Gustaaf Van [Electron Microscopy for Materials Research (EMAT), University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium; Gatel, Christophe [Centre d’Elaboration de Matériaux et d’Etudes Structurales (CEMES-CNRS), 29 rue Jeanne Marvig, B.P. 94347, 31055 Toulouse, France; Soulantica, Katerina [Laboratoire de Physique et Chimie des Nano-objets (LPCNO), Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, 31077 Toulouse, France

    2015-02-25

    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.

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

    International Nuclear Information System (INIS)

    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

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

    Science.gov (United States)

    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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Optical and structural properties of noble-metal nanoparticles; Optische und strukturelle Eigenschaften von Edelmetallnanopartikeln

    Energy Technology Data Exchange (ETDEWEB)

    Dahmen, C.

    2006-06-23

    Noble-metal nanoparticles exhibit rich optical behavior, such as resonant light scattering and absorption and non-linear signal enhancement. This makes them attractive for a multitude of physical, chemical, and biophysical applications. For instance, recent biomedical experiments demonstrate the suitability of noble-metal nanoparticles for selective photothermal apoptosis by heat transport by laser irradiation. The applications of nanoparticles largely exploit that plasmons, i. e. collective oscillations of the conduction electrons, can be optically excited in these nanoparticles. In optical spectroscopy, these are seen as pronounced resonances. In the first part of this work, model calculations are employed to elucidate how radiation damping in noble-metal nanoparticles, i. e. the transformation of plasmons into photons, depends on particle size, particle shape, and on electromagnetic coupling between individual particles. Exact electrodynamic calculations are carried out for individual spheroidal particles and for pairs of spherical particles. These calculations for spheroidal particles demonstrate for the first time that radiative plasmon decay is determined by both the particle volume and the particle shape. Model calculations for pairs of large spherical particles reveal that the electromagnetic fields radiated by the particles mediate electromagnetic coupling at interparticle distances in the micrometer range. This coupling can lead to immense modulations of the plasmonic linewidth. The question whether this coupling is sufficiently strong to mediate extended, propagating, plasmon modes in nanoparticle arrays is addressed next. Detailed analysis reveals that this is not the case; instead, for the particle spacings regarded here, a non-resonant, purely diffractive coupling is observed, which is identified by steplike signatures in reflection spectra of the particle arrays. In the second part of this work, structural and optical properties of noble-metal

  3. Efficient recovery of gold and other noble metals from electronic and other scraps

    Energy Technology Data Exchange (ETDEWEB)

    Baba, Hidetoshi

    1987-01-01

    Pure gold is extracted from crude gold by the solvent extraction method in the recovery and refining process for Noble metals recovered from electronic and other scraps. This solvent extraction method is advantageous in that it facilitates rapid processing, thereby reducing the interest burden of gold staying too long in the unit. Therefore, the method is also used in the refining of platinum and palladium. Technological innovation has created more complex and diversified types of scraps, and efforts are being made to accommodate ourselves to such a trend.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Nanostructure analysis of friction welded Pd-Ni-P/Pd-Cu-Ni-P metallic glass interface

    International Nuclear Information System (INIS)

    Ohkubo, T.; Shoji, S.; Kawamura, Y.; Hono, K.

    2005-01-01

    Friction welded Pd 40 Ni 40 P 20 /Pd 40 Cu 30 Ni 10 P 20 metallic glass interface has been characterized by energy filtering transmission electron microscopy. The interface is fully amorphous with a gradual compositional change of Cu and Ni in the range of 30 nm. By annealing above T g , the interdiffusion of Cu and Ni progressed in the supercooled liquid region, and the crystallization occurred from the Pd 40 Ni 40 P 20 glass

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Simulated optical properties of noble metallic nanopolyhedra with different shapes and structures

    Science.gov (United States)

    Zhang, An-Qi; Qian, Dong-Jin; Chen, Meng

    2013-11-01

    The optical properties of nanostructured architectures are highly sensitive to their compositions, structures, dimensions, geometries and embedding mediums. Nanopolyhedra, including homogeneous metal nanoparticles and core-shell structures, have unique optical properties. In the beginning of this study, Discrete Dipole Approximation (DDA) method has been introduced. Then the simulated extinction spectra of single-component metal nanoparticles and Au@Ag polyhedra were calculated using both Mie and DDA methods. The influence of morphology and components on the optical response is discussed and well-supported by previously published experimental results. It is observed that the Localized Surface Plasmon Resonance peaks are mainly decided by sharp vertexes and symmetry of noble metallic polyhedra, as well as the structure of the Au@Ag core-shell nanoparticles.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-06

    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.

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

    KAUST Repository

    Li, Zhenzhen

    2015-06-12

    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.

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

    Science.gov (United States)

    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.

  12. Tailoring the supercapacitive performances of noble metal oxides, porous carbons and their composites

    Directory of Open Access Journals (Sweden)

    Panić Vladimir V.

    2013-01-01

    Full Text Available Porous electrochemical supercapacitive materials, as an important type of new-generation energy storage devices, require a detailed analysis and knowledge of their capacitive performances upon different charging/discharging regimes. The investigation of the responses to dynamic perturbations of typical representatives, noble metal oxides, carbonaceous materials and RuO2-impregnated carbon blacks, by electrochemical impedance spectroscopy (EIS is presented. This presentation follows a brief description of supercapacitive behavior and origin of pseudocapacitive response of noble metal oxides. For all investigated materials, the electrical charging/discharging equivalent of the EIS response was found to obey the transmission line model envisaged as so-called „resistor/capacitor (RC ladder“. The ladder features are correlated to material physicochemical properties, its composition and the composition of the electrolyte. Fitting of the EIS data of different supercapacitive materials to appropriate RC ladders enables the in-depth profiling of the capacitance and pore resistance of their porous thin-layers and finally the complete revelation of capacitive energy storage issues. [Projekat Ministarstva nauke Republike Srbije, br. 172060

  13. Automated ion-exchange system for the radiochemical separation of the noble metals

    International Nuclear Information System (INIS)

    Parry, S.J.

    1980-01-01

    Ion-exchange separation is particularly suitable for mechanisation and automated ion exchange has been applied to the activation analysis of biological and environmental samples. In this work a system has been designed for experimental studies, which can be adapted for different modes of operation. The equipment is based on a large-volume sampler for the automatic presentation of 500 ml of liquid to a sampling probe. The sample is delivered to the ion-exchange column by means of a peristaltic pump. The purpose of this work was to automate a procedure for separating the noble metals from irradiated geological samples, for neutron-activation analysis. The process of digesting the rock sample is carried out manually in 30 min and is not suited to unattended operation. The volume of the resulting liquid sample may be 100 ml and so the manual separation step may take as long as 1.25 h per sample. The reason for automating this part of the procedure is to reduce the separation time for a group of five samples and consequently to improve the sensitivity of the analysis for radionuclides with short half-lives. This paper describes the automatic ion-exchange system and the ways in which it can be used. The mode of operation for the separation of the noble metals is given in detail. The reproducibility of the system has been assessed by repeated measurements on a standard reference matte. (author)

  14. Examining changes in cellular communication in neuroendocrine cells after noble metal nanoparticle exposure.

    Science.gov (United States)

    Love, Sara A; Liu, Zhen; Haynes, Christy L

    2012-07-07

    As nanoparticles enjoy increasingly widespread use in commercial applications, the potential for unintentional exposure has become much more likely during any given day. Researchers in the field of nanotoxicity are working to determine the physicochemical nanoparticle properties that lead to toxicity in an effort to establish safe design rules. This work explores the effects of noble metal nanoparticle exposure in murine chromaffin cells, focusing on examining the effects of size and surface functionality (coating) in silver and gold, respectively. Carbon-fibre microelectrode amperometry was utilized to examine the effect of exposure on exocytosis function, at the single cell level, and provided new insights into the compromised functions of cells. Silver nanoparticles of varied size, between 15 and 60 nm diameter, were exposed to cells and found to alter the release kinetics of exocytosis for those cells exposed to the smallest examined size. Effects of gold were examined after modification with two commonly used 'bio-friendly' polymers, either heparin or poly (ethylene glycol), and gold nanoparticles were found to induce altered cellular adhesion or the number of chemical messenger molecules released, respectively. These results support the body of work suggesting that noble metal nanoparticles perturb exocytosis, typically altering the number of molecules and kinetics of release, and supports a direct disruption of the vesicle matrix by the nanoparticle. Overall, it is clear that various nanoparticle physicochemical properties, including size and surface coating, do modulate changes in cellular communication via exocytosis.

  15. In Situ Studies of Surface Mobility on Noble Metal Model Catalysts Using STM and XPS at Ambient Pressure

    Energy Technology Data Exchange (ETDEWEB)

    Butcher, Derek Robert [Univ. of California, Berkeley, CA (United States)

    2010-06-01

    are present on the Pt(100) hex reconstructed phase, but not the (100)-(1x1) surface. The increase in ethylene pressure caused the adsorbate interactions to dominate the crystal morphology and imposed a surface layer structure that matched the ethylidyne binding geometry. The STM results also showed that the surface was reversibly deformed during imaging due to increases in Pt mobility at high pressure. The size dependence on the activity and surface chemistry of Rh nanoparticles was studied using AP-XPS. The activity was found to increase with particle size. The XPS spectra show that in reaction conditions the particle surface has an oxide layer which is chemically distinct from the surface structure formed by heating in oxygen alone. This surface oxide which is stabilized in the catalytically active CO oxidation conditions was found to be more prevalent on the smaller nanoparticles. The reaction-induced surface segregation behavior of bimetallic noble metal nanoparticles was observed with APXPS. Monodisperse 15 nm RhPd and PdPt nanoparticles were synthesized with well controlled Rh/Pd and Pd/Pt compositions. In-situ XPS studies showed that at 300 C in the presence of an oxidizing environment (100 mTorr NO or O2) the surface concentration of the more easily oxidized element (Rh in RhPd and Pd in PdPt) was increased. Switching the gas environment to more reducing conditions (100 mTorr NO and 100 mTorr CO) caused the surface enrichment of the element with the lowest surface energy in its metallic state. Using in-situ characterization, the redox chemistry and the surface composition of bimetallic nanoparticle samples were monitored in reactive conditions. The particle surfaces were shown to reversibly restructure in response to the gas environment at high temperature. The oxidation behavior of the Pt(110) surface was studied using surface sensitive in-situ characterization by APXPS and STM. In the presence of 500 mTorr O2 and temperatures between 25

  16. Shear bond strength of a ceromer to noble and base metal alloys

    Directory of Open Access Journals (Sweden)

    Dorriz H.

    2006-08-01

    Full Text Available Background and Aim: The improvement of the physical and chemical properties of resins as well as great advances achieved in the field of chemical bonding of resin to metal has changed the trend of restorative treatments. Today the second generation of laboratory resins have an important role in the restoration of teeth. The clinical bond strength should be reliable in order to gain successful results. In this study the shear bond strength (SBS between targis (a ceromer and two alloys (noble and base metal was studied and the effect of thermocycling on the bond investigated. Materials and Methods: In this experimental study, alloys samples were prepared according to the manufacturer. After sandblasting of bonding surfaces with 50µ AI2o3 Targis was bonded to the alloy using Targis I link. All of the samples were placed in 37°C water for a period of 24 hours. Then half of the samples were subjected to 1000 cycles of thermocycling at temperatures of 5°C and 55°C. Planear shear test was used to test the bond strength in the Instron machine with the speed rate of 0.5mm/min. Data were analyzed by SPSS software. Two-way analysis of variance was used to compare the bond strength among the groups. T test was used to compare the alloys. The influence of thermocycling and alloy type on bond strength was studied using Mann Whitney test. P<0.05 was considered as the limit of significance. Result: The studied alloys did not differ significantly, when the samples were not thermocycled (P=0.136 but after thermocycling a significant difference was observed in SBS of resin to different alloys (P=000.1. Thermal stress and alloy type had significant interaction, with regard to shear bond strength (P=0.003. There was a significant difference in SBS before and after thermocycling in noble alloys (P=0.009, but this was not true in base metals (P=0.29. Maximum SBS (19.09 Mpa belonged to Degubond 4, before thermocycling. Minimum SBS (8.21 Mpa was seen in Degubond 4

  17. TiO2structures doped with noble metals and/or graphene oxide to improve the photocatalytic degradation of dichloroacetic acid.

    Science.gov (United States)

    Ribao, Paula; Rivero, Maria J; Ortiz, Inmaculada

    2017-05-01

    Noble metals have been used to improve the photocatalytic activity of TiO 2 . Noble metal nanoparticles prevent charge recombination, facilitating electron transport due to the equilibration of the Fermi levels. Furthermore, noble metal nanoparticles show an absorption band in the visible region due to a high localized surface plasmon resonance (LSPR) effect, which contributes to additional electron movements. Moreover, systems based on graphene, titanium dioxide, and noble metals have been used, considering that graphene sheets can carry charges, thereby reducing electron-hole recombination, and can be used as substrates of atomic thickness. In this work, TiO 2 -based nanocomposites were prepared by blending TiO 2 with noble metals (Pt and Ag) and/or graphene oxide (GO). The nanocomposites were mainly characterized via transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transformed infrared (FTIR), Raman spectroscopy, and photocurrent analysis. Here, the photocatalytic performance of the composites was analyzed via oxidizing dichloroacetic acid (DCA) model solutions. The influence of the noble metal load on the composite and the ability of the graphene sheets to improve the photocatalytic activity were studied, and the composites doped with different noble metals were compared. The results indicated that the platinum structures show the best photocatalytic degradation, and, although the presence of graphene oxide in the composites is supposed to enhance their photocatalytic performance, graphene oxide does not always improve the photocatalytic process. Graphical abstract It is a schematic diagram. Where NM is Noble Metal and LSPR means Localized Surface Plasmon Resonance.

  18. Synthesis, fabrication, and spectroscopy of nano-scale photonic noble metal materials

    Science.gov (United States)

    Egusa, Shunji

    Nanometer is an interesting scale for physicists, chemists, and materials scientists, in a sense that it lies between the macroscopic and the atomic scales. In this regime, materials exhibit distinct physical and chemical properties that are clearly different from those of atoms or macroscopic bulk. This thesis is concerned about both physics and chemistry of noble metal nano-structures. Novel chemical syntheses and physical fabrications of various noble metal nano-structures, and the development of spectroscopic techniques for nano-structures are presented. Scanning microscopy/spectroscopy techniques inherently perturbs the true optical responses of the nano-structures. However, by using scanning tunneling microscope (STM) tip as the nanometer-confined excitation source of surface plasmons in the samples, and subsequently collecting the signals in the Fourier space, it is shown that the tip-perturbed part of the signals can be deconvoluted. As a result, the collected signal in this approach is the pure response of the sample. Coherent light is employed to study the optical response of nano-structures, in order to avoid complication from tip-perturbation as discussed above. White-light super-continuum excites the nano-structure, the monolayer of Au nanoparticles self-assembled on silicon nitride membrane substrates. The coherent excitation reveals asymmetric surface plasmon resonance in the nano-structures. One of the most important issues in nano-scale science is to gain control over the shape, size, and assembly of nanoparticles. A novel method is developed to chemically synthesize ligand-passivated atomic noble metal clusters in solution phase. The method, named thermal decomposition method, enables facile yet robust synthesis of fluorescent atomic clusters. Thus synthesized atomic clusters are very stable, and show behaviors of quantum dots. A novel and versatile approach for creation of nanoparticle arrays is developed. This method is different from the

  19. A noble metal-free proton-exchange membrane fuel cell based on bio-inspired molecular catalysts.

    Science.gov (United States)

    Tran, P D; Morozan, A; Archambault, S; Heidkamp, J; Chenevier, P; Dau, H; Fontecave, M; Martinent, A; Jousselme, B; Artero, V

    2015-03-01

    Hydrogen is a promising energy vector for storing renewable energies: obtained from water-splitting, in electrolysers or photoelectrochemical cells, it can be turned back to electricity on demand in fuel cells (FCs). Proton exchange membrane (PEM) devices with low internal resistance, high compactness and stability are an attractive technology optimized over decades, affording fast start-up times and low operating temperatures. However, they rely on the powerful catalytic properties of noble metals such as platinum, while lower cost, more abundant materials would be needed for economic viability. Replacing these noble metals at both electrodes has long proven to be a difficult task, so far incompatible with PEM technologies. Here we take advantage of newly developed bio-inspired molecular H 2 oxidation catalysts and noble metal-free O 2 -reducing materials, to fabricate a noble metal-free PEMFC, with an 0.74 V open circuit voltage and a 23 μW cm -2 output power under technologically relevant conditions. X-ray absorption spectroscopy measurements confirm that the catalysts are stable and retain their structure during turnover.

  20. Substrate-Based Noble-Metal Nanomaterials: Shape Engineering and Applications

    Science.gov (United States)

    Hajfathalian, Maryam

    Nanostructures have potential for use in state-of-the-art applications such as sensing, imaging, therapeutics, drug delivery, and electronics. The ability to fabricate and engineer these nanoscale materials is essential for the continued development of such devices. Because the morphological features of nanomaterials play a key role in determining chemical and physical properties, there is great interest in developing and improving methods capable of controlling their size, shape, and composition. While noble nanoparticles have opened the door to promising applications in fields such as imaging, cancer targeting, photothermal treatment, drug delivery, catalysis and sensing, the synthetic processes required to form these nanoparticles on surfaces are not well-developed. Herein is a detailed account on efforts for adapting established solution-based seed-mediated synthetic protocols to structure in a substrate-based platform. These syntheses start by (i) defining heteroepitaxially oriented nanostructured seeds at site-specific locations using lithographic or directed-assembly techniques, and then (ii) transforming the seeds using either a solution or vapor phase processing route to activate kinetically- or thermodynamically-driven growth modes, to arrive at nanocrystals with complex and useful geometries. The first series of investigations highlight synthesis-routes based on heterogeneous nucleation, where templates serve as nucleation sites for metal atoms arriving in the vapor phase. In the first research direction, the vapor-phase heterogeneous nucleation of Ag on Au was carried out at high temperatures, where the Ag vapor was sourced from a sublimating foil onto adjacent Au templates. This process transformed both the composition and morphology of the initial Au Wulff-shaped nanocrystals to a homogeneous AuAg nanoprism. In the second case, the vapor-phase heterogeneous nucleation of Cu atoms on Au nanocrystal templates was investigated by placing a Cu foil next

  1. Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

    KAUST Repository

    Al-ShaikhAli, Anaam H.

    2016-11-30

    Liquid organic chemical hydride is a promising candidate for hydrogen storage and transport. Methylcyclohexane (MCH) to toluene (TOL) cycle has been considered as one of the feasible hydrogen carrier systems, but selective dehydrogenation of MCH to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based catalysts. Mono-metallic Ni based catalyst is a well-known dehydrogenation catalyst, but the major drawback with Ni is its hydrogenolysis activity to cleave C-C bonds, which leads to inferior selectivity towards dehydrogenation of MCH to TOL. This study elucidate addition of the second metal to Ni based catalyst to improve the TOL selectivity. Herein, ubiquitous bi-metallic nanoparticles catalysts were investigated including (Ni–M, M: Ag, Zn, Sn or In) based catalysts. Among the catalysts investigated, the high TOL selectivity (> 99%) at low conversions was achieved effectively using the supported NiZn catalyst under flow of excess H2. In this work, a combined study of experimental and computational approaches was conducted to determine the main role of Zn over Ni based catalyst in promoting the TOL selectivity. A kinetic study using mono- and bimetallic Ni based catalysts was conducted to elucidate reaction mechanism and site requirement for MCH dehydrogenation reaction. The impact of different reaction conditions (feed compositions, temperature, space velocity and stability) and catalyst properties were evaluated. This study elucidates a distinctive mechanism of MCH dehydrogenation to TOL reaction over the Ni-based catalysts. Distinctive from Pt catalyst, a nearly positive half order with respect to H2 pressure was obtained for mono- and bi-metallic Ni based catalysts. This kinetic data was consistent with rate determining step as (somewhat paradoxically) hydrogenation

  2. Matrix Sputtering Method: A Novel Physical Approach for Photoluminescent Noble Metal Nanoclusters.

    Science.gov (United States)

    Ishida, Yohei; Corpuz, Ryan D; Yonezawa, Tetsu

    2017-12-19

    Noble metal nanoclusters are believed to be the transition between single metal atoms, which show distinct optical properties, and metal nanoparticles, which show characteristic plasmon absorbance. The interesting properties of these materials emerge when the particle size is well below 2 nm, such as photoluminescence, which has potential application particularly in biomedical fields. These photoluminescent ultrasmall nanoclusters are typically produced by chemical reduction, which limits their practical application because of the inherent toxicity of the reagents used in this method. Thus, alternative strategies are sought, particularly in terms of physical approaches, which are known as "greener alternatives," to produce high-purity materials at high yields. Thus, a new approach using the sputtering technique was developed. This method was initially used to produce thin films using solid substrates; now it can be applied even with liquid substrates such as ionic liquids or polyethylene glycol as long as these liquids have a low vapor pressure. This revolutionary development has opened up new areas of research, particularly for the synthesis of colloidal nanoparticles with dimensions below 10 nm. We are among the first to apply the sputtering technique to the physical synthesis of photoluminescent noble metal nanoclusters. Although typical sputtering systems have relied on the effect of surface composition and viscosity of the liquid matrix on controlling particle diameters, which only resulted in diameters ca. 3-10 nm, that were all plasmonic, our new approach introduced thiol molecules as stabilizers inspired from chemical methods. In the chemical syntheses of metal nanoparticles, controlling the concentration ratio between metal ions and stabilizing reagents is a possible means of systematic size control. However, it was not clear whether this would be applicable in a sputtering system. Our latest results showed that we were able to generically produce a

  3. Binding of noble metal clusters with rare gas atoms: theoretical investigation.

    Science.gov (United States)

    Jamshidi, Zahra; Far, Maryam Fakhraei; Maghari, Ali

    2012-12-27

    Binding of noble metal clusters (M(n), M = Cu, Ag, and Au; n = 2-4) with rare gas atoms (Rg = Kr, Xe, and Rn) has been investigated at the density functional (CAM-B3LYP) and ab initio (MP2) levels of theory. The calculation shows significant affinity of neutral metal clusters for interaction with rare gas atoms. The binding energies indicate that gold clusters have the highest and silver clusters have the lowest affinity for interaction with rare gas atoms, and for the same metal clusters, there is a continuous increase in E(b) from Kr to Rn. The M-Rg bonding mechanism have been interpreted by means of the quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO), and energy decomposition analysis (EDA). According to these theories, the M-Rg bonds are found to be partially electrostatic and partially covalent. EDA results identify that these bonds have less than 40% covalent character and more than 60% electrostatic, and also NBO calculations predict the amount of charge transfer from the lone pair of rare gas to σ* and n*orbitals of metal clusters.

  4. Hot-Electron Intraband Luminescence from Single Hot Spots in Noble-Metal Nanoparticle Films

    Science.gov (United States)

    Haug, Tobias; Klemm, Philippe; Bange, Sebastian; Lupton, John M.

    2015-08-01

    Disordered noble-metal nanoparticle films exhibit highly localized and stable nonlinear light emission from subdiffraction regions upon illumination by near-infrared femtosecond pulses. Such hot spot emission spans a continuum in the visible and near-infrared spectral range. Strong plasmonic enhancement of light-matter interaction and the resulting complexity of experimental observations have prevented the development of a universal understanding of the origin of light emission. Here, we study the dependence of emission spectra on excitation irradiance and provide the most direct evidence yet that the continuum emission observed from both silver and gold nanoparticle aggregate surfaces is caused by recombination of hot electrons within the conduction band. The electron gas in the emitting particles, which is effectively decoupled from the lattice temperature for the duration of emission, reaches temperatures of several thousand Kelvin and acts as a subdiffraction incandescent light source on subpicosecond time scales.

  5. Synthesis of noble metal nanoparticles and their superstructures; Darstellung von Edelmetallnanopartikeln und deren Ueberstrukturen

    Energy Technology Data Exchange (ETDEWEB)

    Bigall, Nadja-Carola

    2009-08-18

    A modified synthesis procedure for citrate-stabilized gold nanoparticles in aqueous solution is transferred under application of equal concentrations to the systems silver, platinum, and palladium. The nanoparticles are analyzed by means of absorption spectroscopy and electron microscopy. Ordered superstructures of the noble-metal nanoparticles can be synthesized by infiltration of templates of block-copolymer films with aqueous nanoparticle solution. In dependence on the pre-treatment of the polymer films either two-dimensional periodical arrangements with a periodicity of less than 30 nm or fingerprint-like arrangements with a groove distance in the same order of magnitude. By removal of the polymer one- respectively two-dimensional arrangements of platinum nanowires respectively nanoparticles on a silicon waver arise.

  6. Atomic structure of nanoscale quasicrystal-forming Zr-noble metal binary metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Saida, J., E-mail: jsaida@cir.tohoku.ac.jp [Center for Interdisciplinary Research, Tohoku University, Aramaki Aoba, Aoba-ku, Sendai 980-8578 (Japan); Itoh, K. [Graduate School of Education, Okayama University, Tsushimanaka, Kita-ku, Okayama 700-8530 (Japan); Sanada, T. [Research Department, Nissan ARC Ltd., Natsushima, Yokosuka 237-0061 (Japan); Sato, S. [Institute for Materials Research, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577 (Japan); Imafuku, M. [Faculty of Engineering, Tokyo City University, Setagaya-ku, Tokyo 158-8557 (Japan); Ohnuma, M. [National Institute of Materials Science (NIMS), Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Inoue, A. [WPI-AIMR, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577 (Japan)

    2011-06-15

    Research highlights: > Zr{sub 70}Pd{sub 30} and Zr{sub 80}Pt{sub 20} are the quasicrystal (QC)-forming glassy alloys. > The QC phase precipitates by a cooperative motion of atoms or clusters. > Relatively perfect icosahedrons frequently exist around Zr in Zr{sub 70}Pd{sub 30}, however, distorted icosahedral-like clusters are formed around Zr and Pt in Zr{sub 80}Pt{sub 20}. > The QC phase formation originates from a different mechanism in the two alloys. - Abstract: We report the results of the local structural evaluation and mechanism of QC formation in the Zr{sub 70}Pd{sub 30} and Zr{sub 80}Pt{sub 20} glassy alloys. Voronoi analysis indicates the difference of local environment between two alloys. The perfect icosahedron frequently exists around Zr atom and major polyhedra have prism-like structure around Pd in Zr{sub 70}Pd{sub 30}. In contrast, icosahedral-like distorted polyhedra formation is favorable around Pt as well as Zr in Zr{sub 80}Pt{sub 20}. It is therefore, concluded that the quasicrystallization originates from the medium-range order based on the Zr-centered perfect icosahedron and the Pd-centered prism-like ones remain during the QC phase formation in Zr{sub 70}Pd{sub 30}. Icosahedral-like local structure around Zr and Pt might contribute together to the nucleation of QC phase in Zr{sub 80}Pt{sub 20}. This feature with a different mechanism of QC formation in the two alloys may correlate to the difference of solute concentration and the structure of stable crystalline phase after the decomposition of QC phase.

  7. Conversion of ion-exchange resins, catalysts and sludges to glass with optional noble metal recovery using the GMODS process

    International Nuclear Information System (INIS)

    Forsberg, C.W.; Beahm, E.C.

    1996-01-01

    Chemical processing and cleanup of waste streams (air and water) typically result in products, clean air, clean water, and concentrated hazardous residues (ion exchange resins, catalysts, sludges, etc.). Typically, these streams contain significant quantities of complex organics. For disposal, it is desirable to destroy the organics and immobilize any heavy metals or radioactive components into stable waste forms. If there are noble metals in the residues, it is desirable to recover these for reuse. The Glass Material Oxidation and Dissolution System (GMODS) is a new process that directly converts radioactive and hazardous chemical wastes to borosilicate glass. GMODS oxidizes organics with the residue converted to glass; converts metals, ceramics, and amorphous solids to glass; converts halides (eg chlorides) to borosilicate glass and a secondary sodium halide stream; and recovers noble metals. GMODS has been demonstrated on a small laboratory scale (hundreds of grams), and the equipment needed for larger masses has been identified

  8. Multiple deuterium occupancy of vacancies in Pd and related metals

    DEFF Research Database (Denmark)

    Nordlander, P.; Nørskov, Jens Kehlet; Besenbacher, F.

    1989-01-01

    The binding energies of up to six deuterium atoms into monovacancies of Pd, Ni, Fe, Cu, Nb, and Mo have been calculated using the effective-medium theory. For all metals it is found that at least six D atoms can be accommodated in the vacancy. Of the systems studied the deuterium-deuterium intera......The binding energies of up to six deuterium atoms into monovacancies of Pd, Ni, Fe, Cu, Nb, and Mo have been calculated using the effective-medium theory. For all metals it is found that at least six D atoms can be accommodated in the vacancy. Of the systems studied the deuterium......-deuterium interaction is found to be least repulsive for Pd. This multiple occupancy of the vacancy defect can have potentially significant implications for the recently proposed fusion of D atoms in Pd....

  9. The determination, by x-ray-fluorescence spectrometry, of noble and base metals in matte-leach residues

    International Nuclear Information System (INIS)

    Austen, C.E.

    1977-01-01

    An accurate and precise method is described for the determination of noble and base metals in matte-leach residues. Preparation of the samples essentially involves fusion with sodium peroxide in a zirconium crucible and leaching with hydrochloric and nitric acids. Matrix correction and calibration are achieved by use of the single-standard calibration method with reference solutions prepared from pure metals or from compounds of the element to be determined

  10. Update on the use of dissolved oxygen addition to monitor the effectiveness of noble metal applications in external manifolds

    International Nuclear Information System (INIS)

    Electrochemical corrosion potential (ECP) measurements in a Mitigation Monitoring System (MMS) ECP manifold have historically been a primary indicator of the effectiveness of an On-Line NobleChem™ (OLNC) application, with the MMS ECP intended to measure the catalytic effect of noble metal deposited on the ECP manifold surface. In some plants ECP measurements made on untreated surfaces prior to an OLNC application were significantly lower than what would be expected for stainless steel under reactor bulk chemistry conditions. This is due to the consumption and depletion of bulk liquid dissolved oxygen (DO) in the lines supplying reactor water to these external ECP measurement locations. This phenomenon degrades the ability to use these external manifolds to confirm noble metal deposition. Previous papers have described how the injection of an oxygen-rich stream to the MMS supply stream (DO Addition) can be used to re-establish the capability of external ECP measurements to monitor the catalytic behavior of platinum deposited during an OLNC injection. This paper will provide an update of how this method is being successfully used in operating BWRs to monitor OLNC injections. The paper will outline the overall approach used to characterize the catalytic behavior of external ECP manifolds before and after the noble metal application and present plant data collected during DO Additions performed under various conditions. (author)

  11. Interactions of noble metal nanoparticles with their environment; Wechselwirkungen von Edelmetallnanopartikeln mit ihrer Umgebung

    Energy Technology Data Exchange (ETDEWEB)

    Reismann, Maximilian

    2009-12-08

    Upon irradiating noble metal nanoparticles with light, unique optical phenomena can occur, such as resonantly enhanced light-scattering and light-absorption, or a tremendous enhancement of the exciting optical field close to the surface of the nanoparticles. These phenomena rely on the excitations of collective oscillations of the conduction electrons within a nanoparticle. The optical properties of a nanoparticle are determined by the resonance frequency of these so-called plasmon oscillations. This resonance frequency and the light-scattering spectrum of a nanoparticle depend (among other effects) on the dielectric environment of the particle. Due to this effect, noble metal nanoparticles can be applied for local optical sensing of chemical substances. The large light-absorption properties of a nanoparticle also enable the usage of light-irradiation to deposit heat in the nanoparticle in a selective and highly localized manner. Therefore, a local temperature increase can be induced in the nanoparticle and its immediate environment. This temperature increase could be used to trigger chemical or biological reactions, or it could be used for a selective hyperthermia of biological material. These and further possible applications rely on the detection or the systematic excitation of interactions between the noble metal nanoparticle and its environment. These interactions are the central subject of this thesis. Particular attention is paid to photothermal interactions. An interesting question is to what extend a nanoparticle-supported, photothermally-induced temperature rise can be applied to trigger a biomolecular reaction in a spatially confined volume. By carefully adjusting the photothermal treatment, one aims at affecting the molecules without damaging their chemical functionality. The photothermal interaction is addressed in two projects: First, networks built up by gold nanoparticles are investigated. In these networks, double-stranded DNA-molecules are used to

  12. N-acyl thioureas - selective ligands for complexing of heavy metals and noble metals

    International Nuclear Information System (INIS)

    Schuster, M.

    1992-01-01

    Acyl thioureas are complexing agents for heavy metals that are easily produced and very stable. Their favourable toxicological data make them particularly suitable for industrial applications, e.g. detoxification of metallic process solutions or solvent extraction of metals. (orig.) [de

  13. Titanium-Niobium Oxides as Non-Noble Metal Cathodes for Polymer Electrolyte Fuel Cells

    Directory of Open Access Journals (Sweden)

    Akimitsu Ishihara

    2015-07-01

    Full Text Available In order to develop noble-metal- and carbon-free cathodes, titanium-niobium oxides were prepared as active materials for oxide-based cathodes and the factors affecting the oxygen reduction reaction (ORR activity were evaluated. The high concentration sol-gel method was employed to prepare the precursor. Heat treatment in Ar containing 4% H2 at 700–900 °C was effective for conferring ORR activity to the oxide. Notably, the onset potential for the ORR of the catalyst prepared at 700 °C was approximately 1.0 V vs. RHE, resulting in high quality active sites for the ORR. X-ray (diffraction and photoelectron spectroscopic analyses and ionization potential measurements suggested that localized electronic energy levels were produced via heat treatment under reductive atmosphere. Adsorption of oxygen molecules on the oxide may be governed by the localized electronic energy levels produced by the valence changes induced by substitutional metal ions and/or oxygen vacancies.

  14. Noble metal, oxide and chalcogenide-based nanomaterials from scalable phototrophic culture systems.

    Science.gov (United States)

    Dahoumane, Si Amar; Wujcik, Evan K; Jeffryes, Clayton

    2016-12-01

    Phototrophic cell or tissue cultures can produce nanostructured noble metals, oxides and chalcogenides at ambient temperatures and pressures in an aqueous environment and without the need for potentially toxic solvents or the generation of dangerous waste products. These "green" synthesized nanobiomaterials can be used to fabricate biosensors and bio-reporting tools, theranostic vehicles, medical imaging agents, as well as tissue engineering scaffolds and biomaterials. While successful at the lab and experimental scales, significant barriers still inhibit the development of higher capacity processes. While scalability issues in traditional algal bioprocess engineering are well known, such as the controlled delivery of photons and gas-exchange, the large-scale algal synthesis of nanomaterials introduces additional parameters to be understood, i.e., nanoparticle (NP) formation kinetics and mechanisms, biological transport of metal cations and the effect of environmental conditions on the final form of the NPs. Only after a clear understanding of the kinetics and mechanisms can the strain selection, photobioreactor type, medium pH and ionic strength, mean light intensity and other relevant parameters be specified for an optimal bioprocess. To this end, this mini-review will examine the current best practices and understanding of these phenomena to establish a path forward for this technology. Copyright © 2016 Elsevier Inc. All rights reserved.

  15. Activation of noble metals on metal-carbide surfaces: novel catalysts for CO oxidation, desulfurization and hydrogenation reactions.

    Science.gov (United States)

    Rodriguez, José A; Illas, Francesc

    2012-01-14

    This perspective article focuses on the physical and chemical properties of highly active catalysts for CO oxidation, desulfurization and hydrogenation reactions generated by depositing noble metals on metal-carbide surfaces. To rationalize structure-reactivity relationships for these novel catalysts, well-defined systems are required. High-resolution photoemission, scanning tunneling microscopy (STM) and first-principles periodic density-functional (DF) calculations have been used to study the interaction of metals of Groups 9, 10 and 11 with MC(001) (M = Ti, Zr, V, Mo) surfaces. DF calculations give adsorption energies that range from 2 eV (Cu, Ag, Au) to 6 eV (Co, Rh, Ir). STM images show that Au, Cu, Ni and Pt grow on the carbide substrates forming two-dimensional islands at very low coverage, and three-dimensional islands at medium and large coverages. In many systems, the results of DF calculations point to the preferential formation of admetal-C bonds with significant electronic perturbations in the admetal. TiC(001) and ZrC(001) transfer some electron density to the admetals facilitating bonding of the adatom with electron-acceptor molecules (CO, O(2), C(2)H(4), SO(2), thiophene, etc.). For example, the Cu/TiC(001) and Au/TiC(001) systems are able to cleave both S-O bonds of SO(2) at a temperature as low as 150 K, displaying a reactivity much larger than that of TiC(001) or extended surfaces of bulk copper and gold. At temperatures below 200 K, Au/TiC is able to dissociate O(2) and perform the 2CO + O(2)→ 2CO(2) reaction. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(001) or Au(111), a Au/TiC(001) surface displays an activity for the hydrodesulfurization of thiophene higher than that of conventional Ni/MoS(x) catalysts. In general, the Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces. Thus, metal carbides are excellent supports for enhancing the chemical

  16. Noble metals determination in ancient jewels with portable ED-XRF system

    International Nuclear Information System (INIS)

    Parreira, Paulo S.; Galvao, Tiago D.; Appoloni, Carlos R.

    2009-01-01

    A handmade system of Energy Dispersive X-Ray Fluorescence (ED-XRF) was used to perform the analysis of some jewels of the XIX century, as napkin holder, tobacco case, cigarette case, pen, pendant shrines, bracelets and a crucifix from the collection of the Museu Historico Nacional do Rio de Janeiro (MHN), Brazil. It was possible to verify the presence of Cu, Au and Ag as macro elements of the alloys, besides Hg as contaminant for one silver piece. Some gold and silver coins with well-known concentrations of gold and silver were also analysed, as reference material, to check out the methodology. To determine the concentrations of the metals, a methodology based on the equation of the fundamental parameters was used. For the jewels with silver aspect, it was possible to determine in average 90.4% of Ag for the napkin holder and 46.6% of Ag for one the bracelets, this last one presented also a high concentration of copper. For the jewels with golden aspect, it was possible to determine, in average, 88.6% to 98.9% for the Au content . For one special piece it was observed 62.5% of Au and 37.5% of Cu. For the coins, the obtained values showed a deviation of 0.4 and 7.6 percent for the average concentration of noble metals Ag and Au, respectively. The portable X-ray system showed to be a powerful tool in the investigation of metallic alloys with high concentration of major elements, allowing in situ measurements.(author)

  17. Low-pressure hydrogenation of carbon dioxide catalyzed by an iron pincer complex exhibiting noble metal activity.

    Science.gov (United States)

    Langer, Robert; Diskin-Posner, Yael; Leitus, Gregory; Shimon, Linda J W; Ben-David, Yehoshoa; Milstein, David

    2011-10-10

    A highly active iron catalyst for the hydrogenation of carbon dioxide and bicarbonates works under remarkably low pressures and achieves activities similar to some of the best noble metal catalysts. A mechanism is proposed involving the direct attack of an iron trans-dihydride on carbon dioxide, followed by ligand exchange and dihydrogen coordination. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Catalytic activity of polypyrrole nanotubes decorated with noble-metal nanoparticles and their conversion to carbonized analogues

    Czech Academy of Sciences Publication Activity Database

    Sapurina, Irina; Stejskal, Jaroslav; Šeděnková, Ivana; Trchová, Miroslava; Kovářová, Jana; Hromádková, Jiřina; Kopecká, J.; Cieslar, M.; Abu El-Nasr, A.; Ayad, M. M.

    2016-01-01

    Roč. 214, April (2016), s. 14-22 ISSN 0379-6779 R&D Projects: GA ČR(CZ) GA13-00270S; GA MŠk(CZ) LH14199; GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : conducting polymer * polypyrrole nanotubes * noble metals Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.435, year: 2016

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

    Energy Technology Data Exchange (ETDEWEB)

    Rijpstra, Kim; Van Yperen-De Deyne, Andy [Center for Molecular Modeling (CMM), Ghent University, Technologiepark 903, 9052 Ghent (Belgium); Maugeri, Emilio Andrea; Neuhausen, Jörg [Laboratory for Radiochemistry, Paul Scherrer Institute (PSI), 5232 Villigen (Switzerland); Waroquier, Michel; Van Speybroeck, Veronique [Center for Molecular Modeling (CMM), Ghent University, Technologiepark 903, 9052 Ghent (Belgium); Cottenier, Stefaan, E-mail: stefaan.cottenier@ugent.be [Center for Molecular Modeling (CMM), Ghent University, Technologiepark 903, 9052 Ghent (Belgium); Department of Materials Science and Engineering, Ghent University, Technologiepark 903, 9052 Ghent (Belgium)

    2016-04-15

    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 {sup 210}Po. 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 Po{sub 2}, PoBi and PoPb on this gold filter.

  20. Non-enzymatic electrochemical immunoassay using noble metal nanoparticles: a review

    International Nuclear Information System (INIS)

    Tang, Juan; Tang, Dianping

    2015-01-01

    Electrochemical immunodetection has attracted considerable attention due to its high sensitivity, low cost and simplicity. Large efforts have recently made in order to design ultrasensitive assays. Noble metal nanoparticles (NM-NPs) offer advantages such as high conductivity and large surface-to-volume ratio. NM-NPs therefore are excellent candidates for developing electrochemical platforms for immunodetection and as signal tags. The use of biofunctionalized NM-NPs often results in amplified recognition via stronger loading of signal tags, and also in enhanced signal. This review (with 87 references) gives an overview on the current state in the use of NM-NPs in Non-enzymatic electrochemical immunosensing. We discuss the application of NM-NPs as electrode matrices and as electroactive labels (either as a carrier or as electrocatalytic labels), and compare the materials (mainly nanoparticles of gold, platinum, or of bimetallic materials) in terms of performance (for example by increasing sensitivity via label amplification or via high densities of capture molecules). A conclusion covers current challenges and gives an outlook. Rather than being exhaustive, the review focuses on representative examples that illustrate novel concepts and promising applications. NM-NPs based immunosensing opens a series of concepts for basic research and offers new tools for determination of trace amounts of protein-related analytes in environment and clinical applications. (author)

  1. Structural Stability and Performance of Noble Metal-Free SnO2-Based Gas Sensors

    Directory of Open Access Journals (Sweden)

    Antonio Tricoli

    2012-05-01

    Full Text Available The structural stability of pure SnO2 nanoparticles and highly sensitive SnO2-SiO2 nanocomposites (0–15 SiO2 wt% has been investigated for conditions relevant to their utilization as chemoresistive gas sensors. Thermal stabilization by SiO2 co-synthesis has been investigated at up to 600 °C determining regimes of crystal size stability as a function of SiO2-content. For operation up to 400 °C, thermally stable crystal sizes of ca. 24 and 11 nm were identified for SnO2 nanoparticles and 1.4 wt% SnO2-SiO2 nanocomposites, respectively. The effect of crystal growth during operation (TO = 320 °C on the sensor response to ethanol has been reported, revealing possible long-term destabilization mechanisms. In particular, crystal growth and sintering-neck formation were discussed with respect to their potential to change the sensor response and calibration. Furthermore, the effect of SiO2 cosynthesis on the cross-sensitivity to humidity of these noble metal-free SnO2-based gas sensors was assessed.

  2. An Amorphous Noble-Metal-Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions.

    Science.gov (United States)

    Lv, Chade; Yan, Chunshuang; Chen, Gang; Ding, Yu; Sun, Jingxue; Zhou, Yansong; Yu, Guihua

    2018-02-23

    N 2 fixation by the electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is regarded as a potential approach to achieve NH 3 production, which still heavily relies on the Haber-Bosch process at the cost of huge energy and massive production of CO 2 . A noble-metal-free Bi 4 V 2 O 11 /CeO 2 hybrid with an amorphous phase (BVC-A) is used as the cathode for electrocatalytic NRR. The amorphous Bi 4 V 2 O 11 contains significant defects, which play a role as active sites. The CeO 2 not only serves as a trigger to induce the amorphous structure, but also establishes band alignment with Bi 4 V 2 O 11 for rapid interfacial charge transfer. Remarkably, BVC-A shows outstanding electrocatalytic NRR performance with high average yield (NH 3 : 23.21 μg h -1  mg -1 cat. , Faradaic efficiency: 10.16 %) under ambient conditions, which is superior to the Bi 4 V 2 O 11 /CeO 2 hybrid with crystalline phase (BVC-C) counterpart. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  5. Characterization of the electrochemical behavior of coating by steel welding 308l and in presence of noble metals deposits; Caracterizacion del comportamiento electroquimico de recubrimiento por soldadura de acero 308L y en presencia de depositos de metales nobles

    Energy Technology Data Exchange (ETDEWEB)

    Piedras, P.; Arganis J, C. R., E-mail: pedro.piedras@hotmail.es [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2014-10-15

    In this work the oxide deposits and noble metals deposit were characterized (Ag and Pt) on a coating of stainless steel 308l that were deposited by the shield metal arc welding (SMAW) on steel A36 by means of scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. The extrapolation of Tafel technique was also used to obtain the corrosion potential (Ec) for the pre-rusty steel and for the samples with deposits of Pt and Ag under conditions of hydrogen water chemistry (HWC), demonstrating that this parameter diminishes with the presence of this deposits. (Author)

  6. Cross-laboratory experimental study of non-noble-metal electrocatalysts for the oxygen reduction reaction.

    Science.gov (United States)

    Jaouen, Frédéric; Herranz, Juan; Lefèvre, Michel; Dodelet, Jean-Pol; Kramm, Ulrike I; Herrmann, Iris; Bogdanoff, Peter; Maruyama, Jun; Nagaoka, Toru; Garsuch, Arnd; Dahn, Jeff R; Olson, Tim; Pylypenko, Svitlana; Atanassov, Plamen; Ustinov, Eugene A

    2009-08-01

    Nine non-noble-metal catalysts (NNMCs) from five different laboratories were investigated for the catalysis of O(2) electroreduction in an acidic medium. The catalyst precursors were synthesized by wet impregnation, planetary ball milling, a foaming-agent technique, or a templating method. All catalyst precursors were subjected to one or more heat treatments at 700-1050 degrees C in an inert or reactive atmosphere. These catalysts underwent an identical set of electrochemical characterizations, including rotating-disk-electrode and polymer-electrolyte membrane fuel cell (PEMFC) tests and voltammetry under N(2). Ex situ characterization was comprised of X-ray photoelectron spectroscopy, neutron activation analysis, scanning electron microscopy, and N(2) adsorption and its analysis with an advanced model for carbonaceous powders. In PEMFC, several NNMCs display mass activities of 10-20 A g(-1) at 0.8 V versus a reversible hydrogen electrode, and one shows 80 A g(-1). The latter value corresponds to a volumetric activity of 19 A cm(-3) under reference conditions and represents one-seventh of the target defined by the U.S. Department of Energy for 2010 (130 A cm(-3)). The activity of all NNMCs is mainly governed by the microporous surface area, and active sites seem to be hosted in pore sizes of 5-15 A. The nitrogen and metal (iron or cobalt) seem to be present in sufficient amounts in the NNMCs and do not limit activity. The paper discusses probable directions for synthesizing more active NNMCs. This could be achieved through multiple pyrolysis steps, ball-milling steps, and control of the powder morphology by the addition of foaming agents and/or sulfur.

  7. Characterization of the electrochemical behavior of coating by steel welding 308l and in presence of noble metals deposits

    International Nuclear Information System (INIS)

    Piedras, P.; Arganis J, C. R.

    2014-10-01

    In this work the oxide deposits and noble metals deposit were characterized (Ag and Pt) on a coating of stainless steel 308l that were deposited by the shield metal arc welding (SMAW) on steel A36 by means of scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. The extrapolation of Tafel technique was also used to obtain the corrosion potential (Ec) for the pre-rusty steel and for the samples with deposits of Pt and Ag under conditions of hydrogen water chemistry (HWC), demonstrating that this parameter diminishes with the presence of this deposits. (Author)

  8. Mitigation of hydrogen by oxidation using nitrous oxide and noble metal catalysts

    International Nuclear Information System (INIS)

    Britton, M.D.

    1995-01-01

    This test studied the ability of a blend of nuclear-grade, noble-metal catalysts to catalyze a hydrogen/nitrous oxide reaction in an effort to mitigate a potential hydrogen (H 2 ) gas buildup in the Hanford Site Grout Disposal Facility. For gases having H 2 and a stoichiometric excess of either nitrous oxide or oxygen, the catalyst blend can effectively catalyze the H 2 oxidation reaction at a rate exceeding 380 μmoles of H 2 per hour per gram of catalyst (μmol/h/g) and leave the gas with less than a 0.15 residual H 2 Concentration. This holds true in gases with up to 2.25% water vapor and 0.1% methane. This should also hold true for gases with up to 0.1% carbon monoxide (CO) but only until the catalyst is exposed to enough CO to block the catalytic sites and stop the reaction. Gases with ammonia up to 1% may be slightly inhibited but can have reaction rates greater than 250 μmol/h/g with less than a 0.20% residual H 2 concentration. The mechanism for CO poisoning of the catalyst is the chemisorption of CO to the active catalyst sites. The CO sorption capacity (SC) of the catalyst is the total amount of CO that the catalyst will chemisorb. The average SC for virgin catalyst was determined to be 19.3 ± 2.0 μmoles of CO chemisorbed to each gram of catalyst (μmol/g). The average SC for catalyst regenerated with air was 17.3 ± 1.9 μmol/g

  9. A simple alkali-metal and noble gas ion source for SIMS equipments with mass separation of the primary ions

    International Nuclear Information System (INIS)

    Duesterhoeft, H.; Pippig, R.

    1986-01-01

    An alkali-metal ion source working without a store of alkali-metals is described. The alkali-metal ions are produced by evaporation of alkali salts and ionization in a low-voltage arc discharge stabilized with a noble gas plasma or in the case of small alkali-metal ion currents on the base of the well known thermic ionization at a hot tungsten wire. The source is very simple in construction and produces a stable ion current of 0.3 μA for more than 100 h. It is possible to change the ion species in a short time. This source is applicable to all SIMS equipments using mass separation for primary ions. (author)

  10. Thermodynamics of Pore Filling Metal Clusters in Metal Organic Frameworks: Pd in UiO-66

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Sholl, David S.

    2012-01-01

    Metal organic frameworks (MOFs) have experimentally been demonstrated to be capable of supporting isolated transition-metal clusters, but the stability of these clusters with respect to aggregation is unclear. In this letter we use a genetic algorithm together with density functional theory...... calculations to predict the structure of Pd clusters in UiO-66. The cluster sizes examined are far larger than those in any previous modeling studies of metal clusters in MOFs and allow us to test the hypothesis that the physically separated cavities in UiO-66 could stabilize isolated Pd clusters. Our...

  11. Synergistic effects of semiconductor substrate and noble metal nano-particles on SERS effect both theoretical and experimental aspects

    Science.gov (United States)

    Yang, Chen; Liang, Pei; Tang, Lisha; Zhou, Yongfeng; Cao, Yanting; Wu, Yanxiong; Zhang, De; Dong, Qianmin; Huang, Jie; He, Peng

    2018-04-01

    As a means of chemical identification and analysis, Surface enhanced Raman spectroscopy (SERS), with the advantages of high sensitivity and selectivity, non-destructive, high repeatability and in situ detection etc., has important significance in the field of composition detection, environmental science, biological medicine etc. Physical model of coupling effect between different semiconductor substrates and noble metal particles were investigated by using 3D-FDTD method. Mechanism and the effects of excitation wavelength, particle spacing and semiconductor substrate types on the SERS effect were discussed. The results showed that the optimal excitation wavelengths of three noble metals of Ag, Au, Cu, were located at 510, 600 and 630 nm, respectively; SERS effect of Ag, Au, Cu increases with the decreasing of the inter distance of particles, while the distance of the NPs reaches the critical value of 3 nm, the strength of SERS effect will be greatly enhanced. For the four different types of substrate of Ge, Si, SiO2 (glass) and Al2O3, the SERS effect of Ag on SiO2 > Ge > Al2O3 > Si. For Au and Cu nanoparticles, the SERS effect of them on oxide substrate is stronger than that on non-oxide substrate. In order to verify FDTD simulations, taking silver nanoparticles as an example, and silver nanoparticles prepared by chemical method were spinning coating on the four different substrates with R6G as probe molecules. The results show that the experimental results are consistent with FDTD theoretical simulations, and the SERS enhancement effect of Ag-SiO2 substrate is best. The results of this study have important theoretical significance to explain the variations of SERS enhancement on different noble metals, which is also an important guide for the preparation of SERS substrates, especially for the microfluidics. The better Raman effect can be realized by choosing proper substrate type, particle spacing and excitation wavelength, result in expanding the depth and width

  12. Experimental and computational approaches to evaluate the environmental mitigation effect in narrow spaces by noble metal chemical addition (NMCA)

    International Nuclear Information System (INIS)

    Shimizu, Ryosuke; Ota, Nobuyuki; Nagase, Makoto; Aizawa, Motohiro; Ishida, Kazushige; Wada, Yoichi

    2014-01-01

    The environmental mitigation effect of NMCA in a narrow space was evaluated by experimental and computational approaches. In the experiment at 8 MPa and 553K, T-tube whose branched line had a narrow space was prepared, and the Zr electrodes were set in the branched line at certain intervals, which were 1, 3, 5, 7, 9, 11, 15 and 29 cm from the opening section of the branched line. Electrochemical corrosion potential (ECP) at the tip of the branched narrow space varied in response to the water chemistry in the main line which was at right angle with the branched line. Computational fluid dynamics (CFD) analysis reproduced the experimental results. It was also confirmed by CFD analysis that the ingress of water from the main line into the narrow space was accelerated by cavity flow and thermal convection. By CFD analysis in a thermal sleeve of actual plant condition, which had a narrow space, the concentration of dissolved oxygen at a tip of the thermal sleeve reached at 250 ppb within 300 sec, which was the same concentration of the main line. Noble metal deposition on the surface of the thermal sleeve was evaluated by mass transfer model. Noble metal deposition was the largest near the opening section of the branched line, and gradually decreased toward the tip section. In light of the consumption of dissolved oxygen in the branched line, noble metal deposition in the thermal sleeve was sufficient to reduce the ECP. It was expected that NMCA could mitigate the corrosion environment in the thermal sleeve. (author)

  13. Performance evaluation of a biodiesel fuelled transportation engine retrofitted with a non-noble metal catalysed diesel oxidation catalyst for controlling unregulated emissions.

    Science.gov (United States)

    Shukla, Pravesh Chandra; Gupta, Tarun; Agarwal, Avinash Kumar

    2018-02-15

    In present study, engine exhaust was sampled for measurement and analysis of unregulated emissions from a four cylinder transportation diesel engine using a state-of-the-art FTIR (Fourier transform infrared spectroscopy) emission analyzer. Test fuels used were Karanja biodiesel blend (B20) and baseline mineral diesel. Real-time emission measurements were performed for raw exhaust as well as exhaust sampled downstream of the two in-house prepared non-noble metal based diesel oxidation catalysts (DOCs) and a baseline commercial DOC based on noble metals. Two prepared non-noble metal based DOCs were based on Co-Ce mixed oxide and Lanthanum based perovskite catalysts. Perovskite based DOC performed superior compared to Co-Ce mixed oxide catalyst based DOC. Commercial noble metal based DOC was found to be the most effective in reducing unregulated hydrocarbon emissions in the engine exhaust, followed by the two in-house prepared non-noble metal based DOCs. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Occurrence Forms of Carbon, Sulfur, and Noble Metals in Deposits of the Black-Shale Formation by the Example of the Degdekan Gold-Ore Deposit (Northeastern Russia)

    Science.gov (United States)

    Tauson, V. L.; Kravtsova, R. G.; Akimov, V. V.; Lipko, S. V.; Spiridonov, A. M.; Budyak, A. E.; Voronova, I. Yu.; Belozerova, O. Yu.; Arsentev, K. Yu.

    2018-01-01

    Pyrite crystals and ore-bearing shales of the Degdekan deposit were studied by means of XPS, SEM-EDX, EPMA, and AAS. Five peaks of carbon organic forms were identified, conforming to polymer compounds containing either double bonds of carbon or alkyne groups and compounds containing C-OH and C=O bonds, as well as, probably, small amounts of S-containing compounds and those with functional groups of carboxylic acids. Sulfate prevails over sulfite in pyrites; among the surface sulfide forms, disulfide prevails over monosulfide; the presence of polysulfide is registered. The occurrence of various chemical forms of sulfur on the surface might provide for concentrating of microelements including the noble metals (NMs) in their surface-bound forms. The regular behavior of NMs (Au, Pt, Pd, and Ru) depending on the grain sizes (specific surfaces) of pyrite crystals along with the narrow range of the ratios of structural and surface components of the concentrations of different NMs points to NM coprecipitation with pyrite during the same productive stage. No capture of NM-containing carbonaceous phases took place, which should violate the regularity of Au distribution in pyrites of the Sukhoi Log deposit.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

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

    Science.gov (United States)

    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 ...

  17. Scattering of low energy noble gas ions from a metal surface

    International Nuclear Information System (INIS)

    Luitjens, S.B.

    1980-01-01

    Reflection of low energy (0.1-10 keV) noble gas ions can be used to analyse a solid surface. To study charge exchange processes, the ion fractions of neon and of argon, scattered from a Cu(100) surface, have been determined. (Auth.)

  18. A real-time comparison of mercury accumulation on noble metal thin films using gravimetric device

    Science.gov (United States)

    Kabir, K. M. Mohibul; Kandjani, Ahmad Esmaielzadeh; Harrison, Christopher J.; Ippolito, Samuel J.; Sabri, Ylias M.; Bhargava, Suresh K.

    2016-12-01

    We simultaneously compared and analyzed the mercury sorption and sensing performance of gold, silver, palladium and platinum using quartz crystal microbalance (QCM). Overall, the Au- and Ag-QCM showed superior Hg sensing performance over the Pd- and Pt-counterparts when tested toward a range of concentrations (24-365 ppbv) at various operating temperatures (35-105 °C). However, it was also found that the Hg sensing performance of each metal varied significantly with the operating temperature and is dependent on the concentration tested. For instance, the Ag-QCM exhibited 57% higher response magnitude than the Au-QCM when exposed toward 24 ppbv of Hg0 vapor at 35 °C; however, the opposite trend was observed when the same concentration of Hg0 vapor was tested at 105 °C, with Au-QCM showing 104% higher response magnitudes compared to the Ag-QCM. Moreover, the Ag-QCM showed higher response magnitudes than the Au-QCM for exposure toward 365 ppbv of Hg0 vapor regardless of the operating temperature.

  19. Noble metals nanoparticles on titanium dioxide nanostructured films and the influence of their photocatalytic activity

    International Nuclear Information System (INIS)

    Nakamura, Liana Key Okada

    2012-01-01

    Currently, nanoscience and nanotechnology are considered an emerging field and continuously breaking the barrier among various disciplines. The main focus of study involves controlling structures at molecular level, arranging the atoms in order to achieve an understanding and controlling the fundamental properties of matter. In this study, molecular changes on the basis of morphology, optical and crystalline properties of TiO 2 hin films in order to increase their photon efficiency were proposed. The TiO 2 thin films were prepared by sol gel process evaluating the influence of different acids and templates to obtain the nano structured arrangements. Then, metal nanoparticles like Au, Ag, Pd and Pt were incorporated on TiO 2 thin films. This incorporation might minimize the electron-hole recombination, so it could improve the photon efficiency. From the several routes studied, the TiO 2 thin films prepared with acetic acid showed the best performance by the reason of low agglomeration of TiO 2 grains, which favors the exposure of the photoactive sites. The presence of template in the formulation had a slightly effect on photon efficiency, possible due to the higher agglomeration of the grains on the TiO 2 thin films. The addition of Pt and Au nanoparticles on TiO 2 thin films showed superior photon efficiency. The TiO 2 thin films with hexamine and metallic nanoparticles did not show the improvement on photon efficiency except for Pt and Au nanoparticles. On these situations, the improvement on photon efficiency is might be due to a possible decrease at the electron-hole recombination's velocity. Thus, the present work demonstrates the great influence of preparation conditions on the optical, morphological properties and the photon efficiency. In the future, with greater understanding of the mechanism of this influence, the properties of TiO 2 thin films will be able tailoring depending on the application. (author)

  20. Molecular dynamics simulations of Pd-Ni transition metal alloys

    International Nuclear Information System (INIS)

    Kart, S. O.; Kart, H. H.; Uludogan, M.; Tomak, M.; Cagin, T.

    2002-01-01

    Molecular Dynamics simulations are performed to study bulk properties of fcc metals and metal alloys by using the quantum Sutton-Chen many-body potentials within the context of the tight-binding approach. The Molecular Dynamics algorithms we used in the simulations of Pd-Ni alloys are based on an extended Hamiltonian formalism arising from the works of Andersen (1980), Parinello and Rahman (1980), Nose (1984), Hoover (1985) and Cagin (1988). In these simulations, the effect of temperature and concentration on the solid and liquid properties are studied. Elastic constants and phonon dispersion relation are the solid properties we simulated in this work. Dynamic and static properties of liquid Pd-Ni are also computed by examining the behavior of density, enthalpy, pair distribution function and structure factor. The melting temperatures of Pd-Ni alloys are investigated. The diffusion coefficients are calculated from the mean square displacement using Einstein relation and from velocity auto-correlation function using Green-Kubo relations. The simulation results are in good agreement with the experiments

  1. NO reduction by CO over noble-metal catalysts under cycled feedstreams

    International Nuclear Information System (INIS)

    Muraki, H.; Fujitani, Y.

    1986-01-01

    The reduction of NO with CO was studied over α-Al/sub 2/O/sub 3/-supported Pt, Pd, Rh, Ru, and Ir catalysts. The activities were measured by using cycled feeds and steady noncycled feed. The activity sequence of the catalysts tested was Rh > Ru > Ir > Pd > Pt. The activities of Pt and Pd catalysts were increased under the cycled feed. The periodic operation effect on the Pt catalyst was more predominant than that on the Pd catalyst. The order of periodic operation effect corresponded to the order of their susceptibility to CO self-poisoning

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

    Science.gov (United States)

    Baksi, Ananya; Pradeep, T.

    2013-11-01

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

  3. Tailoring of the PS surface with low energy ions: Relevance to growth and adhesion of noble metals

    International Nuclear Information System (INIS)

    Zaporojtchenko, V.; Zekonyte, J.; Wille, S.; Schuermann, U.; Faupel, F.

    2005-01-01

    Ion-polymer interaction induces different phenomena in the near surface layer of polymers, and promotes its adhesion to metals. Using XPS, TEM and AFM, polystyrene surface was examined after 1 keV ion-beam treatments with oxygen, nitrogen and argon ions in the ion fluence range from 10 12 to 10 16 cm -2 to clarify the following points: chemical reaction after treatment in vacuum and after exposure to air, identification of adsorption-relevant species for metal atoms, formation of cross-links in the outermost polymer layer. The early stages of metal-polymer interface formation during metallization play a crucial role in the metal-polymer adhesion. Therefore, the influence of the ion fluence and ion chemistry on the condensation of noble metals, film growth and peel strength were measured. The peel strength showed a maximum at a certain fluence depending on ion chemistry. For example, the surface treatment with very low fluence of oxygen ions improved the adhesion between copper and polystyrene by two orders of magnitude without significantly increasing the surface roughness measured with AFM. The locus of failure changed at the same time from interfacial failure for untreated polymer surfaces to cohesive failure in the polymer for modified surfaces. A multilayer model of the metal-polymer interface after ion treatment is suggested

  4. Crystal phase-based epitaxial growth of hybrid noble metal nanostructures on 4H/fcc Au nanowires

    Science.gov (United States)

    Lu, Qipeng; Wang, An-Liang; Gong, Yue; Hao, Wei; Cheng, Hongfei; Chen, Junze; Li, Bing; Yang, Nailiang; Niu, Wenxin; Wang, Jie; Yu, Yifu; Zhang, Xiao; Chen, Ye; Fan, Zhanxi; Wu, Xue-Jun; Chen, Jinping; Luo, Jun; Li, Shuzhou; Gu, Lin; Zhang, Hua

    2018-03-01

    Crystal-phase engineering offers opportunities for the rational design and synthesis of noble metal nanomaterials with unusual crystal phases that normally do not exist in bulk materials. However, it remains a challenge to use these materials as seeds to construct heterometallic nanostructures with desired crystal phases and morphologies for promising applications such as catalysis. Here, we report a strategy for the synthesis of binary and ternary hybrid noble metal nanostructures. Our synthesized crystal-phase heterostructured 4H/fcc Au nanowires enable the epitaxial growth of Ru nanorods on the 4H phase and fcc-twin boundary in Au nanowires, resulting in hybrid Au-Ru nanowires. Moreover, the method can be extended to the epitaxial growth of Rh, Ru-Rh and Ru-Pt nanorods on the 4H/fcc Au nanowires to form unique hybrid nanowires. Importantly, the Au-Ru hybrid nanowires with tunable compositions exhibit excellent electrocatalytic performance towards the hydrogen evolution reaction in alkaline media.

  5. Effectiveness of non-noble metal based diesel oxidation catalysts on particle number emissions from diesel and biodiesel exhaust.

    Science.gov (United States)

    Shukla, Pravesh Chandra; Gupta, Tarun; Labhasetwar, Nitin Kumar; Khobaragade, Rohini; Gupta, Neeraj K; Agarwal, Avinash Kumar

    2017-01-01

    Two new formulations of non-noble metal based diesel oxidation catalysts based on CoCe based mixed oxide (DOC 2 ) and perovskite catalysts (DOC 3 ) were prepared and retrofitted in a 4-cylinder diesel engine fueled by diesel and Karanja biodiesel blend (KB20). In this study, their effectiveness in reducing raw exhaust particulate emissions vis-à-vis a commercial diesel oxidation catalyst (DOC 1 ) was evaluated. Emission characteristics such as particle number-size distribution, mass-size distribution, and surface area-size distribution, total particle number concentration and count mean diameter as a function of engine load at constant engine speed were evaluated. Variations in total particle number concentration as a function of engine speed were also determined. The prepared DOCs and the commercial DOC showed varying degrees of performance as a function of engine operating conditions. Overall, effectiveness of the prepared DOC's appeared to be more fuel specific. For diesel exhaust, overall performance of DOC 1 was more effective compared to both prepared DOCs, with DOC 2 being superior to DOC 3 . In case of KB20 exhaust, the overall performance of DOC 2 was either more effective or nearly comparable to DOC 1, while DOC 3 being not so effective. This showed that the DOCs based on CoCe based mixed oxide catalysts have potential to replace commercial noble metal based DOC's, especially in engines fueled by biodiesel. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Noble metal-free RGO/TiO2 composite nanofiber with enhanced photocatalytic H2-production performance

    Science.gov (United States)

    Xu, Difa; Li, Lingling; He, Rongan; Qi, Lifang; Zhang, Liuyang; Cheng, Bei

    2018-03-01

    1D reduced graphene oxide (RGO)/TiO2 nanocomposite fibers were fabricated by a facile two-step method. These samples demonstrated high photocatalytic H2-production activity from methanol aqueous solution, even without the aid of noble metal. When the ratio of RGO is 0.25 wt%, the highest H2-production rate was achieved. It increased by 10 fold than bare TiO2, reaching 149 μmol h-1 g-1 with quantum efficiency (QE) of 0.75%. The reasons were as follows. Firstly, the RGO nanosheets acted as electron acceptors. Secondly, some shallow trap states at the surface or interface of TiO2 were created by the reduction of GO during calcination. Thirdly, the redox potential position of graphene/graphene- was suitable. Fourthly, RGO could efficiently promote the separation of photogenerated electron-hole pairs and significantly enhance the photocatalytic H2-production activity. This interpretation was corroborated by transient photocurrent response. The aforementioned marvelous results provided a probable solution to replace noble metals (such as Pt) by graphene as an effective cocatalyst.

  7. Cálculo del esfuerzo ideal de metales nobles mediante primeros principios en la dirección

    Science.gov (United States)

    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 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 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.

  8. 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

    Science.gov (United States)

    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.

  9. Magnetic domains and frustration in metallic CePdAl

    Energy Technology Data Exchange (ETDEWEB)

    Lucas, Stefan; Huesges, Zita; Huang, Chien-Lung; Stockert, Oliver [Max Planck Institute CPfS, Dresden (Germany); Fritsch, Veronika; Sakai, Akito [EP 6, Electronic Correlations and Magnetism, University of Augsburg (Germany); Grube, Kai; Taubenheim, Christian; Loehneysen, Hilbert von [Karlsruhe Institute of Technology (Germany)

    2016-07-01

    Magnetic frustration is an exciting topic in condensed matter physics, since it can lead to new ground states of materials, e.g. a spin liquid or spin glass state. Effects of magnetic frustration have been investigated intensively for insulating materials. However, the existence of magnetic frustration in metallic systems is still under debate. CePdAl is a metallic Kondo system, where geometric magnetic frustration arises from the formation of Ce ions on a distorted Kagome lattice. Neutron scattering experiments revealed, that only two thirds of the magnetic Ce moments order antiferromagnetically below T{sub N}=2.7 K, whereas the other third remains mainly disordered. Thermodynamic as well as neutron scattering measurements are presented to verify the existence of partial magnetic frustration in CePdAl. Recently neutron diffraction experiments under magnetic fields applied along two orthogonal directions in the magnetically hard basal plane were performed. They show opposite effects on the magnetic intensity of a selected magnetic domain depending on the field direction with respect to the propagation vector. If this is only an effect of different domain population or also due to a change in magnetic frustration shall be discussed.

  10. Noble-metal-free tungsten oxide/carbon (WOx/C) hybrid manowires for highly efficient hydrogen evolution

    Science.gov (United States)

    Liu, Changhai; Qiu, Yangyang; Xia, Yujian; Wang, Fang; Liu, Xiaocun; Sun, Xuhui; Liang, Qian; Chen, Zhidong

    2017-11-01

    Developing active, stable, and low-cost electrocatalysts to generate hydrogen is a great challenge in the fields of chemistry and energy. Nonprecious metal catalysts comprised of inexpensive and earth-abundant transition metals are regarded as a promising substitute for noble metal catalysts used in hydrogen evolution reaction (HER), but are still practically unfeasible mainly due to unsatisfactory activity and durability. Here we report a facile two-step preparation method for WOx nanowires with high concentration of oxygen vacancies (OVs) via calcination of W-polydopamine compound precursors. The resulting hybrid material possesses a uniform and ultralong 1D nanowires structure and a rough and raised surface, which can effectively improve the specific surface area. The products exhibit excellent performance for H2 generation: the required overpotentials for 1 and 10 mA cm-2 are 18 and 108 mV, the Tafel slope is 46 mV/decade, and the electrochemically active surface area is estimated to be ˜77.0 m2 g-1. After 1000 cycles, the catalyst works well without significant current density drop. Our experimental results verified metallic transition metal oxides as superior non-Pt electrocatalysts for practical hydrogen evolution reactions.

  11. Radiological analysis by the addition of hydrogen and noble metals in the reactors of the Laguna Verde central; Analisis radiologico por la adicion de hidrogeno y metales nobles en los reactores de la Central Laguna Verde

    Energy Technology Data Exchange (ETDEWEB)

    Padilla C, I. [CFE, Proteccion Radiologica (Mexico)]. e-mail: ipadilla@cfe.gob.mx

    2006-07-01

    During the operation of the nuclear power stations there are metals that are subject to condition and agents that cause that these they present indications of intergranular corrosion and for their importance they are subject to a continuous surveillance to assure their integrity. During the time of operation, for the level of indications, it can be necessary the substitution of these. The internal components of the vessel and particularly those of the structure of the reactor core are exposed during the operation to a neutron flow that causes that these they are activated and, in consequence, before an eventual repair it will be necessary to face high radiation levels. At the moment a technique that controls exists and it reduces the growth rate of the indications in the metals and it increases its useful life: the addition of hydrogen. The addition of hydrogen it is an ALARA measure from long term when protecting the internals of the vessel that requires to establish radiological controls in the stage of their application to avoid unnecessary dose to the personnel. The addition of hydrogen to the primary system has as objective to reduce the growth of indications taken place by intergranular corrosion in metals of the reactor core and this is achieved when the electrochemical thresholds are reached. Hydrogen to interacting with the metal surfaces it generates reductive reactions causing in consequence an increment in the concentration of soluble cobalt in the coolant one and an increment in the nitrogen concentration. To reduce the magnitude of the radiological impact that in some NC reach up to factors 10, its are injected to the system noble metals as the rhodium and the platinum, to reduce the concentration of hydrogen to the system and to be below the threshold electrochemical potential necessary to protect the internals of the reactor vessel. The external and internal operational experience generated on this protection technique to the internals of the vessel

  12. Structure and Mobility of Metal Clusters in MOFs: Au, Pd, and AuPd Clusters in MOF-74

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Walton, Krista S.; Sholl, David S.

    2012-01-01

    Understanding the adsorption and mobility of metal–organic framework (MOF)-supported metal nanoclusters is critical to the development of these catalytic materials. We present the first theoretical investigation of Au-, Pd-, and AuPd-supported clusters in a MOF, namely MOF-74. We combine density...... functional theory (DFT) calculations with a genetic algorithm (GA) to reliably predict the structure of the adsorbed clusters. This approach allows comparison of hundreds of adsorbed configurations for each cluster. From the investigation of Au8, Pd8, and Au4Pd4 we find that the organic part of the MOF...... is just as important for nanocluster adsorption as open Zn or Mg metal sites. Using the large number of clusters generated by the GA, we developed a systematic method for predicting the mobility of adsorbed clusters. Through the investigation of diffusion paths a relationship between the cluster...

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

    Science.gov (United States)

    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

  14. Promotion of Mo/Al2O3 Sulfide Catalyst by Noble Metals in Simultaneous Hydrodesulfurization of Thiophene and Hydrodenitrogenation of Pyridine: A Comparative Study

    Czech Academy of Sciences Publication Activity Database

    Vít, Zdeněk; Cinibulk, Josef; Gulková, Daniela

    2004-01-01

    Roč. 272, 1-2 (2004), s. 99-107 ISSN 0926-860X R&D Projects: GA AV ČR IAA4072103 Institutional research plan: CEZ:AV0Z4072921 Keywords : Mo catalyst * noble metal * HDS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor : 2.378, year: 2004

  15. Laser ablation in liquid media of noble metals. The physics of plasma plume and the optical properties of the produced colloids

    International Nuclear Information System (INIS)

    Cataliotti, R.S.; Messina, E.

    2009-01-01

    In experiments of pulsed laser ablation in liquids (PLAL), performed on noble metal targets, many physical aspects regarding the characteristics of the plasma plume generated in the confining liquid, and the optical properties of the produced nano colloids deserve a clear definition and discussion. In this paper we present the relevant theories and the results of experiments performed in our laboratory on this argument.

  16. The pH-sensitive Pd nanoparticles as ink for ink-jet printing technology and electroless Cu metallic patterns on indium-doped tin oxide substrate

    Energy Technology Data Exchange (ETDEWEB)

    Tseng, Chun-Chieh; Lin, Yi [Medical Device Section, Medical Devices and Opto-Electronics Equipment Department, Metal Industries Research and Development Centre, Kaohsiung 802, Taiwan (China); Liu, Tsai-Yun [Department of Mechanical Engineering and Graduate Institute of Mechanical and Precision Engineering, National Kaohsiung University of Applied Sciences, Kaohsiung 807, Taiwan (China); Nian, Yan-Yu [Graduate School of Defense Science, Chung Cheng Institute of Technology, National Defense University, 335 Taiwan (China); Wang, Min-Wen, E-mail: mwwang@cc.kuas.edu.tw [Department of Mechanical Engineering and Graduate Institute of Mechanical and Precision Engineering, National Kaohsiung University of Applied Sciences, Kaohsiung 807, Taiwan (China); Ger, Ming-Der, E-mail: mingderger@gmail.com [Department of Chemical and Materials Engineering, Chung Cheng Institute of Technology, National Defense University, 335 Taiwan (China)

    2013-06-01

    In this work, a method to fabricate copper pattern on an indium-doped tin oxide (ITO) glass substrate is described. This method involves ink-jet printing of a pH-sensitive chitosan-g-polyvinyl acetate/Pd nanoparticle (CTS-g-PVAc-Pd) based ink on an untreated ITO plate to create the catalytic sites, onto which copper is subsequently deposited by an electroless plating method. To prepare the CTS-g-PVAc-Pd nanoparticles, a pH-sensitive chitosan-g-polyvinyl acetate (CTS-g-PVAc) copolymer is utilized to self-reduce Pd nanoparticles. The pH-sensitive CTS chains function as stabilizing agent for noble metal nanoparticles in acidic ink solution. On the other hand, CTS-g-PVAc copolymers convert to hydrophilic CTS-g-poly(vinyl alcohol) via alkali hydrolysis during the electroless copper plating. Therefore, the copper film with dramatically enhanced adhesion is formed on the surface of ITO glass without special pretreatment step before electroless deposition of copper film. Our results show that this process yields copper line with width down to 60 μm and ITO plated with the copper coating has good electrical conductivity, with an electrical resistivity of about 5.4 μΩ cm. - Highlights: • Chitosan-g-polyvinyl acetate copolymer provides reducing environment for Pd nanoparticles. • pH-sensitive Pd nanoparticles as ink for ink-jet printing. • Patterning Pd catalyst for the electroless deposition of copper patterns. • Method to fabricate copper patterns on In-doped tin oxide substrates. • Ink-jet printing can be directly and easily applied to fabricate metal patterns.

  17. Radiological analysis by the addition of hydrogen and noble metals in the reactors of the Laguna Verde central

    International Nuclear Information System (INIS)

    Padilla C, I.

    2006-01-01

    During the operation of the nuclear power stations there are metals that are subject to condition and agents that cause that these they present indications of intergranular corrosion and for their importance they are subject to a continuous surveillance to assure their integrity. During the time of operation, for the level of indications, it can be necessary the substitution of these. The internal components of the vessel and particularly those of the structure of the reactor core are exposed during the operation to a neutron flow that causes that these they are activated and, in consequence, before an eventual repair it will be necessary to face high radiation levels. At the moment a technique that controls exists and it reduces the growth rate of the indications in the metals and it increases its useful life: the addition of hydrogen. The addition of hydrogen it is an ALARA measure from long term when protecting the internals of the vessel that requires to establish radiological controls in the stage of their application to avoid unnecessary dose to the personnel. The addition of hydrogen to the primary system has as objective to reduce the growth of indications taken place by intergranular corrosion in metals of the reactor core and this is achieved when the electrochemical thresholds are reached. Hydrogen to interacting with the metal surfaces it generates reductive reactions causing in consequence an increment in the concentration of soluble cobalt in the coolant one and an increment in the nitrogen concentration. To reduce the magnitude of the radiological impact that in some NC reach up to factors 10, its are injected to the system noble metals as the rhodium and the platinum, to reduce the concentration of hydrogen to the system and to be below the threshold electrochemical potential necessary to protect the internals of the reactor vessel. The external and internal operational experience generated on this protection technique to the internals of the vessel

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

    Directory of Open Access Journals (Sweden)

    X. H. Liu

    2015-10-01

    Full Text Available 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 87Rb D1 line absorption cross sections. We then measured the absorption profile of the sample cell, from which we calculated the 87Rb number densities at different temperatures. Then we measured the frequency shifts resulted from the spin polarization of the 87Rb 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.

  19. Carbon nanotubes and other nanostructures as support material for nanoparticulate noble-metal catalysts in fuel cells

    DEFF Research Database (Denmark)

    Veltzé, Sune; Larsen, Mikkel Juul; Elina, Yli-Rantala

    or platinum-alloy catalysts in the electrodes are required. To maximize the utilization of the noble metal it is frequently deposited as nanoparticles (1–5 nm) on a stabilizing support of carbon black. Carbon black provides good anchoring of the catalyst particles, but is prone to severe destructive oxidation...... carbon black they can conduct electrons to and from the reaction sites, and in addition their resistance to electrochemical degradation is better than that of carbon black due to their much higher structural perfection. This latter feature is indeed highly desired with a view to the durability...... for difficulties in contacting the nanotubes with other substances in the electrode or electrode preparation. Other promising candidate structures for catalyst support include carbon nanofibers (CNF) and various modifications of CNTs. We present some of our work with the investigation of surface properties...

  20. Carbon Nanotubes and Other Nanostructures as Support Material for Nanoparticulate Noble-Metal Catalysts in Fuel Cells

    DEFF Research Database (Denmark)

    Larsen, Mikkel Juul; Veltzé, Sune; Skou, Eivind Morten

    or platinum-alloy catalysts in the electrodes are required. To maximize the utilization of the noble metal it is frequently deposited as nanoparticles (1-5 nm) on a stabilizing support of carbon black. Carbon black provides good anchoring of the catalyst particles, but is prone to severe destructive oxidation...... carbon black they can conduct electrons to and from the reaction sites, and in addition their resistance to electrochemical degradation is better than that of carbon black due to their much higher structural perfection. This latter feature is indeed highly desired with a view to the durability...... for difficulties in contacting the nanotubes with other substances in the electrode or electrode preparation. Other promising candidate structures for catalyst support include carbon nanofibers (CNF) and various modifications of CNTs. We present some of our work with the investigation of surface properties...

  1. Plasmon Modulation Spectroscopy of Noble Metals to Reveal the Distribution of the Fermi Surface Electrons in the Conduction Band

    Directory of Open Access Journals (Sweden)

    Kentaro Takagi

    2017-12-01

    Full Text Available To directly access the dynamics of electron distribution near the Fermi-surface after plasmon excitation, pump-probe spectroscopy was performed by pumping plasmons on noble-metal films and probing the interband transition. Spectral change in the interband transitions is sensitive to the electron distribution near the Fermi-surface, because it involves the d valence-band to the conduction band transitions and should reflect the k-space distribution dynamics of electrons. For the continuous-wave pump and probe experiment, the plasmon modulation spectra are found to differ from both the current modulation and temperature difference spectra, possibly reflecting signatures of the plasmon wave function. For the femtosecond-pulse pump and probe experiment, the transient spectra agree well with the known spectra upon the excitation of the respective electrons resulting from plasmon relaxation, probably because the lifetime of plasmons is shorter than the pulse duration.

  2. Solar hydrogen from an aqueous, noble-metal-free hybrid system in a continuous-flow sampling reaction system.

    Science.gov (United States)

    Li, Xiaobo; Ward, Antony J; Masters, Anthony F; Maschmeyer, Thomas

    2014-06-10

    We introduce the visible-light photocatalytic H2 evolution reaction as catalyzed by a cobaloxime/carbon nitride (C3N4) noble-metal-free hybrid photosystem by using a continuous-flow sampling reaction system. The photocatalytic H2 evolution rate is highly dependent on the structure of C3N4, in which porous C3N4 shows the best activity compared with bulk C3N4 (lamellar) and C3N4 nanosheets. When using porous C3N4, the system is neither affected by the solution pH, nor the C3N4 concentration, nor the structure of the cobaloxime complex. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. High-pressure phase transition of alkali metal-transition metal deuteride Li2PdD2

    Science.gov (United States)

    Yao, Yansun; Stavrou, Elissaios; Goncharov, Alexander F.; Majumdar, Arnab; Wang, Hui; Prakapenka, Vitali B.; Epshteyn, Albert; Purdy, Andrew P.

    2017-06-01

    A combined theoretical and experimental study of lithium palladium deuteride (Li2PdD2) subjected to pressures up to 50 GPa reveals one structural phase transition near 10 GPa, detected by synchrotron powder x-ray diffraction, and metadynamics simulations. The ambient-pressure tetragonal phase of Li2PdD2 transforms into a monoclinic C2/m phase that is distinct from all known structures of alkali metal-transition metal hydrides/deuterides. The structure of the high-pressure phase was characterized using ab initio computational techniques and from refinement of the powder x-ray diffraction data. In the high-pressure phase, the PdD2 complexes lose molecular integrity and are fused to extended [PdD2]∞ chains. The discovered phase transition and new structure are relevant to the possible hydrogen storage application of Li2PdD2 and alkali metal-transition metal hydrides in general.

  4. Experimental study on the surface characteristics of Pd-based bulk metallic glass

    International Nuclear Information System (INIS)

    Zhang, Xiang; Sun, Bingli; Zhao, Na; Li, Qian; Hou, Jianhua; Feng, Weina

    2014-01-01

    Highlights: • Wetting behavior of four polymer melts on Pd-based bulk metallic glass was investigated. • From results, in general, the contact angle of polymer on Pd-based BMG decreases with temperature increasing. • We find a critical temperature for each polymer, above this temperature, contact angle on Pd-based BMG does not decrease with temperature increasing. • Surface free energy of Pd-based BMG was estimated by Owens–Wendt method. - Abstract: The metallic glass has many unique and desirable physical and chemical characteristics for their long-range disordered atomic structure, among them the interfacial properties of the metallic glasses are crucial for their applications and manufacturing. In this work, the contact wetting angles between the polymer melts and Pd 40 Cu 30 Ni 10 P 20 bulk metallic glass (Pd-BMG) with four kinds of roughness were analyzed. Experiments show the order of four polymers wettability on Pd-BMG was PP > HDPE > COC > PC. The surface free energy of Pd-BMG was estimated by Owens–Wendt method using the contact angles of three testing liquids. Neumann method was also used to further evidence the surface free energy of Pd-BMG comparing with PTFE, mold steels NAK80 and LKM2343ESR. The results provide theoretical and technical supports for the fabrication of metallic glass micro mold and the parameter optimization of polymer micro injection molding

  5. Composite of Au-Pd nanoalloys/reduced graphene oxide toward catalytic selective organic transformation to fine chemicals

    Science.gov (United States)

    Zhang, Yanhui; Gao, Fei; Fu, Ming-Lai

    2018-01-01

    A facile, stabilizing-molecules-free strategy has been utilized for anchoring Au-Pd alloy nanoparticles onto the flat surface of two-dimensional (2D) reduced graphene oxide (RGO) nanosheets. Formation of Au-Pd nanoalloys and loading onto the RGO are accomplished simultaneously. The Au-Pd/reduced graphene oxide (Au-Pd/RGO) exhibits higher catalytic activity than both Au/RGO and Pd/RGO, prepared by the same approach toward selective oxidation of benzyl alcohol and selective reduction of nitroaromatics, the catalytic activity order can be in good agreement with the noble metal particles size distribution of the Au, Pd and Au-Pd/RGO.

  6. Visible-Near-Infrared-Light-Driven Oxygen Evolution Reaction with Noble-Metal-Free WO2-WO3 Hybrid Nanorods.

    Science.gov (United States)

    Wang, Song Ling; Mak, Yan Lin; Wang, Shijie; Chai, Jianwei; Pan, Feng; Foo, Maw Lin; Chen, Wei; Wu, Kai; Xu, Guo Qin

    2016-12-13

    Understanding and manipulating the one half-reaction of photoinduced hole-oxidation to oxygen are of fundamental importance to design and develop an efficient water-splitting process. To date, extensive studies on oxygen evolution from water splitting have focused on visible-light harvesting. However, capturing low-energy photons for oxygen evolution, such as near-infrared (NIR) light, is challenging and not well-understood. This report presents new insights into photocatalytic water oxidation using visible and NIR light. WO 2 -WO 3 hybrid nanorods were in situ fabricated using a wet-chemistry route. The presence of metallic WO 2 strengthens light absorption and promotes the charge-carrier separation of WO 3 . The efficiency of the oxygen evolution reaction over noble-metal-free WO 2 -WO 3 hybrids was found to be significantly promoted. More importantly, NIR light (≥700 nm) can be effectively trapped to cause the photocatalytic water oxidation reaction. The oxygen evolution rates are even up to around 220 (λ = 700 nm) and 200 (λ = 800 nm) mmol g -1 h -1 . These results demonstrate that the WO 2 -WO 3 material is highly active for water oxidation with low-energy photons and opens new opportunities for multichannel solar energy conversion.

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

    Science.gov (United States)

    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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Synthesis, Characterization and Spectral Studies of Noble Heterobinuclear Complexes of Transition Metal Ions and their Biological Activity

    Directory of Open Access Journals (Sweden)

    Netra Pal Singh

    2011-01-01

    Full Text Available Some noble heterobinuclear complexes of transition metal ions with bis(salicylaldehydemalonyl-dihydrazone in the presence of 5-nitroindazole Cu(II / Ni(II- chloride of the type [ML1M‘L2Cl2] or [ML1FeL2Cl2]Cl, where M = Ni(II, Cu(II and M' = Mn(II, Co(II, have been prepared. All the complexes have been characterized by IR, UV vis and EPR spectroscopy, elemental analysis, magnetic moment and molar conductance measurement. Spectral studies and magnetic moment measurement in DMF suggest the covalent nature of the complexes, except the [ML1FeL2Cl2]Cl complex which is 1:1 electrolyte. An octahedral geometry is proposed for M‘ and square planer for M for the heterobinuclear complexes. The low value of magnetic moment and overlapping EPR signals are due to spin crossover since both of the metals have unpaired electrons with same molecular symmetry. The lowering of the magnetic moment has been discussed. The biological activity (antifungal and antibacterial of the represented compounds has been studied.

  9. Study of the Stability of Copper Fixed Point in Sealed Cells for Calibration of Noble Metal Thermocouples

    Directory of Open Access Journals (Sweden)

    Yasser A. Abdel-Aziz

    2009-12-01

    Full Text Available This paper reports the realization and stability of the freezing point of high purity copper (99.9999% Cu (1084.62 °C in a sealed cell by noble metal thermocouples of Pt-l0%Rh/Pt (type S and Pt-30%Rh/Pt-6%Rh (type B, using a three zone heating furnace. The graphite crucible in the sealed cell is made of ultra high purity carbon to contain 99.9999 % purity Cu metal. The individual difference at Cu freezing point, measured by each thermocouple at the National Institute for Standards (NIS with respect to the value as stated in the ITS-90, is lying within the overall uncertainty of measurements. The expanded uncertainty of measurements was evaluated and expressed as 95% confidence level. The Cu freezing point as measured with type-S thermocouple was found to be 1084.62 °C ± 0.666 °C and that with type B thermocouple was found to be 1084.62 °C ± 0.532 °C.

  10. A fast response hydrogen sensor with Pd metallic grating onto a fiber's end-face

    Science.gov (United States)

    Yan, Haitao; Zhao, Xiaoyan; Zhang, Chao; Li, Qiu-Ze; Cao, Jingxiao; Han, Dao-Fu; Hao, Hui; Wang, Ming

    2016-01-01

    We demonstrated an integrated hydrogen sensor with Pd metallic grating fabricated on a fiber end-face. The grating consists of three thin metal layers in stacks, Au, WO3 and Pd. The WO3 is used as a waveguide layer between the Pd and Au layer. The Pd layer is etched by using a focused ion beam (FIB) method, forming a Pd metallic grating with period of 450 nm. The sensor is experimentally exposed to hydrogen gas environment. Changing the concentration from 0% to 4% which is the low explosive limit (LEL), the resonant wavelength measured from the reflection experienced 28.10 nm spectral changes in the visible range. The results demonstrated that the sensor is sensitive for hydrogen detection and it has fast response and low temperature effect.

  11. Solution-phase epitaxial growth of noble metal nanostructures on dispersible single-layer molybdenum disulfide nanosheets.

    Science.gov (United States)

    Huang, Xiao; Zeng, Zhiyuan; Bao, Shuyu; Wang, Mengfei; Qi, Xiaoying; Fan, Zhanxi; Zhang, Hua

    2013-02-05

    Compared with the conventional deposition techniques used for the epitaxial growth of metallic structures on a bulk substrate, wet-chemical synthesis based on the dispersible template offers several advantages, including relatively low cost, high throughput, and the capability to prepare metal nanostructures with controllable size and morphology. Here we demonstrate that the solution-processable two-dimensional MoS(2) nanosheet can be used to direct the epitaxial growth of Pd, Pt and Ag nanostructures at ambient conditions. These nanostructures show the major (111) and (101) orientations on the MoS(2)(001) surface. Importantly, the Pt-MoS(2) hybrid nanomaterials exhibit much higher electrocatalytic activity towards the hydrogen evolution reaction compared with the commercial Pt catalysts with the same Pt loading. We believe that nanosheet-templated epitaxial growth of nanostructures via wet-chemical reaction is a promising strategy towards the facile and high-yield production of novel functional materials.

  12. Pd Metal Catalysts for Cross-Couplings and Related Reactions in the 21st Century: A Critical Review.

    Science.gov (United States)

    Biffis, Andrea; Centomo, Paolo; Del Zotto, Alessandro; Zecca, Marco

    2018-02-28

    Cross-couplings and related reactions are a class of highly efficient synthetic protocols that are generally promoted by molecular Pd species as catalysts. However, catalysts based on more or less highly dispersed Pd metal have been also employed for this purpose, and their use, which was largely limited to the Heck reaction until the turn of the century, has been extended in recent years to most reactions of this class. This review provides a critical overview on these recent applications of Pd metal catalysts. Particular attention is devoted to the discussion of the mechanistic pathways that have been proposed to explain the catalytic role of Pd metal. Furthermore, the most outstanding Pd metal based catalytic systems that have emerged are illustrated, together with the development of novel approaches to boost the reactivity of Pd metal. A section summarizing the current industrial applications of Pd metal catalyzed reactions of this kind concludes the review.

  13. Investigation of the Hydrogenation of 5-Methylfurfural by Noble Metal Nanoparticles in a Microcapillary Reactor.

    Science.gov (United States)

    Gmeiner, Julia; Seibicke, Max; Behrens, Silke; Spliethoff, Bernd; Trapp, Oliver

    2016-03-21

    On-column reaction gas chromatography (ocRGC) was successfully utilized as high-throughput platform for monitoring of the conversion and selectivity of hydrogenation of 5-methylfurfural catalyzed by polymer-stabilized Ru and Pd nanoparticles. We were able to elucidate the effect of various reaction conditions, mainly together with the catalyst loading on the conversion rate and the selectivity of the reaction. Our strategy yields significant improvements in reaction analysis times and cost effectiveness in comparison to standard methods. We are able to demonstrate that ocRGC approach provides valuable information about the reaction system that gives scientists a tool to design suitable catalytic systems for enhanced sustainable chemistry in the future. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. The Simple, Effective Synthesis of Highly Dispersed Pd/C and CoPd/C Heterogeneous Catalysts via Charge-Enhanced Dry Impregnation

    Directory of Open Access Journals (Sweden)

    Lawrence D’Souza

    2016-05-01

    Full Text Available Pd/C and CoPd/C heterogeneous catalysts have been synthesized by adopting Charge Enhanced Dry Impregnation (CEDI. The particles size distribution, their high metal surface-to-bulk ratios, and synthesis feasibility are unmatchable to any known noble metal bimetallic heterogeneous catalyst preparation techniques. Next generation Fuel Cells and Fischer-Tropsch catalytic processes economy will be benefited from the proposed methodology.

  15. Recycling of spent noble metal catalysts with emphasis on pyrometallurgical processing

    Energy Technology Data Exchange (ETDEWEB)

    Hagelueken, C. [Degussa Huels AG, Hanau (Germany)

    1999-09-01

    Precious metal catalysts for catalytic Naphta Reforming, Isomerization, Hydrogenation and other chemical and petrochemical processes are valuable assets for oil refineries and chemical companies. At the end of the service life of a reactor load of catalyst, the efficient and reliable recovery of the precious metals contained in the catalyst is of paramount importance. More than 150 years of technological advances at Degussa-Huels have resulted in refining methods for all kinds of precious metal containing materials which guarantee an optimum technical yield of the precious metals included. The refining of catalysts today is one of the important activities in the precious metals business unit. In the state-of-the-art precious metal refinery at Hanau in the centre of Germany, a wide variety of processes for the recovery of all precious metals is offered. These processes include accurate preparation, sampling and analysis as well as both wet-chemical and pyrometallurgical recovery techniques. Special emphasis in this presentation is laid on the advantages of pyrometallurgical processes for certain kinds of catalysts. To avoid any risks during transport, sampling and treatment of the spent catalyst, all parties involved in the recycling chain strictly have to follow the relevant safety regulations. Under its commitment to 'Responsible Care' standard procedures have been developed which include pre-shipment samples, safety data sheets/questionnaires and inspection of spent catalysts. These measures not only support a safe and environmentally sound catalyst recycling but also enable to determine the most suitable and economic recovery process - for the benefit of the customer. (orig.)

  16. Three dimensional nano-assemblies of noble metal nanoparticle-infinite coordination polymers as specific oxidase mimetics for degradation of methylene blue without adding any cosubstrate.

    Science.gov (United States)

    Wang, Lihua; Zeng, Yi; Shen, Aiguo; Zhou, Xiaodong; Hu, Jiming

    2015-02-07

    Novel three-dimensional (3D) nano-assemblies of noble metal nanoparticle (NP)-infinite coordination polymers (ICPs) are conveniently fabricated through the infiltration of HAuCl4 into hollow Au@Ag@ICPs core-shell nanostructures and its replacement reaction with Au@Ag NPs. The present 3D nano-assemblies exhibit highly efficient and specific intrinsic oxidase-like activity even without adding any cosubstrate.

  17. Effects of metal composition and ratio on peptide-templated multimetallic PdPt nanomaterials

    International Nuclear Information System (INIS)

    Merrill, Nicholas A.; Nitka, Tadeusz T.; McKee, Erik M.; Merino, Kyle C.; Drummy, Lawrence F.

    2017-01-01

    It can be difficult to simultaneously control the size, composition, and morphology of metal nanomaterials under benign aqueous conditions. For this, bioinspired approaches have become increasingly popular due to their ability to stabilize a wide array of metal catalysts under ambient conditions. In this regard, we used the R5 peptide as a three-dimensional template for formation of PdPt bimetallic nanomaterials. Monometallic Pd and Pt nanomaterials have been shown to be highly reactive toward a variety of catalytic processes, but by forming bimetallic species, increased catalytic activity may be realized. The optimal metal-to-metal ratio was determined by varying the Pd:Pt ratio to obtain the largest increase in catalytic activity. To better understand the morphology and the local atomic structure of the materials, the bimetallic PdPt nanomaterials were extensively studied by transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and pair distribution function analysis. The resulting PdPt materials were determined to form multicomponent nanostructures where the Pt component demonstrated varying degrees of oxidation based upon the Pd:Pt ratio. To test the catalytic reactivity of the materials, olefin hydrogenation was conducted, which indicated a slight catalytic enhancement for the multicomponent materials. Finally, these results suggest a strong correlation between the metal ratio and the stabilizing biotemplate in controlling the final materials morphology, composition, and the interactions between the two metal species.

  18. Noble metal emissions. Final presentation, Hanover, October 17/18, 1996; Edelmetall - Emissionen. Abschlusspraesentation, Hannover, 17. und 18. Oktober 1996. Kurzfassung der Vortraege

    Energy Technology Data Exchange (ETDEWEB)

    Pohl, D. [comp.

    1997-12-31

    The discussion concerning noble metal emissions, in particular platinum emissions, and their environmental effects, started with the introduction of catalytical cleaning of gasoline engine exhaust. The Research Association for Noble Metal Emissions (Forschungsverbund Edelmetallemissionen) ws founded for the purpose of investigating problems concerning the types and volumes of noble metal emissions as well as their toxicological and allergological potential. In order to make valid statements on physiological and toxicological effects, it was necessary to identify the chemical forms of platinum and to develop powerful methods of analysis. Investigations of platinum concentrations in environmental samples suggest a 10 percent bioavailability. [Deutsch] Mit der Einfuehrung der katalytischen Abgasreinigung von Ottomotoren begann gleichzeitig die Diskussion ueber moegliche Emissionen von Edelmetallen, insbesondere von Platin, sowie ueber ihre eventuell moeglichen negativen Wirkungen in der Umwelt. Zur Erforschung der Fragestellungen zur Art und Menge der emittierten Platinmetalle, ihrer Aufnahme und dem Uebergang in den Nahrungskreislauf, sowie zu ihrem toxikologischen und allergologischen Potential wurde der Forschungsverbund ``Edelmetallemissionen`` gegruendet. Um Aussagen ueber physiologische und toxikologische Einfluesse zu machen, war es notwendig, die chemischen Erscheinungsformen des Platins zu identifizieren und nachweisstarke Analysenmethoden zu entwickeln. Untersuchungen zu Platinkonzentrationen in Umweltproben deuten auf eine Bioverfuegbarkeit von ca. 10 % hin. (ABI)

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

    Directory of Open Access Journals (Sweden)

    Christopher Knoblauch

    2014-10-01

    Full Text Available 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.

  20. Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.

    2015-08-25

    Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic properties by altering the pH. We have utilized the oxygen functional moieties such as carboxylate, epoxide, and hydroxyl groups on the edge and basal planes of the GO for binding the Cu2+ ions through dative bonds. The GO-Cu2+ hybrid materials were characterized by cyclic voltammetry in sodium acetate buffer solution. The morphology of the hybrid GO-Cu2+ was characterized by atomic force microscopy. The GO-Cu2+ hybrid electrodes show good electrocatalytic activity for HER with low overpotential in acidic solution. The Tafel slope for the GO-Cu2+ hybrid electrode implies that the primary discharge step is the rate determining step and HER proceed with Volmer step. © 2015 American Institute of Chemical Engineers Environ Prog.

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

    Science.gov (United States)

    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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. TiO2 promoted by two different non-noble metal cocatalysts for enhanced photocatalytic H2 evolution

    International Nuclear Information System (INIS)

    Lin, Jing-Dong; Yan, Shi; Huang, Qin-Dong; Fan, Mei-Ting; Yuan, You-Zhu; Tan, Timothy Thatt-Yang; Liao, Dai-Wei

    2014-01-01

    TiO 2 photocatalysts modified by cobalt and nickel cocatalysts were prepared via polymerized complex method (PCM) and evaluated by photocatalytic hydrogen evolution. Hydrogen generation in 6 h for the TiO 2 promoted by cobalt and nickel (0.1%Co + 0.2%Ni/TiO 2 ) is about two times (2456 μmol H 2 ) compared to that of TiO 2 promoted only by cobalt (1180 μmol H 2 for 0.1%Co/TiO 2 ) or nickel (1127 μmol H 2 for 0.2%Ni/TiO 2 ), and mechanically mixed TiO 2 promoted by cobalt and TiO 2 promoted by nickel (0.1%Co/TiO 2 :0.2%Ni/TiO 2 = 1:1 (m/m), 1282 μmol H 2 ). The high photocatalytic H 2 evolution activity over TiO 2 promoted by cobalt and nickel is ascribed to enhanced photo response due to the presence of cobalt and nickel impurity level, and effective separation of photogenerated electrons and holes due to the synergistic effect of cobalt and nickel, which serve as active sites for H 2 evolution reaction (HER) and oxidation reaction (OR) respectively. This study demonstrates a viable strategy to design more active photocatalysts for photocatalytic H 2 evolution by substituting noble metals with more abundant elements using as HER and OR cocatalysts, respectively.

  3. Noble Metal-Free Ceria-Zirconia Solid Solutions Templated by Tobacco Materials for Catalytic Oxidation of CO

    Directory of Open Access Journals (Sweden)

    Donglai Zhu

    2016-09-01

    Full Text Available A series of ceria-zirconia solid solutions were synthesized using tobacco leaves, stems and stem-silks as biotemplates. A combination of physicochemical techniques such as powder X-ray diffraction (XRD, N2 adsorption/desorption measurement, scanning electron microscopy (SEM, and transmission electron microscopy (TEM were used to characterize the as-synthesized samples. The results show that the morphologies of the templates were well replicated in the obtained ceria-zirconia solid solutions. Catalytic oxidation activities of CO over the ceria-zirconia solid solutions were then investigated. The catalyst templated by tobacco stem-silk exhibited higher conversion of CO at lower temperature than that of ceria-zirconia solid solutions templated by tobacco leaves and stems or without templates due to its special morphology. The catalyst even showed similar CO conversion when compared to ceria-zirconia solid solutions doped with 1.0 wt % noble metals such as Pt, Ag and Au. The results highlighted the advantages of using tobacco as biotemplate.

  4. Cobalt Nanoparticles Supported on Nitrogen-Doped Carbon: An Effective Non-Noble Metal Catalyst for the Upgrade of Biofuels.

    Science.gov (United States)

    Jiang, Liang; Zhou, Peng; Liao, Chanjuan; Zhang, Zehui; Jin, Shiwei

    2018-03-09

    A new method has been developed for the deoxygenation of vanillin to produce 2-methoxy-4-methylphenol (MMP) as a promising liquid fuel over a heterogeneous non-noble metal catalyst. Cobalt nanoparticles supported on nitrogen-doped carbon (Co/N-C-600) exhibit high activity and stability for the deoxygenation of vanillin into MMP under mild conditions (150 °C, 10 bar H 2 ). Nearly quantitative MMP yield is obtained in isopropanol after 8 h at 150 °C and 10 bar H 2 pressure. According to the distribution of products with time, the deoxygenation of vanillin into MMP mainly proceeds through the hydrogenation of vanillin into vanillyl alcohol and the subsequent hydrogenolysis of vanillyl alcohol into MMP, of which the latter is the rate-determining step, owing to a much higher activation energy. Moreover, after being recycled several times, the loss of catalytic activity is negligible, which demonstrates that the Co/N-C-600 catalyst shows good resistance to deactivation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Energy-Saving Electrolytic Hydrogen Generation: Ni2P Nanoarray as a High-Performance Non-Noble-Metal Electrocatalyst.

    Science.gov (United States)

    Tang, Chun; Zhang, Rong; Lu, Wenbo; Wang, Zao; Liu, Danni; Hao, Shuai; Du, Gu; Asiri, Abdullah M; Sun, Xuping

    2017-01-16

    It is highly attractive but challenging to develop earth-abundant electrocatalysts for energy-saving electrolytic hydrogen generation. Herein, we report that Ni 2 P nanoarrays grown in situ on nickel foam (Ni 2 P/NF) behave as a durable high-performance non-noble-metal electrocatalyst for hydrazine oxidation reaction (HzOR) in alkaline media. The replacement of the sluggish anodic oxygen evolution reaction with such the more thermodynamically favorable HzOR enables energy-saving electrochemical hydrogen production with the use of Ni 2 P/NF as a bifunctional catalyst for anodic HzOR and cathodic hydrogen evolution reaction. When operated at room temperature, this two-electrode electrolytic system drives 500 mA cm -2 at a cell voltage as low as 1.0 V with strong long-term electrochemical durability and 100 % Faradaic efficiency for hydrogen evolution in 1.0 m KOH aqueous solution with 0.5 m hydrazine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Quantum electron states and resonances in thin monocrystal layers of noble metals on W (110) substrate

    CERN Document Server

    Vyalykh, D V; Prudnikova, G V; Grigoriev, A Y; Starodubov, A G; Adamchuk, V K

    2002-01-01

    For the first time in monocrystal layers of gold, silver and copper formed at W (110) single crystal surface one observed experimentally electron states and resonances of s p-type. They resulted from spatial localization of the Bloch type electron wave functions in quantum pit with potential barriers formed by vacuum/metal and metal/W (110) interfaces. One applied photoelectron spectroscopy with angular resolution to investigate experimentally into quantization of an electron structure of a valence band in Au/W (110), Ag/W (110) and Cu/W (110) systems

  7. Oxidative coupling of 1-naphthols over noble and base metal catalysts

    CSIR Research Space (South Africa)

    Maphoru, MV

    2014-01-01

    Full Text Available by the competitive cleavage of one of the two O[BOND]Me bonds at higher temperature. Unpromoted platinum and a range of other metallic catalysts, including gold and Raney nickel, were also found to be active. The products obtained are brightly colored solids...

  8. Oxygen permeation through oxygen ion oxide-noble metal dual phase composites

    NARCIS (Netherlands)

    Chen, C.S.; Chen, C.S.; Kruidhof, H.; Bouwmeester, Henricus J.M.; Verweij, H.; Burggraaf, Anthonie; Burggraaf, A.J.

    1996-01-01

    Oxygen permeation behaviour of three composites, yttria-stabilized zirconia-palladium, erbia-stabilized bismuth oxidenoble metal (silver, gold) was studied. Oxygen permeation measurements were performed under controlled oxygen pressure gradients at elevated temperatures. Air was supplied at one side

  9. Highly stable noble-metal nanoparticles in tetraalkylphosphonium ionic liquids for in situ catalysis.

    Science.gov (United States)

    Banerjee, Abhinandan; Theron, Robin; Scott, Robert W J

    2012-01-09

    Gold and palladium nanoparticles were prepared by lithium borohydride reduction of the metal salt precursors in tetraalkylphosphonium halide ionic liquids in the absence of any organic solvents or external nanoparticle stabilizers. These colloidal suspensions remained stable and showed no nanoparticle agglomeration over many months. A combination of electrostatic interactions between the coordinatively unsaturated metal nanoparticle surface and the ionic-liquid anions, bolstered by steric protection offered by the bulky alkylated phosphonium cations, is likely to be the reason behind such stabilization. The halide anion strongly absorbs to the nanoparticle surface, leading to exceptional nanoparticle stability in halide ionic liquids; other tetraalkylphosphonium ionic liquids with non-coordinating anions, such as tosylate and hexafluorophosphate, show considerably lower affinities towards the stabilization of nanoparticles. Palladium nanoparticles stabilized in the tetraalkylphosphonium halide ionic liquid were stable, efficient, and recyclable catalysts for a variety of hydrogenation reactions at ambient pressures with sustained activity. Aerial oxidation of the metal nanoparticles occurred over time and was readily reversed by re-reduction of oxidized metal salts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Study of interaction of ethylene glycol/PVP phase on noble metal ...

    Indian Academy of Sciences (India)

    They have been characterized by both microscopic (TEM and SEM) as well as spectroscopic techniques (FT-IR and XPS). Infrared spectroscopy was employed to study the colloid particles in the presence of ethylene glycol and PVP and the results show that the interaction between the organic phase and the metal particles ...

  11. Properties and modification of two-dimensional electronic states on noble metals; Eigenschaften und Modifikation zweidimensionaler Elektronenzustaende auf Edelmetallen

    Energy Technology Data Exchange (ETDEWEB)

    Forster, F.

    2007-07-06

    In this thesis investigations on two-dimensional electronic structures of (111)-noble metal surfaces and the influence of various adsorbates upon them is presented. It chiefly focuses on the surface-localized Shockley states of Cu, Ag and Au and their band dispersion (binding energy, band mass, and spin-orbit splitting) which turns out to be a sensitive probe for surface modifications induced by adsorption processes. Angular resolved photoelectron spectroscopy enables the observation of even subtle changes in the electronic band structure of these two dimensional systems. Different mechanisms taking place at surfaces and the substrate/adsorbate interfaces influence the Shockley state in a different manner and will be analyzed using suitable adsorbate model systems. The experimental results are matched with appropriate theoretical models like the phase accumulation model and the nearly-free electron model and - if possible - with ab initio calculations based on density functional theory. This allows for the integration of the results into a stringent overall picture. The influence of sub-monolayer adsorption of Na upon the surface state regarding the significant change in surface work function is determined. A systematic study of the physisorption of noble gases shows the effect of the repulsive adsorbate-substrate interaction upon the electrons of the surface state. A step-by-step coverage of the Cu and Au(111) surfaces by monolayers of Ag creates a gradual change in the surface potential and causes the surface state to become increasingly Ag-like. For N=7 ML thick and layer-by-layer growing Ag films on Au(111), new two-dimensional electronic structures can be observed, which are attributed to the quantum well states of the Ag adsorbate. The question whether they are localized within the Ag-layer or substantially within the substrate is resolved by the investigation of their energetic and spatial evolution with increasing Ag-film thicknesses N. For this, beside the

  12. Ni/CeO{sub 2}-Al{sub 2}O{sub 3} catalysts promoted with noble metals for the hydrogen production by ethanol vapor reforming; Catalisadores de Ni/CeO{sub 2}-Al{sub 2}O{sub 3} promovidos com metais nobres para a producao de hidrogenio por reforma a vapor de etanol

    Energy Technology Data Exchange (ETDEWEB)

    Profeti, Luciene P.R.; Ticianelli, Edson Antonio; Assaf, Elisabete Moreira [Universidade de Sao Paulo (IQSC/USP), Sao Carlos, SP (Brazil). Inst. de Quimica]. E-mail: eassaf@iqsc.usp.br

    2008-07-01

    The catalytic activity of Ni/CeO{sub 2}-Al{sub 2}O{sub 3} catalysts modified with noble metals (Ru, Ir, Pt and Pd) was investigated in the steam reforming of ethanol. The catalysts were characterized by energy dispersive spectroscopy, X-ray diffraction, UV-Vis diffuse reflectance spectroscopy and H{sub 2} temperature-programmed reduction-X-ray absorption fine structure (XANES). The results showed that the formation of inactive nickel aluminate was avoided due to the presence of a CeO{sub 2} dispersed on the alumina. The promoting effect of noble metals included a decrease of the reduction temperatures of NiO species interacting with the support due to the hydrogen spillover effect, leading to an increase of the reducibilities of the promoted catalysts The better catalytic performance for the ethanol steam reforming was obtained for the NiPd/CeAl catalyst, which presented an effluent gaseous mixture with the highest H{sub 2} yield. (author)

  13. Effect of electric arc, gas oxygen torch and induction melting techniques on the marginal accuracy of cast base-metal and noble metal-ceramic crowns.

    Science.gov (United States)

    Gómez-Cogolludo, Pablo; Castillo-Oyagüe, Raquel; Lynch, Christopher D; Suárez-García, María-Jesús

    2013-09-01

    The aim of this study was to identify the most appropriate alloy composition and melting technique by evaluating the marginal accuracy of cast metal-ceramic crowns. Seventy standardised stainless-steel abutments were prepared to receive metal-ceramic crowns and were randomly divided into four alloy groups: Group 1: palladium-gold (Pd-Au), Group 2: nickel-chromium-titanium (Ni-Cr-Ti), Group 3: nickel-chromium (Ni-Cr) and Group 4: titanium (Ti). Groups 1, 2 and 3 were in turn subdivided to be melted and cast using: (a) gas oxygen torch and centrifugal casting machine (TC) or (b) induction and centrifugal casting machine (IC). Group 4 was melted and cast using electric arc and vacuum/pressure machine (EV). All of the metal-ceramic crowns were luted with glass-ionomer cement. The marginal fit was measured under an optical microscope before and after cementation using image analysis software. All data was subjected to two-way analysis of variance (ANOVA). Duncan's multiple range test was run for post-hoc comparisons. The Student's t-test was used to investigate the influence of cementation (α=0.05). Uncemented Pd-Au/TC samples achieved the best marginal adaptation, while the worst fit corresponded to the luted Ti/EV crowns. Pd-Au/TC, Ni-Cr and Ti restorations demonstrated significantly increased misfit after cementation. The Ni-Cr-Ti alloy was the most predictable in terms of differences in misfit when either torch or induction was applied before or after cementation. Cemented titanium crowns exceeded the clinically acceptable limit of 120μm. The combination of alloy composition, melting technique, casting method and luting process influences the vertical seal of cast metal-ceramic crowns. An accurate use of the gas oxygen torch may overcome the results attained with the induction system concerning the marginal adaptation of fixed dental prostheses. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Competing interactions of noble metals and fullerenes with the Si(111)7x7 surface

    International Nuclear Information System (INIS)

    O'Shea, J.N.; Phillips, M.A.; Taylor, M.D.R.; Beton, P.H.; Moriarty, P.; Kanai, M.; Dennis, T.S.J.; Dhanak, V.R.

    2004-01-01

    Full text: Synchrotron-based photoelectron spectroscopy (PES) has been used to investigate the interaction of atomic gold and silver with a covalently bound C 60 -monolayer adsorbed on Si(111)7x7. In contrast to the relatively benign interaction of silver with the C 60 /Si(111)7x7 surface, core-level photoemission data reveal a strong interaction of the gold with the underlying silicon despite the presence of a chemisorbed fullerene monolayer. The Si 2p PES data exhibit dramatic changes consistent with the formation of a gold silicide, which is also evident from the corresponding Au 4f spectra. Valence band photoemission also reveals the absence of appreciable density of states at the Fermi level following the adsorption of either metal, indicating a negligible transfer of electrons from the adsorbed metal to the C 60 cage

  15. Non-Noble Metal Oxide Catalysts for Methane Catalytic Combustion: Sonochemical Synthesis and Characterisation.

    Science.gov (United States)

    Jodłowski, Przemysław J; Jędrzejczyk, Roman J; Chlebda, Damian K; Dziedzicka, Anna; Kuterasiński, Łukasz; Gancarczyk, Anna; Sitarz, Maciej

    2017-07-07

    The aim of this study was to obtain nanocrystalline mixed metal-oxide-ZrO₂ catalysts via a sonochemically-induced preparation method. The effect of a stabiliser's addition on the catalyst parameters was investigated by several characterisation methods including X-ray Diffraction (XRD), nitrogen adsorption, X-ray fluorescence (XRF), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and µRaman. The sonochemical preparation method allowed us to manufacture the catalysts with uniformly dispersed metal-oxide nanoparticles at the support surface. The catalytic activity was tested in a methane combustion reaction. The activity of the catalysts prepared by the sonochemical method was higher than that of the reference catalysts prepared by the incipient wetness method without ultrasonic irradiation. The cobalt and chromium mixed zirconia catalysts revealed their high activities, which are comparable with those presented in the literature.

  16. Study of conditions of production and characterization of noble metal micro-particles suspensions

    International Nuclear Information System (INIS)

    Malabre, Catherine

    1983-01-01

    As the production and identification of metal micro-particle suspensions are some aspects of issues related to nuclear fuel reprocessing, this research thesis reports the use of ruthenium, molybdenum, niobium, palladium and rhodium (fission metals) to generate such micro-particles. They are produced by erosion of two electrodes between which occurs an electric arc discharge in aqueous media. Different analytic methods are developed to determine the characteristics of so-produced colloidal solutions. A granulometry study is performed by transmission electronic microscopy, light quasi-elastic scattering, and turbidimetry associated to centrifugation. This has lead to the production of steady micro-particle suspensions which have been used in a first set of industrial trials [fr

  17. Physical properties of Pd and Al transition metals and Pd-Al binary metal alloy investigated by using molecular dynamics simulation

    International Nuclear Information System (INIS)

    Coruh, A.; Uludogan, M.; Tomak, M.; Cagin, T.

    2002-01-01

    In this study, physical properties, such as Pair Distribution Function g(r), Structure Factor S(k)''1'',''4, Diffusion Coefficient D''2''.''4, Intermediate Scattering function S(k,t)''3'',''4 and Dynamical Structure Factor S(k,w)''3'',''4 of some transition metals and metal alloys are investigated by using molecular dynamics simulation method. The simulation is specified for Pd, Al transition metals and Pd-Al binary metal alloys in the liquid form for different concentrations and at various temperatures by using Quantum Sutton-Chen (Q-SC) inter atomic potential. Intermediate scattering function and dynamical structure factor are calculated for various values of wave vector k. Results are in good agreement with published data''1'',''3'',''4

  18. One-Pot Synthesis of Monodisperse Noble Metal @ Resorcinol-Formaldehyde (M@RF) and M@Carbon Core-Shell Nanostructure and Their Catalytic Applications.

    Science.gov (United States)

    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.

  19. Beneficial effects of microwave-assisted heating versus conventional heating in noble metal nanoparticle synthesis.

    Science.gov (United States)

    Dahal, Naween; García, Stephany; Zhou, Jiping; Humphrey, Simon M

    2012-11-27

    An extensive comparative study of the effects of microwave versus conventional heating on the nucleation and growth of near-monodisperse Rh, Pd, and Pt nanoparticles has revealed distinct and preferential effects of the microwave heating method. A one-pot synthetic method has been investigated, which combines nucleation and growth in a single reaction via precise control over the precursor addition rate. Using this method, microwave-assisted heating enables the convenient preparation of polymer-capped nanoparticles with improved monodispersity, morphological control, and higher crystallinity, compared with samples heated conventionally under otherwise identical conditions. Extensive studies of Rh nanoparticle formation reveal fundamental differences during the nucleation phase that is directly dependent on the heating method; microwave irradiation was found to provide more uniform seeds for the subsequent growth of larger nanostructures of desired size and surface structure. Nanoparticle growth kinetics are also markedly different under microwave heating. While conventional heating generally yields particles with mixed morphologies, microwave synthesis consistently provides a majority of tetrahedral particles at intermediate sizes (5-7 nm) or larger cubes (8+ nm) upon further growth. High-resolution transmission electron microscopy indicates that Rh seeds and larger nanoparticles obtained from microwave-assisted synthesis are more highly crystalline and faceted versus their conventionally prepared counterparts. Microwave-prepared Rh nanoparticles also show approximately twice the catalytic activity of similar-sized conventionally prepared particles, as demonstrated in the vapor-phase hydrogenation of cyclohexene. Ligand exchange reactions to replace polymer capping agents with molecular stabilizing agents are also easily facilitated under microwave heating, due to the excitation of polar organic moieties; the ligand exchange proceeds with excellent retention of

  20. Noble-metal nanoparticles produced with colloidal lithography: fabrication, optical properties and applications

    Energy Technology Data Exchange (ETDEWEB)

    Bocchio, Noelia Laura

    2008-08-15

    In this work, metal nanoparticles produced by nanosphere lithography were studied in terms of their optical properties (in connection to their plasmon resonances), their potential application in sensing platforms - for thin layer sensing and bio-recognition events -, and for a particular case (the nanocrescents), for enhanced spectroscopy studies. The general preparation procedures introduced early in 2005 by Shumaker-Parry et al. to produce metallic nanocrescents were extended to give rise to more complex (isolated) structures, and also, by combining colloidal monolayer fabrication and plasma etching techniques, to arrays of them. The fabrication methods presented in this work were extended not only to new shapes or arrangements of particles, but included also a targeted surface tailoring of the substrates and the structures, using different thiol and silane compounds as linkers for further attachment of, i.e. polyelectrolyte layers, which allow for a controlled tailoring of their nanoenvironment. The optical properties of the nanocrescents were studied with conventional transmission spectroscopy; a simple multipole model was adapted to explain their behaviour qualitatively. In terms of applications, the results on thin film sensing using these particles show that the crescents present an interesting mode-dependent sensitivity and spatial extension. Parallel to this, the penetrations depths were modeled with two simplified schemes, obtaining good agreement with theory. The multiple modes of the particles with their characteristic decay lengths and sensitivities represent a major improvement for particle-sensing platforms compared to previous single resonance systems. The nanocrescents were also used to alter the emission properties of fluorophores placed close to them. In this work, green emitting dyes were placed at controlled distances from the structures and excited using a pulsed laser emitting in the near infrared. The fluorescence signal obtained in this

  1. Decoration of size-tunable CuO nanodots on TiO2 nanocrystals for noble metal-free photocatalytic H2 production

    Science.gov (United States)

    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

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

    Science.gov (United States)

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

    2008-01-01

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

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

    Science.gov (United States)

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

    2011-01-01

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

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

    OpenAIRE

    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 us...

  5. Three-dimensional characterization of noble-metal nanoparticles and their assemblies by electron tomography.

    Science.gov (United States)

    Bals, Sara; Goris, Bart; Liz-Marzán, Luis M; Van Tendeloo, Gustaaf

    2014-09-26

    New developments in the field of nanomaterials drive the need for quantitative characterization techniques that yield information down to the atomic scale. In this Review, we focus on the three-dimensional investigations of metal nanoparticles and their assemblies by electron tomography. This technique has become a versatile tool to understand the connection between the properties and structure or composition of nanomaterials. The different steps of an electron tomography experiment are discussed and we show how quantitative three-dimensional information can be obtained even at the atomic scale. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Supported noble metal catalysts in the catalytic wet air oxidation of industrial wastewaters and sewage sludges.

    Science.gov (United States)

    Besson, M; Descorme, C; Bernardi, M; Gallezot, P; di Gregorio, F; Grosjean, N; Minh, D Pham; Pintar, A

    2010-12-01

    This paper reviews some catalytic wet air oxidation (CWAO) investigations of industrial wastewaters over platinum and ruthenium catalysts supported on TiO2 and ZrO2 formulated to be active and resistant to leaching, with particular focus on the stability of the catalyst. Catalyst recycling experiments were performed in batch reactors and long-term stability tests were conducted in trickle-bed reactors. The catalyst did not leach upon treatment of Kraft bleaching plant and olive oil mill effluents, and could be either recycled or used for long periods of time in continuous reactors. Conversely, these catalysts were rapidly leached when used to treat effluents from the production of polymeric membranes containing N,N-dimethylformamide. The intermediate formation of amines, such as dimethylamine and methylamine with a high complexing capacity for the metal, was shown to be responsible for the metal leaching. These heterogeneous catalysts also deactivated upon CWAO of sewage sludges due to the adsorption of the solid organic matter. Pre-sonication of the sludge to disintegrate the flocs and improve solubility was inefficient.

  7. Plasmon-Mediated Solar Energy Conversion via Photocatalysis in Noble Metal/Semiconductor Composites.

    Science.gov (United States)

    Wang, Mengye; Ye, Meidan; Iocozzia, James; Lin, Changjian; Lin, Zhiqun

    2016-06-01

    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.

  8. Plasmon‐Mediated Solar Energy Conversion via Photocatalysis in Noble Metal/Semiconductor Composites

    Science.gov (United States)

    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. PMID:27818901

  9. Bifunctional metal-free catalysis of mesoporous noble carbons for oxygen reduction and evolution reactions.

    Science.gov (United States)

    Sakaushi, Ken; Fellinger, Tim-Patrick; Antonietti, Markus

    2015-04-13

    Electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are key reactions in lithium-oxygen batteries (LOBs) being a promising candidate to store renewable energies due to their high specific energy. However current development on LOBs is suffering from unsuitable catalysts. In particular, carbon-based catalysts were found to perform poorly in this system. Here, we show that metal-free mesoporous nitrogen-doped carbons (meso-NdCs) offer highly promising performances in both ORR and OER; they act as bifunctional catalysts, and can be synthesized by a very simple method. The efficient electrocatalytic activity of ORR and OER was used in a LOB cell during discharge and charge, respectively, and the present system showed a lower overpotential comparable to metal-based catalysts in LOB system. Thus, we demonstrate that meso-NdCs act as a new and affordable candidate for the efficient bifunctional oxygen catalysis, therefore can be applied to many energy-related applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2012-08-01

    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.

  12. Rubber effect and stabilization of martensites in noble metal based alloys

    International Nuclear Information System (INIS)

    Marukawa, K.; Takezawa, K.; Hoshi, H.

    1999-01-01

    In a previous paper, it has been pointed out that the rubber effect and stabilization of the martensite phase are caused by short range reordering during aging [K. Marukawa, K. Tsuchiya, Scripta Metall. Mater. 32 (1995) 77]. This view was further examined by experimental and theoretical studies. It has been found that the change in electrical resistivity produced by aging is well correlated with magnitudes of these effects. The relation between the short range order parameters and the representative quantities of these effects was formulated on the basis of thermodynamics. Quantitative evaluation was performed by numerical calculations utilizing the Monte Carlo method. It was found that the rubber effect is prominent when the aging temperature is in the vicinity of the order-disorder transition temperature. It was also shown that in most cases disordering or lowering in the long range order causes the stabilization. (orig.)

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

    Science.gov (United States)

    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

  14. Mechanical properties, fracture surface characterization, and microstructural analysis of six noble dental casting alloys.

    Science.gov (United States)

    Ucar, Yurdanur; Brantley, William A; Johnston, William M; Dasgupta, Tridib

    2011-06-01

    Because noble dental casting alloys for metal ceramic restorations have a wide range of mechanical properties, knowledge of these properties is needed for rational alloy selection in different clinical situations where cast metal restorations are indicated. The purpose of this study was to compare the mechanical properties and examine both the fracture and polished surfaces of 6 noble casting alloys that span many currently marketed systems. Five alloys were designed for metal ceramic restorations, and a sixth Type GPT has Type IV alloy for fixed prosthodontics (Maxigold KF) was included for comparison. Specimens (n=6) meeting dimensional requirements for ISO Standards 9693 and 8891 were loaded to failure in tension using a universal testing machine at a crosshead speed of 2 mm/min. Values of 0.1% and 0.2% yield strength, ultimate tensile strength, elastic modulus, and percentage elongation were obtained. Statistical comparisons of the alloy mechanical properties were made using 1-way ANOVA and the REGW multiple-range test (α=.05). Following fracture surface characterization using scanning electron microscopy (SEM), specimens were embedded in epoxy resin, polished, and again, examined with the SEM. When the multiple comparisons were considered, there were generally no significant differences in the elastic modulus, 0.1% and 0.2% offset yield strength, and ultimate tensile strength for the d.SIGN 91 (Au-Pd), d.SIGN 59 (Pd-Ag), Capricorn 15 (Pd-Ag-Au) and Maxigold KF (Au-Ag-Pd) alloys, except that the ultimate tensile strength was significantly lower (PAg-Pd alloys. Wide variation was found in percentage elongation, with the Pd-Ag and Pd-Ag-Au alloys having the highest values and the Au-Pd-Pt and Au-Ag-Pd alloys having the lowest values. Copyright © 2011 The Editorial Council of the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, X. J.; Xue, X. L.; Jia, Yu [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Guo, Z. X. [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Department of Chemistry and London Centre for Nanotechnology, University College London, London WC1H (United Kingdom); Li, S. F., E-mail: sflizzu@zzu.edu.cn [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); ICQD, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Zhang, Zhenyu, E-mail: zhangzy@ustc.edu.cn [ICQD, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Gao, Y. F., E-mail: ygao7@utk.edu [Department of Materials Science and Engineering, University of Tennessee, Knoxville, Tennessee 37996 (United States); Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    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.

  16. The effect of noble metals on catalytic methanation reaction over supported Mn/Ni oxide based catalysts

    Directory of Open Access Journals (Sweden)

    Wan Azelee Wan Abu Bakar

    2015-09-01

    Full Text Available Carbon dioxide (CO2 in sour natural gas can be removed using green technology via catalytic methanation reaction by converting CO2 to methane (CH4 gas. Using waste to wealth concept, production of CH4 would increase as well as creating environmental friendly approach for the purification of natural gas. In this research, a series of alumina supported manganese–nickel oxide based catalysts doped with noble metals such as ruthenium and palladium were prepared by wetness impregnation method. The prepared catalysts were run catalytic screening process using in-house built micro reactor coupled with Fourier Transform Infra Red (FTIR spectroscopy to study the percentage CO2 conversion and CH4 formation analyzed by GC. Ru/Mn/Ni(5:35:60/Al2O3 calcined at 1000 °C was found to be the potential catalyst which gave 99.74% of CO2 conversion and 72.36% of CH4 formation at 400 °C reaction temperature. XRD diffractogram illustrated that the supported catalyst was in polycrystalline with some amorphous state at 1000 °C calcination temperature with the presence of NiO as active site. According to FESEM micrographs, both fresh and used catalysts displayed spherical shape with small particle sizes in agglomerated and aggregated mixture. Nitrogen Adsorption analysis revealed that both catalysts were in mesoporous structures with BET surface area in the range of 46–60 m2/g. All the impurities have been removed at 1000 °C calcination temperature as presented by FTIR, TGA–DTA and EDX data.

  17. Preparation and immobilization of noble metal nanoparticles for plasmonic solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ruoli; Pitzer, Martin; Hu, DongZhi; Schaadt, Daniel M. [Institut fuer Angewandte Physik, Karlsruher Institut fuer Technologie (KIT), Karlsruhe (Germany); DFG Centrum fuer Funktionelle Nanostrukturen (CFN), KIT (Germany); Fruk, Ljiljana [DFG Centrum fuer Funktionelle Nanostrukturen (CFN), KIT (Germany)

    2011-07-01

    Thin-film solar cells are of high interest due to good electrical properties and low material consumption. Traditional thin-film cells, however, have considerable transmission losses because of the reduced absorption volume. A promising way to enhance absorption in the active layer is the light-trapping by plasmonic nanostructures. Metallic nanoparticles have in particular shown large enhancement of the photocurrent in thin-film devices. In this poster, we present preparation of Au,Ag and Pt nanoparticles by polyol method and seed mediated methods for use in plasmonic solar cells. Polyol method typically uses ethylene glycol as the solvent and reducing agent,and in seed-mediated synthesis small nanoparticle seeds are first prepared and then used to promote the growth of different shapes of nanoparticles. We particularly focus on the use of nanocubes and nanospheres for solar cell design. Following the nanoparticle preparation, a new method to immobilize particles on GaAs surfaces via covalent chemical bonds has been developed which prevents agglomerations and allows control of the surface density. Photocurrent spectra of GaAs pin solar cells with and without particles have been recorded. These measurements show the dependence of the photocurrent enhancement on particle material, shape and density.

  18. Sputter fabricated Nb-oxide-Nb josephson junctions incorporating post-oxidation noble metal layers

    International Nuclear Information System (INIS)

    Bain, R.J.P.; Donaldson, G.B.

    1985-01-01

    We present an extension, involving other metals, of the work of Hawkins and Clarke, who found that a thin layer of copper prevented the formation of the superconductive shorts which are an inevitable consequence of sputtering niobium counter-electrodes directly on top of niobium oxide. We find gold to be the most satisfactory, and that 0.3 nm is sufficient to guarantee short-free junctions of excellent electrical and mechanical stability, though high excess conductance means they are best suited to shunted-junction applications, as in SQUIDs. We present results for critical current dependence on oxide thickness and on gold thickness. Our data shows that thermal oxide growth is described by the Cabrera-Mott mechanism. We show that the protective effect of the gold layer can be understood in terms of the electro-chemistry of the Nb-oxide-Au structure, and that the reduced quasi-particle resistance of the junctions relative to goldfree junctions with evaporated counterelectrodes can be explained in terms of barrier shape modification, and not by proximity effect mechanisms. The performance of a DC SQUID based on these junctions is described

  19. Principles and Methods for the Rational Design of Core-Shell Nanoparticle Catalysts with Ultralow Noble Metal Loadings.

    Science.gov (United States)

    Hunt, Sean T; Román-Leshkov, Yuriy

    2018-03-06

    Conspecuts Commercial and emerging renewable energy technologies are underpinned by precious metal catalysts, which enable the transformation of reactants into useful products. However, the noble metals (NMs) comprise the least abundant elements in the lithosphere, making them prohibitively scarce and expensive for future global-scale technologies. As such, intense research efforts have been devoted to eliminating or substantially reducing the loadings of NMs in various catalytic applications. These efforts have resulted in a plethora of heterogeneous NM catalyst morphologies beyond the traditional supported spherical nanoparticle. In many of these new architectures, such as shaped, high index, and bimetallic particles, less than 20% of the loaded NMs are available to perform catalytic turnovers. The majority of NM atoms are subsurface, providing only a secondary catalytic role through geometric and ligand effects with the active surface NM atoms. A handful of architectures can approach 100% NM utilization, but severe drawbacks limit general applicability. For example, in addition to problems with stability and leaching, single atom and ultrasmall cluster catalysts have extreme metal-support interactions, discretized d-bands, and a lack of adjacent NM surface sites. While monolayer thin films do not possess these features, they exhibit such low surface areas that they are not commercially relevant, serving predominantly as model catalysts. This Account champions core-shell nanoparticles (CS NPs) as a vehicle to design highly active, stable, and low-cost materials with high NM utilization for both thermo- and electrocatalysis. The unique benefits of the many emerging NM architectures could be preserved while their fundamental limitations could be overcome through reformulation via a core-shell morphology. However, the commercial realization of CS NPs remains challenging, requiring concerted advances in theory and manufacturing. We begin by formulating seven

  20. Formation and Mechanical Properties of Pd-Si Binary Bulk Metallic Glasses

    Directory of Open Access Journals (Sweden)

    Na Chen

    2014-01-01

    Full Text Available Glassy spherical samples in the diameters up to 10 mm were produced in a binary Pd-Si alloy system. These Pd-Si bulk metallic glasses (BMGs combine high strength of about 1600 MPa and superplasticity of over 70% together. In addition to abundant micrometer-scale shear bands, 10–20 nanometer-sized shear bands were also observed on the side surface of the deformed sample. The excellent ductility shown by the Pd-Si BMGs is suggested to arise from the nanoscale structural inhomogeneity.

  1. A survey on the effects of repeated porcelain firing cycles on the marginal integrity of shoulder porcelain made of noble and base-metal alloys

    Directory of Open Access Journals (Sweden)

    Khodadadi R.

    2004-08-01

    Full Text Available Statement of Problem: In order to eliminate the esthetic problem of metal collar in porcelain fused to metal crowns various techniques, such as shoulder porcelain, have been suggested. Purpose: The aim of this study was to investigate the effects of repeated porcelain firing cycles on the marginal integrity of shoulder in porcelain fused to metal crowns, made of two kinds of alloys: noble and base-metal. Materials and Methods: In this experimental study, four groups of ten brazen models (Die were used. Metal crowns of groups A&B were made of a noble alloy and those of C&D of a base-metal alloy. Groups A&C had the shoulder width of 1mm and groups B&D had the shoulder width of 1.5mm. After degassing and opaqing, shoulder porcelain was completed in the area of shoulder. At this stage, the average vertical gap of margin was measured by a reflective microscope (400. Data were analyzed using ANOVA and Duncan tests. Results: No simoltaneouse interaction between the type of alloy and the shoulder width was found (P=0.709. The type of alloy had a significant effect on marginal integrity (P=0.021 attributing the best marginal integrity of shoulder porcelain to base-metal alloys. Shoulder width played also a significant role on marginal integrity (P=0.00 indicating that the reduction of shoulder width would increase the marginal integrity. Conclusion: According to these findings, the best marginal integrity of shoulder porcelain is achieved through shoulder width of 1mm along with base-metal alloys.

  2. Stabilisation of late transition metal and noble metal films in hexagonal and body centred tetragonal phases by epitaxial growth

    Energy Technology Data Exchange (ETDEWEB)

    Hueger, E.

    2005-08-26

    In this work ultrathin metallic films with a crystal phase different to their natural bulk structure were produced by hetero-epitaxial growth on metallic substrates. A further aim of this work was to understand the initiation, growth and stability of crystal phase modifications of these films. there exist cases where the films turn beyond the pseudomorphic-growth to a crystal phase different from their natural bulk structure. The present work presents and discusses such a case in addition to the general phenomenon of pseudomorphic-growth. In particular it is shown that metals whose natural phase is face centred cubic (fcc) can be grown in body centred tetragonal (bct) or hexagonal close packed (hcp) phases in the form of thin films on (001) surfaces of appropriate substrates. The growth behavior, electron diffraction analysis, appearance conditions, geometric fit considerations, examples and a discussion of the phase stability of non-covered films and superlattices is given reviewing all epitaxial-systems whose diffraction pattern can be explained by the hexagonal or pseudomorphic bct phase. (orig.)

  3. Catalytic Conversion of Short-Chain Alcohols on Atomically Dispersed Au and Pd Supported on Nanoscale Metal Oxides

    Science.gov (United States)

    Wang, Chongyang

    dehydrogenation of ethanol. Bare ZnZrOx activate ethanol conversion in the range of 280-300°C and produce undesired ethylene as product of ethanol dehydration, whereas, addition of small amount of gold (product distribution in the low-temperature range (200°C-350°C). As gold passivates the strong Bronsted acid sites of ZrO2 and selectively facilitates the dehydrogenation of ethanol at low-temperature, a wide temperature range was found between the production of acetaldehyde (dehydrogenation products) and ethylene (dehydration product), which can be harnessed for the industrial application. Interestingly, the steam reforming of ethanol did not take place in the low-temperature region, thus the selectivity to acetaldehyde and hydrogen was 100% even in the presence of water. In addition to gold, palladium was also studied in this thesis work on the ZnZrOx composite oxides, and its activity and selectivity were compared to Au/ZnZrOx. Monometallic Pd catalyzes the decomposition of methanol and ethanol, resulting in different product distribution for C 1-C2 alcohol reactions. With ZnZrOx employed as the catalyst support in this thesis work, the finely dispersed ZnO species in ZrO2 were found to alloy with the supported palladium under reduction treatment. Alloying with Zn tunes the chemistry of Pd to catalyze the SRM reaction through the methanol coupling mechanism, shutting off the undesired methanol decomposition pathway. A preliminary study of the Pd/ZnZrO x system for ethanol dehydrogenation also demonstrated the modification of Pd when in the PdZn alloy form. Different from the monometallic Pd catalyst, which primarily catalyzes the C-C bond scission of ethanol, high selectivity to ethanol dehydrogenation products was found on PdZn, over the temperature range of 200-400°C. Formation of the PdZn alloy broadens the application of Pd and potentially other Group VIII metals for selective alcohol conversion reactions. In summary, this thesis work has investigated two noble metals

  4. Promotion of Phenol Photodecomposition over TiO2 Using Au, Pd, and AuPd Nanoparticles

    DEFF Research Database (Denmark)

    Su, Ren; Tiruvalam, Ramchandra; He, Qian

    2012-01-01

    Noble metal nanoparticles (Au, Pd, AuPd alloys) with a narrow size distribution supported on nanocrystalline TiO2 (M/TiO2) have been synthesized via a sol-immobilization route. The effect of metal identity and size on the photocatalytic performance of M/TiO2 has been systematically investigated...... using phenol as a probe molecule. A different phenol degradation pathway was observed when using M/TiO2 catalysts as compared to pristine TiO2.We propose a mechanism to illustrate how the noble metal nanoparticles enhance the efficiency of phenol decomposition based on photoreduction of p......-benzoquinone under anaerobic conditions. Our results suggest that the metal nanoparticles not only play a role in capturing photogenerated electrons, but are strongly involved in the photocatalytic reaction mechanism. The analysis of the reaction intermediates allows us to conclude that on M/TiO2 undesired redox...

  5. An Fe(TCNQ)2nanowire array on Fe foil: an efficient non-noble-metal catalyst for the oxygen evolution reaction in alkaline media.

    Science.gov (United States)

    Xie, Maowen; Xiong, Xiaoli; Yang, Lin; Shi, Xifeng; Asiri, Abdullah M; Sun, Xuping

    2018-02-27

    It is highly desirable to develop efficient and durable oxygen evolution reaction (OER) electrocatalysts. Herein, we report the in situ development of an Fe-(tetracyanoquinodimethane) 2 nanowire array on Fe foil (Fe(TCNQ) 2 /Fe) via a solution immersion method. As a non-noble-metal OER electrocatalyst, such Fe(TCNQ) 2 /Fe needs an overpotential of only 340 mV to drive a geometrical catalytic current density of 10 mA cm -2 in 1.0 M KOH. Notably, it also shows strong long-term electrochemical durability capable of maintaining its catalytic activity for at least 110 h.

  6. Electronic Structure of the fcc Transition Metals Ir, Rh, Pt, and Pd

    DEFF Research Database (Denmark)

    Andersen, O. Krogh

    1970-01-01

    /atom)/Ry, respectively. Spin-orbit coupling is important for all four metals and the coupling parameter varies by 30% over the d bandwidth. Detailed comparisons with de Haas—van Alphen Fermi-surface dimensions have previously been presented and the agreement was very good. Comparison with measured electronic specific......We give a complete description of a relativistic augmented-plane-wave calculation of the band structures of the paramagnetic fcc transition metals Ir, Rh, Pt, and Pd. The width and position of the d band decrease in the sequence Ir, Pt, Rh, Pd; and N(EF)=13.8,23.2,18.7, and 32.7 (states...

  7. Structure determination of chitosan-stabilized Pt and Pd based bimetallic nanoparticles by X-ray photoelectron spectroscopy and transmission electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Lihua; Shafii, Salimah [Faculty of Industrial Science and Technology, Universiti Malaysia Pahang, 26300 Kuantan, Pahang (Malaysia); Nordin, Mohd Ridzuan, E-mail: mridzuan@ump.edu.my [Faculty of Industrial Science and Technology, Universiti Malaysia Pahang, 26300 Kuantan, Pahang (Malaysia); Liew, Kong Yong [Faculty of Industrial Science and Technology, Universiti Malaysia Pahang, 26300 Kuantan, Pahang (Malaysia); Li, Jinlin [Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, Hubei Province, South-Central University for Nationalities, 430074 Wuhan (China)

    2012-12-14

    Chitosan (CTS)-stabilized bimetallic nanoparticles were prepared at room temperature (rt.) in aqueous solution. Palladium (Pd) and platinum (Pt) were selected as the first metals while iron (Fe) and nickel (Ni) functioned as the second metals. In order to obtain the noble metal core-transition metal shell structures, bimetallic nanoparticles were prepared in a two-step process: the preparation of mono noble metallic (Pd or Pt) nanoparticles and the deposition of transition metals (Fe or Ni) on the surface of the monometallic nanoparticles. The structures of the nanoparticles were studied using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The XPS results show that Pd and Pt exist mainly in zero valences. The presence of Fe and Ni in the bimetallic nanoparticles affects the binding energy of Pd and Pt. Moreover, the studies of O 1s spectra indicate the presence of Fe or Ni shells. The analyses of TEM micrographs give the particle size and size distributions while the high-resolution TEM (HRTEM) micrographs show the existence of noble metal core lattices. The results confirm the formation of noble metal core-transition metal shell structures. -- Highlights: Black-Right-Pointing-Pointer Chitosan-stabilized bimetallic nanoparticles were prepared at room temperature in aqueous solution. Black-Right-Pointing-Pointer The presence of Fe or Ni shells was proven by XPS study. Black-Right-Pointing-Pointer The existence of noble metal cores covered by amorphous shells was indicated by TEM study. Black-Right-Pointing-Pointer The formation of noble metal core-transition metal shell structures was confirmed.

  8. Solvent and stabilizer free growth of Ag and Pd nanoparticles using metallic salts/cyclotriphosphazenes mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Díaz Valenzuela, C. [Departamento de Química, Facultad de Química, Universidad de Chile, La Palmeras 3425, Nuñoa, Casilla 653, Santiago de Chile (Chile); Valenzuela, M.L., E-mail: mlvalenzuela@unab.cl [Universidad Andres Bello, Departamento de Ciencias Química, Facultad de Ciencias Exactas, Av. Republica 275, Santiago (Chile); Caceres, S.; Diaz, R. [Departamento de Química, Facultad de Química, Universidad de Chile, La Palmeras 3425, Nuñoa, Casilla 653, Santiago de Chile (Chile); O' Dwyer, C. [Applied Nanoscience Group, Department of Chemistry, University College Cork, Cork (Ireland); Micro and Nanoelectronics Centre, Tyndall National Institute, Lee Maltings, Cork (Ireland)

    2013-12-16

    Cyclotriphosphazene is used as a sacrificial solid-state template to synthesize a range of Ag and Pd nanoparticles with diverse geometries by thermal treatment using MLn/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} mixtures. The Pd and Ag nanoparticles are synthesized by solid-state pyrolysis of AgPPh{sub 3}[CF{sub 3}SO{sub 3}]/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} and PdCl{sub 2}/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} mixtures with molar relationships of 1:1, 1:5 and 1:10 respectively, in air and at 800 °C. The morphology of the as-prepared nanoparticles is found to depend on the molar ratio of the precursor mixture, the preparation method and of the nature of the metal. Ag and Pd, microcrystals were thermally grown on Si from the respective 1:1 precursors while that metal foams were grown from 1:5 ratios precursors on SiO{sub 2} wafers. High resolution transmission electron microscopy investigations reveal in most cases small crystals of Pd. HRSTEM measurements indicate that the formation of the Pd and Ag nanoparticles occurs through a phase demixing and dewetting mechanism. This approach has potential to be a useful and facile method to prepare metallic nanoparticles without requiring solutions or surfactants for application in electronic, catalytic and sensor materials and devices. - Highlights: • Pyrolysis MLn/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} mixtures under air, give Pd and Ag nanoparticles. • AgPPh{sub 3}[CF{sub 3}SO{sub 3}] and PdCl{sub 2} in molar ratios 1:1 and 1:5 were used. • Metal foams were obtained from 1:5 ratios when deposited on SiO{sub 2.} • Using crucible supporting in 1:1 metal/trimer <2 nm Pd nanoparticles were obtained. • The probable mechanism involves a dewetting, nucleation and ripening crystallization.

  9. Hydrogen cold plasma for synthesizing Pd/C catalysts: the effect of support–metal ion interaction

    Science.gov (United States)

    Zhuang, LI; Xiuling, ZHANG; Yuzhuo, ZHANG; Dongzhi, DUAN; Lanbo, DI

    2018-01-01

    It has been found that cold plasma is a facile and environmentally benign method for synthesizing supported metal catalysts, and great efforts have been devoted to enlarging its applications. However, little work has been done to disclose the influence mechanism, which is significant for controllable synthesis. In this work, hydrogen cold plasma was adopted to synthesize a palladium catalyst supported on activated carbon (Pd/C-P) using H2PdCl4 as a Pd precursor followed by calcination in hydrogen gas to remove the chlorine ions. The Pd/C-P catalyst was found to be made of larger Pd nanoparticles showing a decreased migration to the support outer surface than that prepared by the conventional thermal hydrogen reduction method (Pd/C-C). Meanwhile, the pore diameter of the activated carbon support is small (∼4 nm). Therefore, Pd/C-P exhibits lower CO oxidation activity than Pd/C-C. It was proposed that the strong interaction between the activated carbon and {{{{PdCl}}}4}2-, and the enhanced metal–support interaction caused by hydrogen cold plasma reduction made it difficult for Pd nanoparticles to migrate to the support outer surface. The larger-sized Pd nanoparticles for Pd/C-P may be due to the Coulomb interaction resulting in the disturbance of the metal–support interaction. This work has important guiding significance for the controllable synthesis of supported metal catalysts by hydrogen cold plasma.

  10. TLC-SERS Plates with a Built-In SERS Layer Consisting of Cap-Shaped Noble Metal Nanoparticles Intended for Environmental Monitoring and Food Safety Assurance

    Directory of Open Access Journals (Sweden)

    H. Takei

    2015-01-01

    Full Text Available We report on a thin layer chromatograph (TLC with a built-in surface enhanced Raman scattering (SERS layer for in-situ identification of chemical species separated by TLC. Our goal is to monitor mixture samples or diluted target molecules suspended in a host material, as happens often in environmental monitoring or detection of food additives. We demonstrate that the TLC-SERS can separate mixture samples and provide in-situ SERS spectra. One sample investigated was a mixture consisting of equal portions of Raman-active chemical species, rhodamine 6 G (R6G, crystal violet (CV, and 1,2-di(4-pyridylethylene (BPE. The three components could be separated and their SERS spectra were obtained from different locations. Another sample was skim milk with a trace amount of melamine. Without development, no characteristic peaks were observed, but after development, a peak was observed at 694 cm−1. Unlike previous TLC-SERS whereby noble metal nanoparticles are added after development of a sample, having a built-in SERS layer greatly facilitates analysis as well as maintaining high uniformity of noble metal nanoparticles.

  11. Axial Changes of Catalyst Structure and Temperature in a Fixed-Bed Microreactor During Noble Metal Catalysed Partial Oxidation of Methane

    DEFF Research Database (Denmark)

    Hannemann, S.; Grunwaldt, Jan-Dierk; Kimmerle, B.

    2009-01-01

    The catalytic partial oxidation of methane (CPO) over flame-made 2.5%Rh-2.5%Pt/Al2O3 and 2.5%Rh/Al2O3 in 6%CH4/3%O-2/He shows the potential of in situ studies using miniaturized fixed-bed reactors, the importance of spatially resolved studies and its combination with infrared thermography and on......-line mass spectrometry. This experimental strategy allowed collecting data on the structure of the noble metal (oxidation state) and the temperature along the catalyst bed. The reaction was investigated in a fixed-bed quartz microreactor (1-1.5 mm diameter) following the catalytic performance by on-line gas...... mass spectrometry (MS). Above the ignition temperature of the catalytic partial oxidation of methane (310-330 A degrees C), a zone with oxidized noble metals was observed in the inlet region of the catalyst bed, accompanied by a characteristic hot spot (over-temperature up to 150 A degrees C), while...

  12. Mono- and bimetallic Rh and Pt NSR-catalysts prepared by controlled deposition of noble metals on support or storage component

    Science.gov (United States)

    Büchel, Robert; Pratsinis, Sotiris E.; Baiker, Alfons

    2013-01-01

    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

  13. Formation and magnetic properties of InFeP:Ag nano-rods fabricated with noble metal Ag using ion milling method.

    Science.gov (United States)

    Sohn, Jae Min; Kim, Hyungsang; Im, Hyunsik; Kim, Hyungbae; Lee, Juwon; Shon, Yoon; Subramaniam, Ganapathi; Kang, Tae Won; Kim, Deuk Young; Koo, Hyun Cheol; Lee, Joo-Hyeon; Song, Jin Dong; Park, Chang-Soo; Kim, Eun Kyu

    2017-11-03

    The formation including density, and height of InFeP:Ag nano-rods doped with noble metal Ag using ion milling method was preponderantly determined from TEM and XRD analyses. We investigate especially the enhanced ferromagnetism of the well aligned InFeP:Ag nano-rods. AES and XPS measurements were carried out in order to investigate the incorporation of Ag and to verify the local chemical bonding of InFeP:Ag nano-rods. The variation of FWHM for DCRC and TAD peaks demonstrates that noble metal Ag is incorporated into InFeP:Ag nano-rods. The noticeable ferromagnetic signature (M-H curve) of the InFeP:Ag nano-rods is observed and Tc persists up to near 350 K (3.9 × 10-4 emu/g) from temperature - dependence magnetization (M-T curve) measurements. This study suggests that the InFeP:Ag nano-rods should be a potential candidate for the application of spintronic devices. © 2017 IOP Publishing Ltd.

  14. Noble metal free photocatalytic H2 generation on black TiO2: On the influence of crystal facets vs. crystal damage

    Science.gov (United States)

    Liu, Ning; Steinrück, Hans-Georg; Osvet, Andres; Yang, Yuyun; Schmuki, Patrik

    2017-02-01

    In this study, we investigate noble metal free photocatalytic water splitting on natural anatase single crystal facets and on wafer slices of the [001] plane before and after these surfaces have been modified by high pressure hydrogenation and hydrogen ion-implantation. We find that on the natural, intact low index planes, photocatalytic H2 evolution (in the absence of a noble metal co-catalyst) can only be achieved when the hydrogenation treatment is accompanied by the introduction of crystal damage, such as simple scratching and miscut in the crystal, or by implantation damage. X-ray reflectivity, Raman, and optical reflection measurements show that plain hydrogenation leads to a ≈ 1 nm thick black titania surface layer without activity, while a colorless, density modified, and ≈7 nm thick layer with broken crystal symmetry is present on the ion implanted surface. These results demonstrate that (i) the H-treatment of an intact anatase surface needs to be combined with defect formation for catalytic activation and (ii) activation does not necessarily coincide with the presence of black color.

  15. Exfoliated carbon nitride nanosheets decorated with NiS as an efficient noble-metal-free visible-light-driven photocatalyst for hydrogen evolution.

    Science.gov (United States)

    Lu, Yongtao; Chu, Dongmei; Zhu, Mingshan; Du, Yukou; Yang, Ping

    2015-07-14

    A binary composite composed of two dimensional (2D) ultrathin carbon nitride (C3N4) nanosheets and NiS nanoparticles was synthesized and applied as a noble-metal-free photocatalyst for hydrogen evolution under visible light irradiation. The ultrathin nanosheets of C3N4 were obtained by a facile liquid exfoliation method and used as 2D supports for the deposition of NiS nanoparticles. In the binary composite, the ultrathin C3N4 nanosheets acted as a visible light responding semiconductor, and the NiS nanoparticles served as a noble-metal-free cocatalyst. The binary composite with an optimized composition gave a hydrogen evolution rate comparable to that of Pt modified C3N4. Moreover, compared to bulk C3N4, the exfoliated C3N4 nanosheets distinctly improve the photocatalytic performance for hydrogen evolution. The photocatalytic results combined with photoelectrochemical experiments show that C3N4 with an ultrathin structure promotes the electron-hole separation and transportation during the process of the photoinduced hydrogen evolution. This study displays a facile method to build a low-cost but effective photocatalyst for hydrogen production under visible light irradiation.

  16. Pressure effect on crystallization temperature in Zr70Pd30 metallic glass

    DEFF Research Database (Denmark)

    Jiang, Jianzhong; Jeppesen, S; Saida, J.

    2004-01-01

    The pressure effect on amorphous-to-quasicrystalline-to-intermetallic phase transformations in a Zr70Pd30 metallic glass has been investigated by in situ x-ray diffraction measurements using synchrotron radiation. It is found that the glass crystallizes in two steps: (1) amorphous-to-icosahedral ...

  17. Proceedings of the 4th seminar of R and D on advanced ORIENT 'strategy and technical requirement for new resource of noble metals in advanced atomic energy science'

    International Nuclear Information System (INIS)

    Sasaki, Yuji; Koyama, Shinichi; Ozawa, Masaki

    2010-12-01

    The 4th Seminar of R and D on advanced ORIENT, 'Strategy and technical requirement for new resource of noble metals in advanced atomic energy science' was held in Swany hall, Rokkasho-Mura, on July 30th, 2010 organized by Japan Atomic Energy Agency. The first meeting of this seminar was held at Oarai, Ibaraki on May, 2007, the second seminar was held at Tokai, on November, 2008, and the third seminar was held at Sendai, on October, 2009. Spent nuclear fuel should be recognized as not only mass of radioactive elements but also potentially useful materials including platinum metals and rare earth elements. Taking the cooperation with universities related companies and research institutes, into consideration, we aimed at expanding and progressing the basic researches. In this seminar, there are many poster presentation included, and the useful discussion with many students are performed. This report records abstracts and figures submitted from the oral speakers in this seminar. (author)

  18. Electrochemistry of conductive polymers 39. Contacts between conducting polymers and noble metal nanoparticles studied by current-sensing atomic force microscopy.

    Science.gov (United States)

    Cho, Shin Hyo; Park, Su-Moon

    2006-12-28

    Electrical properties of contacts formed between conducting polymers and noble metal nanoparticles have been examined using current-sensing atomic force microscopy (CS-AFM). Contacts formed between electrochemically prepared pi-conjugated polymer films such as polypyrrole (PPy), poly(3-methylthiophene) (P3MeT), as well as poly(3,4-ethylenedioxythiophene) (PEDOT) and noble metal nanoparticles including platinum (Pt), gold (Au), and silver (Ag) have been examined. The Pt nanoparticles were electrochemically deposited on a pre-coated PPy film surface by reducing a platinum precursor (PtCl62-) at a constant potential. Both current and scanning electron microscopic images of the film showed the presence of Pt islands. The Au and Ag nanoparticles were dispersed on the P3MeT and PEDOT film surfaces simply by dipping the polymer films into colloid solutions containing Au or Ag particles for specified periods (5 to approximately 10 min). The deposition of Au or Ag particles resulted from either their physical adsorption or chemical bonding between particles and the polymer surface depending on the polymer. When compared with PPy, P3MeT and PEDOT showed a stronger binding to Au or Ag nanoparticles when dipped in their colloidal solutions for the same period. This indicates that Au and Ag particles are predominantly linked with the sulfur atoms via chemical bonding. Of the two, PEDOT was more conductive at the sites where the particles are connected to the polymer. It appears that PEDOT has better aligned sulfur atoms on the surface and is strongly bonded to Au and Ag nanoparticles due to their strong affinity to gold and silver. The current-voltage curves obtained at the metal islands demonstrate that the contacts between these metal islands and polymers are ohmic.

  19. Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu–Cr catalyst

    International Nuclear Information System (INIS)

    Yan, Kai; Chen, Aicheng

    2013-01-01

    Biomass-derived platform intermediate furfural and levulinic acid were efficiently hydrogenated to the value-added furfuryl alcohol and promising biofuel γ-valerolactone, respectively, using a noble-metal-free Cu–Cr catalyst, which was facilely and successfully synthesized by a modified co-precipitation method using the cheap metal nitrates. In the first hydrogenation of furfural, 95% yield of furfuryl alcohol was highly selectively produced at 99% conversion of furfural under the mild conditions. For the hydrogenation of levulinic acid, 90% yield of γ-valerolactone was highly selectively produced at 97.8% conversion. Besides, the physical properties of the resulting Cu–Cr catalysts were studied by XRD (X-ray diffraction), EDX (Energy-dispersive X-ray), TEM (Transmission electron microscopy) and XPS (X-ray photoelectron spectroscopy) to reveal their influence on the catalytic performance. Subsequently, different reaction parameters were studied and it was found that Cu 2+ /Cr 3+ ratios (0.5, 1 and 2), reaction temperature (120–220 °C) and hydrogen pressure (35–70 bar) presented important influence on the catalytic activities. In the end, the stability of the Cu–Cr catalysts was also studied. - Highlights: • A noble-metal-free Cu–Cr catalyst was successfully synthesized using metal nitrates. • Cu–Cr catalysts were highly selective hydrogenation of biomass-derived furfural to FA. • Cu–Cr catalysts were efficient for hydrogenation of biomass-derived LA to biofuel GVL. • The physical properties of the resulting Cu–Cr catalysts were systematically studied. • Reaction parameters and stability in the hydrogenation of furfural were studied in details

  20. Flower-Like ZnO-Assisted One-Pot Encapsulation of Noble Metal Nanoparticles Supported Catalysts with ZIFs

    Science.gov (United States)

    Lin, Lu; Liu, Haiou; Zhang, Xiongfu

    2018-03-01

    Rational design of efficient approaches to fabricate MOFs-coated core-shell composites is promising but challenging. We report here the encapsulation of Pd nanoparticles (Pd NPs) supported flower-like ZnO (F-ZnO) microspheres with ZIF-8 shell through a facile strategy, in which the formation and immobilization of Pd NPs on F-ZnO supports and the subsequent growth of ZIF-8 shells over them are effectively integrated into one-pot synthetic route. Importantly, the utilization of ZnO both as support of Pd NPs and Zn2+ source of ZIF-8 is favorable for the implement of one-pot synthesis, due to its functions in anchoring Pd NPs and inducing ZIF-8 formation. Further insights into the morphological influence of zinc oxide particles on the resulting materials indicate that the flower-like microspheres with 2D nanosheets as subunits also benefit the coating of Pd NPs supported cores with ZIF-8, resulting in a well-defined core-shell catalyst. The achieved catalyst deliveries remarkable performance in terms of selectivity, anti-poisoning and recyclability in the liquid hydrogenations of alkenes.

  1. Fully relativistic study of intermetallic dimers of group-1 elements K through element 119 and prediction of their adsorption on noble metal surfaces

    International Nuclear Information System (INIS)

    Pershina, V.; Borschevsky, A.; Anton, J.

    2012-01-01

    Graphical abstract: The 4c-DFT calculations were performed for M 2 and MAu (M = K though element 119). Trends in atomic and molecular properties are shown to be reversed in group 1 beyond Cs due to relativity. The 8s(119) AO relativistic stabilization and contraction is the reason for the weakest M–Au bond and smallest adsorption enthalpy of element 119 on noble metals in group 1. Highlights: ► Fully relativistic 4c-DFT calculations were performed for M 2 and MAu (M = K though element 119). ► Trends in atomic and molecular properties are reversed in group 1 from Cs on due to relativity. ► The 8s(119) AO stabilization and contraction result in the weakest M–Au bond in group 1. ► The weakest adsorption of element 119 on noble metals is expected among all group-1 elements. - Abstract: Spectroscopic properties of group-1 M 2 and MAu (M = K, Rb, Cs, Fr, and element 119) were calculated using the 4c-DFT method. The results show that the relativistic contraction and stabilization of the ns(M) AO result in the inversion of trends both in atomic and molecular properties in group 1 beyond Cs. Electronegativity χ of the elements proves to decrease from Cs, the most electropositive element of all elements, to element 119, with its χ value approaching that of Na. Due to the largest relativistic effects on the 8s(119) AO in group 1, bonding in (119) 2 appears to be stronger than that of K 2 , while bonding in 119Au should be the weakest out of all group-1 MAu. Using calculated dissociation energies of M 2 , sublimation enthalpies, ΔH sub , of Fr of 77 kJ/mol and element 119 of 94 kJ/mol were estimated using a linear correlation between these quantities in the chemical group. Using the M–Au binding energies, the adsorption enthalpies, −ΔH ads , of 106 kJ/mol on gold, 76 kJ/mol on platinum, and 63 kJ/mol on silver were estimated for element 119 via a correlation with known ΔH ads in the chemical group. These moderate ΔH ads values are indicative of a

  2. Electronic structure of disordered Au-Pd alloys studied by electron spectroscopies

    Science.gov (United States)

    Nahm, Tschang-Uh; Jung, Ranju; Kim, Jae-Young; Park, W.-G.; Oh, S.-J.; Park, J.-H.; Allen, J. W.; Chung, S.-M.; Lee, Y. S.; Whang, C. N.

    1998-10-01

    The occupied and unoccupied electronic structures of disordered AuxPd1-x alloys are studied by valence-band photoemission, bremsstrahlung isochromat spectroscopy (BIS), and x-ray absorption near-edge spectroscopy (XANES). The occupied partial spectral weights (PSW's) of Au 5d and Pd 4d states are obtained from the valence-band photoemission spectra using synchrotron radiation by taking the matrix-element effect into account. We use the Cooper minimum phenomenon of the Pd 4d states with the measured ratios of photoionization cross sections. The Pd 4d PSW's are found to form a virtual bound state in the Pd-diluted alloy but become broader as the Pd concentration increases due to the Pd 4d-Pd 4d hybridization. On the other hand, Au 5d5/2 states show the common-band behavior due to the appreciable mixing with Pd 4d5/2 states, while Au 5d3/2 states retain their sharp structure and show the split-band behavior. These experimental PSW's of Au-Pd alloys are in good qualitative agreement with the results of recent self-consistent-field coherent-potential-approximation calculations. The comparison of the experimental Pd PSW of Au-Pd with those of other Pd-noble-metal alloys clearly shows that in noble-metal-rich alloys, the mixing of Pd 4d states with host d bands increases in the order of Ag-Pd, Au-Pd, Cu-Pd systems. This trend results in the split-band for Au-Pd and Ag-Pd in Pd diluted alloys, but gives the common band for Cu-Pd. The unoccupied Pd 4d states of disordered AuxPd1-x alloys obtained from BIS and XANES spectra show the gradual filling of Pd 4d states as the Au concentration is increased, but it is not completely filled even in the Pd-diluted alloy.

  3. Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

    Science.gov (United States)

    Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

    2018-03-01

    Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.

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

    Science.gov (United States)

    Adzic, Radoslav; Vukmirovic, Miomir; Sasaki, Kotaro

    2010-04-27

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

  5. Noble gases in meteorites and terrestrial planets

    Science.gov (United States)

    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.

  6. Surface Functionalization of g-C 3 N 4 : Molecular-Level Design of Noble-Metal-Free Hydrogen Evolution Photocatalysts

    KAUST Repository

    Chen, Yin

    2015-06-12

    A stable noble-metal-free hydrogen evolution photocatalyst based on graphite carbon nitride (g-C3N4) 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-C3N4. 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 24h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

    KAUST Repository

    Chen, Yin

    2015-11-02

    The graphitic carbon nitride (g-C3N4) usually is thought to be an inert material and it’s difficult to have the surface terminated NH2 groups functionalized. By modifying the g-C3N4 surface with hydrazine, the diazanyl group was successfully introduced onto the g-C3N4 surface, which allows the introduction with many other function groups. Here we illustrated that by reaction of surface hydrazine group modified g-C3N4 with CS2 under basic condition, a water electrolysis active group C(=S)SNi can be implanted on the g-C3N4 surface, and leads to a noble metal free hydrogen evolution catalyst. This catalyst has 40% hydrogen evolution efficiency compare to the 3 wt% Pt photo precipitated g-C3N4, with only less than 0.2 wt% nickel.

  8. Transition metal contacts to graphene

    Energy Technology Data Exchange (ETDEWEB)

    Politou, Maria, E-mail: Maria.Politou@imec.be; De Gendt, Stefan; Heyns, Marc [KU Leuven, 3001 Leuven (Belgium); imec, Kapeldreef 75, 3001 Leuven (Belgium); Asselberghs, Inge; Radu, Iuliana; Conard, Thierry; Richard, Olivier; Martens, Koen; Huyghebaert, Cedric; Tokei, Zsolt [imec, Kapeldreef 75, 3001 Leuven (Belgium); Lee, Chang Seung [SAIT, Samsung Electronics Co., Suwon 443-803 (Korea, Republic of); Sayan, Safak [imec, Kapeldreef 75, 3001 Leuven (Belgium); Intel Corporation, 2200 Mission College Blvd, Santa Clara, California 95054 (United States)

    2015-10-12

    Achieving low resistance contacts to graphene is a common concern for graphene device performance and hybrid graphene/metal interconnects. In this work, we have used the circular Transfer Length Method (cTLM) to electrically characterize Ag, Au, Ni, Ti, and Pd as contact metals to graphene. The consistency of the obtained results was verified with the characterization of up to 72 cTLM structures per metal. Within our study, the noble metals Au, Ag and Pd, which form a weaker bond with graphene, are shown to result in lower contact resistance (Rc) values compared to the more reactive Ni and Ti. X-ray Photo Electron Spectroscopy and Transmission Electron Microscopy characterization for the latter have shown the formation of Ti and Ni carbides. Graphene/Pd contacts show a distinct intermediate behavior. The weak carbide formation signature and the low Rc values measured agree with theoretical predictions of an intermediate state of weak chemisorption of Pd on graphene.

  9. The Precious metals (Au, Ag, Pt, Pd, Rh) adsorption on the Silicon – organic sorbents

    OpenAIRE

    G Burmaa; S Alen; Yu Ganchimeg; I Sukhbaatar

    2014-01-01

    Sorption activity of two types of Silicon-organic sorbents for the previous metals has been studied. A polymer – poly (3- silsesquioxanilpropylthiocarbamate) - 3- silsesquioxanilpropylammonium which was obtained by the hydrolytic poly-condensation reaction and has been determined its physical, chemical characteristics and its sorption activity for the Ag(I), Au(III), Pt(IV), Pd(II), Rh(III). It has been found out that the sorbent shows high static sorption of Gold (III), Mercury (II) at acidi...

  10. The Metal-Support Interaction Concerning the Particle Size Effect of Pd/Al2O3on Methane Combustion.

    Science.gov (United States)

    Murata, Kazumasa; Mahara, Yuji; Ohyama, Junya; Yamamoto, Yuta; Arai, Shigeo; Satsuma, Atsushi

    2017-12-11

    The particle size effect of Pd nanoparticles supported on alumina with various crystalline phases on methane combustion was investigated. Pd/θ, α-Al 2 O 3 with weak metal-support interaction showed a volcano-shaped dependence of the catalytic activity on the size of Pd particles, and the catalytic activity of the strongly interacted Pd/γ-Al 2 O 3 increased with the particle size. Based on a structural analysis of Pd nanoparticles using CO adsorption IR spectroscopy and spherical aberration-corrected scanning/transmission electron microscopy, the dependence of catalytic activity on Pd particle size and the alumina crystalline phase was due to the fraction of step sites on Pd particle surface. The difference in fraction of the step site is derived from the particle shape, which varies not only with Pd particle size but also with the strength of metal-support interaction. Therefore, this interaction perturbs the particle size effect of Pd/Al 2 O 3 for methane combustion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Monometallic Pd and Pt and Bimetallic Pd-Pt/Al2O3-TiO2 for the HDS of DBT: Effect of the Pd and Pt Incorporation Method

    Directory of Open Access Journals (Sweden)

    Reynaldo Martínez Guerrero

    2014-01-01

    Full Text Available The effect of the preparation method of monometallic Pd and Pt and bimetallic Pd-Pt/Al2O3-TiO2 catalysts on the hydrodesulfurization (HDS of dibenzothiophene (DBT was investigated in this study. The synthesis was accomplished using three methods: (A impregnation, (B metal organic chemical vapor deposition (MOCVD, and (C impregnation-MOCVD. The bimetallic Pd-Pt catalyst prepared by the impregnation-MOCVD method was most active for the HDS of DBT compared to those prepared by the single impregnation or MOCVD method due to the synergetic effect between both noble metals. The greater selectivity toward biphenyl indicated that this bimetallic Pd-Pt catalyst preferentially removes sulfur via the direct desulfurization mechanism. However, the bimetallic Pd-Pt catalyst prepared using the single MOCVD method did not produce any cyclohexylbenzene, which is most likely associated with the hydrogenation/dehydrogenation sites.

  12. Panorama 2010: Are Li, Ni, Pt and Pd 'critical' metals?

    International Nuclear Information System (INIS)

    Saniere, A.; Vinot, S.; Christmann, P.

    2010-01-01

    Heavily dependent on petroleum, the transport industry is seeking technological solutions to lessen this reliance and reduce its CO 2 emissions, such as hybrid or electric vehicles or fuel cells cars. But these solutions are in turn dependent on a few metals that have some of the same characteristics as hydrocarbons, e.g. they are finite resources present in geographic concentrations. For how long will lithium, nickel, platinum and palladium be available for our use? Will the importance of their applications and the implications of their geographic distribution make them critical in the world economy? (author)

  13. Potential hazards of particulate noble metal emissions from car exhaust catalysts. Gefaehrdungspotential von partikulaeren Edelmetallemissionen aus Automobilabgas-Katalysatoren

    Energy Technology Data Exchange (ETDEWEB)

    Stoeber, W.

    1985-01-01

    The aim of the present bibliographical study is to investigate into the possibility of health impairment by emissions of eroded and particulate precious metals of catalytic converters for motor-car exhaust gas. Connected therewith is a survey of environmental pollution so far caused by platinum metals and of their biological impact. The risk estimation relates solely to the data on emission obtained during normal operation; research work is still needed with respect to the chemical composition, the size distribution and the particle forms of the precious metals emitted. Besides, only limited data are available as to the environmental behaviour of the precious metals.

  14. Non-Noble Metal Nanoparticles Supported by Postmodified Porous Organic Semiconductors: Highly Efficient Catalysts for Visible-Light-Driven On-Demand H2Evolution from Ammonia Borane.

    Science.gov (United States)

    Zhang, Hao; Gu, Xiaojun; Song, Jin; Fan, Na; Su, Haiquan

    2017-09-27

    From the viewpoint of controlling the visible-light-driven activities of catalysts containing metal nanoparticles (NPs) by tuning the microstructures of semiconducting supports, we employed a postsynthetic thermal modification approach to prepare carbon nitride (C 3 N 4 ) species featuring different microstructures and then we synthesized Co and Ni NPs supported by these C 3 N 4 species, which were used to catalyze the room-temperature H 2 evolution from ammonia borane (NH 3 BH 3 ). The systematic investigation showed that the catalysts had different activities under light irradiation. Compared with the pristine C 3 N 4 -based catalyst, all the modified C 3 N 4 -based catalysts had enhanced activities. The highest active Co catalyst with a total turnover frequency of 93.8 min -1 was successfully obtained, which exceeded the values of all the reported heterogeneous noble metal-free catalysts. The structure characterizations indicated that the postmodified porous C 3 N 4 species had the different band structures, photoluminescence lifetime, and photocurrent density under visible light irradiation, leading to the different separation efficiency of photogenerated charge carriers. These characteristics helped us regulate the electronic characteristics of Co and Ni NPs in the supported catalysts and then led to the significantly different and enhanced activity in the visible-light-driven H 2 evolution.

  15. Crystallization of Pd40CU30Ni10P20 bulk metallic glass with and without pressure

    DEFF Research Database (Denmark)

    Yang, B.; Jiang, Jianzhong; Zhuang, Yanxin

    2007-01-01

    The glass-transition behavior of Pd40Cu30Ni10P20 bulk metallic glass was investigated by differential scanning calorimetry (DSC) and X-ray powder diffraction (XRD). The effect of pressure on the crystallization behavior of Pd40Cu30Ni10P20 bulk glass was studied by in situ high-pressure and high......-temperature X-ray powder diffraction using synchrotron radiation. Phase analyses show at least six crystalline phases in the crystallized sample, namely, monoclinic, tetragonal Cu3Pd-like, rhombohedral, fcc-Ni2Pd2P, fcc-(Ni, Pd) solid solution, and body-centered tetragonal (bct) Ni3P-like phases. The onset...

  16. Redox preparation of mixed-valence cobalt manganese oxide nanostructured materials: highly efficient noble metal-free electrocatalysts for sensing hydrogen peroxide

    Science.gov (United States)

    Kuo, Cheng-Chi; Lan, Wen-Jie; Chen, Chun-Hu

    2013-12-01

    High-performance hydrogen peroxide sensors provide valuable signals of biological interactions, disorders, and developing of diseases. Low-cost metal oxides are promising alternatives but suffer from low conductivity and sensing activity. Multi-component metal oxides are excellent candidates to accomplish these challenges, but the composition inhomogeneity is difficult to manage with conventional material preparation. We demonstrated redox preparation strategies to successfully synthesize highly homogeneous, noble metal-free H2O2 sensors of spinel nanostructured cobalt manganese oxides with enhanced conductivity, multiple mixed-valence features, and efficient H2O2 sensing activities. The designed redox reactions accompanied with material nucleation/formation are the key factors for compositional homogeneity. High conductivity (1.5 × 10-2 S cm-1) and H2O2 sensing activity (12 times higher than commercial Co3O4) were achieved due to the homogeneous multiple mixed-valence systems of Co(ii)/(iii) and Mn(iii)/(iv). A wide linear detection range (from 0.1 to 25 mM) with a detection limit of 15 μM was observed. Manganese species assist the formation of large surface area nanostructures, enhancing the H2O2 reduction activities, and inhibit the sensing interference. The material controls of hierarchical nanostructures, elemental compositions, porosity, and electrochemical performances are highly associated with the reaction temperatures. The temperature-dependent properties and nanostructure formation mechanisms based on a reaction rate competition are proposed.High-performance hydrogen peroxide sensors provide valuable signals of biological interactions, disorders, and developing of diseases. Low-cost metal oxides are promising alternatives but suffer from low conductivity and sensing activity. Multi-component metal oxides are excellent candidates to accomplish these challenges, but the composition inhomogeneity is difficult to manage with conventional material

  17. Nanostructured Ti-Zr-Pd-Si-(Nb) bulk metallic composites: Novel biocompatible materials with superior mechanical strength and elastic recovery.

    Science.gov (United States)

    Hynowska, A; Blanquer, A; Pellicer, E; Fornell, J; Suriñach, S; Baró, M D; Gebert, A; Calin, M; Eckert, J; Nogués, C; Ibáñez, E; Barrios, L; Sort, J

    2015-11-01

    The microstructure, mechanical behaviour, and biocompatibility (cell culture, morphology, and cell adhesion) of nanostructured Ti45 Zr15 Pd35- x Si5 Nbx with x = 0, 5 (at. %) alloys, synthesized by arc melting and subsequent Cu mould suction casting, in the form of rods with 3 mm in diameter, are investigated. Both Ti-Zr-Pd-Si-(Nb) materials show a multi-phase (composite-like) microstructure. The main phase is cubic β-Ti phase (Im3m) but hexagonal α-Ti (P63/mmc), cubic TiPd (Pm3m), cubic PdZr (Fm3m), and hexagonal (Ti, Zr)5 Si3 (P63/mmc) phases are also present. Nanoindentation experiments show that the Ti45 Zr15 Pd30 Si5 Nb5 sample exhibits lower Young's modulus than Ti45 Zr15 Pd35 Si5 . Conversely, Ti45 Zr15 Pd35 Si5 is mechanically harder. Actually, both alloys exhibit larger values of hardness when compared with commercial Ti-40Nb, (HTi-Zr-Pd-Si ≈ 14 GPa, HTi-Zr-Pd-Si-Nb ≈ 10 GPa and HTi-40Nb ≈ 2.7 GPa). Concerning the biological behaviour, preliminary results of cell viability performed on several Ti-Zr-Pd-Si-(Nb) discs indicate that the number of live cells is superior to 94% in both cases. The studied Ti-Zr-Pd-Si-(Nb) bulk metallic system is thus interesting for biomedical applications because of the outstanding mechanical properties (relatively low Young's modulus combined with large hardness), together with the excellent biocompatibility. © 2014 Wiley Periodicals, Inc.

  18. Hierarchical hybrid of Ni3N/N-doped reduced graphene oxide nanocomposite as a noble metal free catalyst for oxygen reduction reaction

    Science.gov (United States)

    Zhao, Qi; Li, Yingjun; Li, Yetong; Huang, Keke; Wang, Qin; Zhang, Jun

    2017-04-01

    Novel nickel nitride (Ni3N) nanoparticles supported on nitrogen-doped reduced graphene oxide nanosheets (N-RGOs) are synthesized via a facile strategy including hydrothermal and subsequent calcination methods, in which the reduced graphene oxide nanosheets (RGOs) are simultaneously doped with nitrogen species. By varying the content of the RGOs, a series of Ni3N/N-RGO nanocomposites are obtained. The Ni3N/N-RGO-30% hybrid nanocomposite exhibits superior catalytic activity towards oxygen reduction reaction (ORR) under alkaline condition (0.1 M KOH). Furthermore, this hybrid catalyst also demonstrates high tolerance to methanol poisoning. The RGO containing rich N confers the nanocomposite with large specific surface area and high electronic conduction ability, which can enhance the catalytic efficiency of Ni3N nanoparticles. The enhanced catalytic activity can be attributed to the synergistic effect between Ni3N and nitrogen doped reduced graphene oxide. In addition, the sufficient contact between Ni3N nanoparticles and the N-RGO nanosheets simultaneously promotes good nanoparticle dispersion and provides a consecutive activity sites to accelerate electron transport continuously, which further enhance the ORR performance. The Ni3N/N-RGO may be further an ideal candidate as efficient and inexpensive noble metal-free ORR electrocatalyst in fuel cells.

  19. The influence of dynamical change of optical properties on the thermomechanical response and damage threshold of noble metals under femtosecond laser irradiation

    Science.gov (United States)

    Tsibidis, George D.

    2018-02-01

    We present a theoretical investigation of the dynamics of the dielectric constant of noble metals following heating with ultrashort pulsed laser beams and the influence of the temporal variation of the associated optical properties on the thermomechanical response of the material. The effect of the electron relaxation time on the optical properties based on the use of a critical point model is thoroughly explored for various pulse duration values (i.e., from 110 fs to 8 ps). The proposed theoretical framework correlates the dynamical change in optical parameters, relaxation processes and induced strains-stresses. Simulations are presented by choosing gold as a test material, and we demonstrate that the consideration of the aforementioned factors leads to significant thermal effect changes compared to results when static parameters are assumed. The proposed model predicts a substantially smaller damage threshold and a large increase of the stress which firstly underlines the significant role of the temporal variation of the optical properties and secondly enhances its importance with respect to the precise determination of laser specifications in material micromachining techniques.

  20. Fluorescence-based high throughput screening for noble metal-free and platinum-poor anode catalysts for the direct methanol fuel cell.

    Science.gov (United States)

    Welsch, F G; Stöwe, K; Maier, W F

    2011-09-12

    We describe here the results of a high throughput screening study for direct methanol fuel cell (DMFC) anode catalysts consisting of new elemental combinations with an optical high-throughput screening method, which allows the quantitative evaluation of the electrochemical activity of catalysts. The method is based on the fluorescence of protonated quinine generated during electrooxidation of methanol. The high-throughput screening included noble-metal free binary and ternary mixed oxides of the elements Al, Co, Cr, Cu, Fe, Mn, Mo, Nb, Ni, Ta, Ti, Zn, and Zr in the oxidized form as well as after prior reduction in hydrogen. In addition 318 ternary and quaternary Pt-containing materials composed out of the mixed oxides of Bi, Ce, Co, Cr, Cu, Fe, Ga, Ge, In, La, Mn, Mo, Nb, Nd, Ni, Pr, Sb, Sn, Ta, Te, Ti, V, Zn, and Zr with a molar Pt-ratio of 10% and 30% were screened. Validation and long time experiments of the hits were performed by cyclovoltammetry (CV). The microstructural stability of the electrode preparations of the lead compositions was studied by X-ray diffraction (XRD) pattern analysis.

  1. Free MoS2 Nanoflowers Grown on Graphene by Microwave-Assisted Synthesis as Highly Efficient Non-Noble-Metal Electrocatalysts for the Hydrogen Evolution Reaction.

    Science.gov (United States)

    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.

  2. Photocatalytic H2 Production Using Pt-TiO2 in the Presence of Oxalic Acid: Influence of the Noble Metal Size and the Carrier Gas Flow Rate

    Science.gov (United States)

    Kmetykó, Ákos; Mogyorósi, Károly; Gerse, Viktória; Kónya, Zoltán; Pusztai, Péter; Dombi, András; Hernádi, Klára

    2014-01-01

    The primary objective of the experiments was to investigate the differences in the photocatalytic performance when commercially available Aeroxide P25 TiO2 photocatalyst was deposited with differently sized Pt nanoparticles with identical platinum content (1 wt%). The noble metal deposition onto the TiO2 surface was achieved by in situ chemical reduction (CRIS) or by mixing chemically reduced Pt nanoparticle containing sols to the aqueous suspensions of the photocatalysts (sol-impregnated samples, CRSIM). Fine and low-scale control of the size of resulting Pt nanoparticles was obtained through variation of the trisodium citrate concentration during the syntheses. The reducing reagent was NaBH4. Photocatalytic activity of the samples and the reaction mechanism were examined during UV irradiation (λmax = 365 nm) in the presence of oxalic acid (50 mM) as a sacrificial hole scavenger component. The H2 evolution rates proved to be strongly dependent on the Pt particle size, as well as the irradiation time. A significant change of H2 formation rate during the oxalic acid transformation was observed which is unusual. It is probably regulated both by the decomposition rate of accumulated oxalic acid and the H+/H2 redox potential on the surface of the catalyst. The later potential is influenced by the concentration of the dissolved H2 gas in the reaction mixture. PMID:28788229

  3. Photocatalytic H2 Production Using Pt-TiO2 in the Presence of Oxalic Acid: Influence of the Noble Metal Size and the Carrier Gas Flow Rate

    Directory of Open Access Journals (Sweden)

    Ákos Kmetykó

    2014-10-01

    Full Text Available The primary objective of the experiments was to investigate the differences in the photocatalytic performance when commercially available Aeroxide P25 TiO2 photocatalyst was deposited with differently sized Pt nanoparticles with identical platinum content (1 wt%. The noble metal deposition onto the TiO2 surface was achieved by in situ chemical reduction (CRIS or by mixing chemically reduced Pt nanoparticle containing sols to the aqueous suspensions of the photocatalysts (sol-impregnated samples, CRSIM. Fine and low-scale control of the size of resulting Pt nanoparticles was obtained through variation of the trisodium citrate concentration during the syntheses. The reducing reagent was NaBH4. Photocatalytic activity of the samples and the reaction mechanism were examined during UV irradiation (λmax = 365 nm in the presence of oxalic acid (50 mM as a sacrificial hole scavenger component. The H2 evolution rates proved to be strongly dependent on the Pt particle size, as well as the irradiation time. A significant change of H2 formation rate during the oxalic acid transformation was observed which is unusual. It is probably regulated both by the decomposition rate of accumulated oxalic acid and the H+/H2 redox potential on the surface of the catalyst. The later potential is influenced by the concentration of the dissolved H2 gas in the reaction mixture.

  4. Noble-metal-free NiO@Ni-ZnO/reduced graphene oxide/CdS heterostructure for efficient photocatalytic hydrogen generation

    Science.gov (United States)

    Chen, Fayun; Zhang, Laijun; Wang, Xuewen; Zhang, Rongbin

    2017-11-01

    Noble-metal-free semiconductor materials are widely used for photocatalytic hydrogen generation because of their low cost. ZnO-based heterostructures with synergistic effects exhibit an effective photocatalytic activity. In this work, NiO@Ni-ZnO/reduced graphene oxide (rGO)/CdS heterostructures are synthesized by a multi-step method. rGO nanosheets and CdS nanoparticles were introduced into the heterostructures via a redox reaction and light-assisted growth, respectively. A novel Ni-induced electrochemical growth method was developed to prepare ZnO rods from Zn powder. NiO@Ni-ZnO/rGO/CdS heterostructures with a wide visible-light absorption range exhibited highly photocatalytic hydrogen generation rates under UV-vis and visible light irradiation. The enhanced photocatalytic activity is attributed to the Ni nanoparticles that act as cocatalysts for capturing photoexcited electrons and the improved synergistic effect between ZnO and CdS due to the rGO nanosheets acting as photoexcited carrier transport channels.

  5. Barrierless growth of precursor-free, ultrafast laser-fragmented noble metal nanoparticles by colloidal atom clusters - A kinetic in situ study.

    Science.gov (United States)

    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. Copyright © 2015. Published by Elsevier Inc.

  6. WS2 as an Effective Noble-Metal Free Cocatalyst Modified TiSi2 for Enhanced Photocatalytic Hydrogen Evolution under Visible Light Irradiation

    Directory of Open Access Journals (Sweden)

    Dongmei Chu

    2016-09-01

    Full Text Available A noble-metal free photocatalyst consisting of WS2 and TiSi2 being used for hydrogen evolution under visible light irradiation, has been successfully prepared by in-situ formation of WS2 on the surface of TiSi2 in a thermal reaction. The obtained samples were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive X-ray spectrometry (EDX, transmission electron microscopy (TEM, and X-ray photoelectron spectroscopy (XPS. The results demonstrate that WS2 moiety has been successfully deposited on the surface of TiSi2 and some kind of chemical bonds, such as Ti-S-W and Si-S-W, might have formed on the interface of the TiSi2 and WS2 components. Optical and photoelectrochemical investigations reveal that WS2/TiSi2 composite possesses lower hydrogen evolution potential and enhanced photogenerated charge separation and transfer efficiency. Under 6 h of visible light (λ > 420 nm irradiation, the total amount of hydrogen evolved from the optimal WS2/TiSi2 catalyst is 596.4 μmol·g−1, which is around 1.5 times higher than that of pure TiSi2 under the same reaction conditions. This study shows a paradigm of developing the effective, scalable and inexpensive system for photocatalytic hydrogen generation.

  7. Electrical conductivity dependence of thin metallic films of Au and Pd as a top electrode in capacitor applications

    International Nuclear Information System (INIS)

    Nazarpour, S.; Langenberg, E.; Jambois, O.; Ferrater, C.; Garcia-Cuenca, M.V.; Polo, M.C.; Varela, M.

    2009-01-01

    Electrical conductivity dependence of thin metallic films of Au and Pd over the different perovskites was investigated. It is found from electrical properties that crystallographic growth orientation of Au and Pd thin layers attained from X-ray diffraction results indicate the slop of current (I)-voltage (V) plots. Besides, surface morphology and topography was considered using Field Emission Scanning Electron Microscopy and Atomic Force Microscopy, respectively. Obtained results showed the Stranski-Krastanov growth of the Pd and Au. Indeed, diminishing of the root-mean-square roughness of Pd/BiMnO 3 /SrTiO 3 following by Au deposition should be concerned due to growth of Au onto the crack-like parts of the substrate. These crack-like parts appeared due to parasitic phases of the Bi-Mn-O system mainly Mn 3 O 4 (l 0 l) and Mn 3 O 4 (0 0 4 l). The different response in the electrical properties of heterostructures suggests that electrical conductance of the Au and Pd thin metallic films have the crystallographic orientation dependence. Furthermore, polycrystallinity of the thin metallic films are desired in electrode applications due to increase the conductivity of the metallic layers.

  8. Study of the interface stability of the metal (Mo, Ni, Pd/HfO2/AlN/InGaAs MOS devices

    Directory of Open Access Journals (Sweden)

    Huy Binh Do

    2017-08-01

    Full Text Available The degeneration of the metal/HfO2 interfaces for Mo, Ni, and Pd gate metals was studied in this paper. An unstable PdOx interfacial layer formed at the Pd/HfO2 interface, inducing the oxygen segregation for the Pd/HfO2/InGaAs metal oxide capacitor (MOSCAP. The low dissociation energy for the Pd-O bond was the reason for oxygen segregation. The PdOx layer contains O2− and OH− ions which are mobile during thermal annealing and electrical stress test. The phenomenon was not observed for the (Mo, Ni/HfO2/InGaAs MOSCAPs. The results provide the guidance for choosing the proper metal electrode for the InGaAs based MOSFET.

  9. Ammonia Gas Sensing Properties of Nanocrystalline Zn1-xCuxFe2O4 Doped with Noble Metal

    Directory of Open Access Journals (Sweden)

    S. V. JAGTAP

    2010-11-01

    Full Text Available The sensors are required basically for monitoring of trace gases in environment. In order to detect, measure and control these gases; one should know the amount and type of gases present in the environment. Among the most toxic and hazardous gases, it is necessary to detect and monitor the ammonia gas because this is enhance in the agricultural sector by the addition of large amounts of NH3 to cultivated farmland in the form of fertilizers. Nanocrystalline spinel type Zn1-xCuxFe2O4 (x=0, 0.2, 0.4 0.6 & 0.8 has been synthesized by sol-gel citrate method. The synthesized powders were characterized by XRD and SEM. The results revealed that the particle size is in the range of 40–45 nm for Cu–Zn ferrite with good crystallinity. The gas sensing properties were studied towards reducing gases like CO, LPG, NH3 and H2S and it is observed that Cu–Zn ferrite shows high response to ammonia gas at relatively lower operating temperature. The Zn0.6Cu0.4Fe2O4 nanomaterial shows better sensitivity towards NH3 gas at an operating temperature 300 0C. Incorporation of Pd improved the sensitivity, selectivity, response time and reduced the operating temperature from 300 0C to 250 0C for NH3 sensor.

  10. ALTERNATIVE MATERIALS TO PD MEMBRANES FOR HYDROGEN PURIFICATION

    Energy Technology Data Exchange (ETDEWEB)

    Korinko, P; T. Adams

    2008-09-12

    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 focal point of the reported work was to evaluate two different classes of materials for potential replacement of conventional Pd-alloy purification/diffuser membranes. Crystalline V-Ni-Ti and Amorphous Fe- and Co-based metallic glass alloys have been evaluated using gaseous hydrogen permeation testing techniques.

  11. Hierarchical hybrid of Ni{sub 3}N/N-doped reduced graphene oxide nanocomposite as a noble metal free catalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Qi; Li, Yingjun; Li, Yetong [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Huang, Keke [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Zhang, Jun, E-mail: cejzhang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

    2017-04-01

    Highlights: • Hybrid of Ni{sub 3}N/N-RGO catalysts are synthesized by using a two-step method. • The catalysts manifest superior catalytic activity towards the ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: Novel nickel nitride (Ni{sub 3}N) nanoparticles supported on nitrogen-doped reduced graphene oxide nanosheets (N-RGOs) are synthesized via a facile strategy including hydrothermal and subsequent calcination methods, in which the reduced graphene oxide nanosheets (RGOs) are simultaneously doped with nitrogen species. By varying the content of the RGOs, a series of Ni{sub 3}N/N-RGO nanocomposites are obtained. The Ni{sub 3}N/N-RGO-30% hybrid nanocomposite exhibits superior catalytic activity towards oxygen reduction reaction (ORR) under alkaline condition (0.1 M KOH). Furthermore, this hybrid catalyst also demonstrates high tolerance to methanol poisoning. The RGO containing rich N confers the nanocomposite with large specific surface area and high electronic conduction ability, which can enhance the catalytic efficiency of Ni{sub 3}N nanoparticles. The enhanced catalytic activity can be attributed to the synergistic effect between Ni{sub 3}N and nitrogen doped reduced graphene oxide. In addition, the sufficient contact between Ni{sub 3}N nanoparticles and the N-RGO nanosheets simultaneously promotes good nanoparticle dispersion and provides a consecutive activity sites to accelerate electron transport continuously, which further enhance the ORR performance. The Ni{sub 3}N/N-RGO may be further an ideal candidate as efficient and inexpensive noble metal-free ORR electrocatalyst in fuel cells.

  12. Performance of CO preferential oxidation reactor with noble-metal catalyst coated on ceramic monolith for on-board fuel processing applications

    Energy Technology Data Exchange (ETDEWEB)

    Ahluwalia, Rajesh K.; Zhang, Qizhi [Nuclear Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Chmielewski, Donald J.; Lauzze, Kevin C. [Department of Chemical and Environmental Engineering, Illinois Institute of Technology, Chicago, IL 60616 (United States); Inbody, Michael A. [Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2005-01-30

    On-board fuel processors are being developed to provide hydrogen-rich gas to the polymer electrolyte fuel cell automotive propulsion systems. Whereas the anode catalyst in the fuel cell has low tolerance for carbon monoxide, 10-100ppm, reforming of gasoline and other hydrocarbon fuels generally produces 1-2% of CO. Of the many methods of removing CO from the reformer gas, preferential oxidation (PrOx) of CO over noble-metal catalysts is practiced most frequently. In this paper, we present experimental data for CO conversion on a Pt-based catalyst that is active at room temperature and was coated on a ceramic monolith. The data is used to develop an empirical correlation for selectivity for CO oxidation as a function of CO concentration and oxygen stoichiometry at 30,000-80,000/h space velocity. The selectivity correlation is used in a model to analyze the performance of multi-stage, adiabatic PrOx reactors with heat exchange between the stages to cool the reformate to 100{sup o}C. An optimization algorithm is used to determine the operating conditions that can reduce CO concentration to 10ppm while minimizing parasitic loss of H{sub 2} in the reformate stream. It is found that the 10ppm constraint limits the maximum inlet CO concentration to 1.05% in a single-stage reactor and to 3.1% in a two-stage reactor. The results clearly show the incremental reduction in parasitic H{sub 2} loss by addition of second and third stages.

  13. The Precious metals (Au, Ag, Pt, Pd, Rh adsorption on the Silicon – organic sorbents

    Directory of Open Access Journals (Sweden)

    G Burmaa

    2014-09-01

    Full Text Available Sorption activity of two types of Silicon-organic sorbents for the previous metals has been studied. A polymer – poly (3- silsesquioxanilpropylthiocarbamate - 3- silsesquioxanilpropylammonium which was obtained by the hydrolytic poly-condensation reaction and has been determined its physical, chemical characteristics and its sorption activity for the Ag(I, Au(III, Pt(IV, Pd(II, Rh(III. It has been found out that the sorbent shows high static sorption of Gold (III, Mercury (II at acidic condition. The second a net structured silicon-organic copolymer {SiO2*2[O1.5Si(CH23NHC5H4N}n was synthesized by hydrolytic co-poly-condensation reaction. It likely to react as an anionit that adsorbs chloro-complex anion of the Au (III, Pt(IV, Pd(II, Rh(III.DOI: http://dx.doi.org/10.5564/mjc.v12i0.167 Mongolian Journal of Chemistry Vol.12 2011: 29-34

  14. Self-assembly and photopolymerization of a novel quaternary-ammonium functionalized diacetylene on noble metal nanoparticles: A comparative study

    Science.gov (United States)

    Martinez-Espinoza, Maria Isabel; Maccagno, Massimo; Thea, Sergio; Alloisio, Marina

    2018-01-01

    Stable hydrosols of gold and silver nanoparticles coated with the quaternary-ammonium group endowed diacetylene DAAMM (N,N,N-trimethyl-3-(pentacosa-10,12-diynamido)propan-1-ammonium) were obtained through a ligand-exchange reaction leaving the morphology of the pristine cores unmodified. Photopolymerization of the chemisorbed diacetylene shell occurred in both red and blue phases thanks to the presence of internal, H-bondable amide functions in the monomer chain, which are supposed to help the formation of a packed bilayer on the metal surfaces. Multidisciplinary characterization of the polymerized samples, including spectroscopic, morphological and thermal techniques, highlighted that differences occur in the polymerization process on gold and silver nanoparticles under different experimental conditions, suggesting a higher affinity of the trimethylammonium headgroup for gold substrates in acidic media. With respect to the extensively investigated PCDA (pentacosa-10,12-diynoic acid), DAAMM showed reduced capability of photogenerating thick polymer shells, especially in the more delocalized blue form, probably because of the inefficiency of the cationic monomer to form the multi-bilayered architecture typical of the highly-performing, carboxyl-terminated diacetylene. On the other end, the inner cross-linked structure gives to poly(DAAMM)-coated nanohybrids increased stability in water with respect to self-assembled counterparts deriving from saturated cationic surfactants, making them a promising sensing platform for rapid and cost effective assays of real samples.

  15. Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting

    Science.gov (United States)

    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

  16. Application of chitosan and its N-heterocyclic derivatives for preconcentration of noble metal ions and their determination using atomic absorption spectrometry.

    Science.gov (United States)

    Azarova, Yu A; Pestov, A V; Ustinov, A Yu; Bratskaya, S Yu

    2015-12-10

    Chitosan and its N-heterocyclic derivatives N-2-(2-pyridyl)ethylchitosan (2-PEC), N-2-(4-pyridyl) ethylchitosan (4-PEC), and N-(5-methyl-4-imidazolyl) methylchitosan (IMC) have been applied in group preconcentration of gold, platinum, and palladium for subsequent determination by atomic absorption spectroscopy (AAS) in solutions with high background concentrations of iron and sodium ions. It has been shown that the sorption mechanism, which was elucidated by XPS, significantly influences the sorption capacity of materials, the efficiency of metal ions elution after preconcentration, and, as a result, the accuracy of metal determination by AAS. We have shown that native chitosan was not suitable for preconcentration of Au(III), if the elution step was used as a part of the analysis scheme. The group preconcentration of Au(III), Pd(II), and Pt(IV) with subsequent quantitative elution using 0.1M HCl/1M thiourea solution was possible only on IMC and 4-PEC. Application of IMC for analysis of the national standard quartz ore sample proved that gold could be accurately determined after preconcentration/elution with the recovery above 80%. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Alloying behaviour of electroplated Ag film with its underlying Pd/Ti film stack for low resistivity interconnect metallization

    Energy Technology Data Exchange (ETDEWEB)

    Ezawa, Hirokazu, E-mail: hirokazu.ezawa@toshiba.co.jp [Toshiba Corporation, Semiconductor and Storage Products Company (Japan); The Graduate School of Information, Production and Systems, Waseda University (Japan); Miyata, Masahiro [Toshiba Corporation, Semiconductor and Storage Products Company (Japan); Tatsumi, Kohei [The Graduate School of Information, Production and Systems, Waseda University (Japan)

    2014-02-25

    Highlights: • Alloying behavior of Ag/Pd/Ti film stack was studied by annealing at 400-800 °C. • The Ag film resistivity decreased with increasing annealing temperature. • Formation of the Pd-Ti intermetallics was found to be dominant over Ag-Pd alloying. • The excess Ti was consumed to form Ti oxides, which inhibited Ti alloying with Ag. -- Abstract: In this paper, viability of electroplated Ag film into device application was studied. Alloying behavior of the Ag film with its underlying Pd(50 nm)/Ti(100 nm) film stack was investigated with respect to heat treatment at different temperatures from 400 °C to 800 °C in an argon ambient. After annealing at 400 °C, the electrical resistivity of the Ag film increased due to Pd alloying with Ag. Formation of Pd–Ti intermetallic phases became dominant over Ag–Pd alloying with increasing annealing temperature, leading to the resistivity decrease of the Ag film. The resistivity of the 800 °C annealed Ag film approached that of its as-plated Ag film. The excess Ti atoms which were not consumed to form the intermetallic phases with the Pd atoms migrated to the Ag film surface to form Ti oxides along the Ag grain boundaries on the topmost film surface. The Ag/Pd/Ti film stack has been confirmed to maintain the resistivity of the Ag film at as-plated low levels after high temperature annealing. This paper also discusses process integration issues to enable the Ag metallization process for future scaled and three dimensionally chip stacked devices.

  18. Alloying behaviour of electroplated Ag film with its underlying Pd/Ti film stack for low resistivity interconnect metallization

    International Nuclear Information System (INIS)

    Ezawa, Hirokazu; Miyata, Masahiro; Tatsumi, Kohei

    2014-01-01

    Highlights: • Alloying behavior of Ag/Pd/Ti film stack was studied by annealing at 400-800 °C. • The Ag film resistivity decreased with increasing annealing temperature. • Formation of the Pd-Ti intermetallics was found to be dominant over Ag-Pd alloying. • The excess Ti was consumed to form Ti oxides, which inhibited Ti alloying with Ag. -- Abstract: In this paper, viability of electroplated Ag film into device application was studied. Alloying behavior of the Ag film with its underlying Pd(50 nm)/Ti(100 nm) film stack was investigated with respect to heat treatment at different temperatures from 400 °C to 800 °C in an argon ambient. After annealing at 400 °C, the electrical resistivity of the Ag film increased due to Pd alloying with Ag. Formation of Pd–Ti intermetallic phases became dominant over Ag–Pd alloying with increasing annealing temperature, leading to the resistivity decrease of the Ag film. The resistivity of the 800 °C annealed Ag film approached that of its as-plated Ag film. The excess Ti atoms which were not consumed to form the intermetallic phases with the Pd atoms migrated to the Ag film surface to form Ti oxides along the Ag grain boundaries on the topmost film surface. The Ag/Pd/Ti film stack has been confirmed to maintain the resistivity of the Ag film at as-plated low levels after high temperature annealing. This paper also discusses process integration issues to enable the Ag metallization process for future scaled and three dimensionally chip stacked devices

  19. Heavy metal (Pd, Cd, Fe, Zn and Mn) levels in sediments from Nigerian Coastal waters.

    Science.gov (United States)

    Oguguah, N. M.

    2016-02-01

    Sediments collected during a pollution monitoring cruise carried out on Nigerian coastal waters by Nigerian Institute for Oceanography and Marine Research Lagos was analysed for heavy metals. A trawler MS Suzzannah with an on board GPS was used to locate bearings of 25 sampling points (N06o30 and E003o30). Eckman grab was deployed and used in collecting bottom sediments. The sediment were air dried and digested using the method of GEF GCLME. The samples were analysed in five replicates for heavy metals (Pd, Cd, Fe, Zn and Mn) using Varian AA 600 Atomic Absorption Spectrometer. The highest concentration of Pb was transect R (10.93) and the least concentration (0.059) was in transect C. The highest concentration of Cd was transect H (0.75) and the least concentration (0.044) was in transect C. The highest concentration of Fe was transect M (203.582) and the least concentration (2.232) was in transect C. The highest concentration of Zn was transect H (4.595) and the least concentration (0.174) was in transect F. The highest concentration of Mn was transect H (209.251) and the least concentration (0.167) was in transect C.

  20. Metal nanostructures with complex surface morphology: The case of supported lumpy Pd and Pt nanoparticles produced by laser processing of metal films

    Science.gov (United States)

    Ruffino, F.; Maugeri, P.; Cacciato, G.; Zimbone, M.; Grimaldi, M. G.

    2016-09-01

    In this work we report on the formation of lumpy Pd and Pt nanoparticles on fluorine-doped tin oxide/glass (FTO/glass) substrate by a laser-based approach. In general, complex-surface morphology metal nanoparticles can be used in several technological applications exploiting the peculiarities of their physical properties as modulated by nanoscale morphology. For example plasmonic metal nanoparticles presenting a lumpy morphology (i.e. larger particles coated on the surface by smaller particles) can be used in plasmonic solar cell devices providing broadband scattering enhancement over the smooth nanoparticles leading, so, to the increase of the device efficiency. However, the use of plasmonic lumpy nanoparticles remains largely unexplored due to the lack of simply, versatile, low-cost and high-throughput methods for the controllable production of such nanostructures. Starting from these considerations, we report on the observation that nanoscale-thick Pd and Pt films (17.6 and 27.9 nm, 12.1 and 19.5 nm, respectively) deposited on FTO/glass surface irradiated by nanosecond pulsed laser at fluences E in the 0.5-1.5 J/cm2 range, produce Pd and Pt lumpy nanoparticles on the FTO surface. In addition, using scanning electron microscopy analyses, we report on the observation that starting from each metal film of fixed thickness h, the fraction F of lumpy nanoparticles increases with the laser fluence E and saturates at the higher fluences. For each fixed fluence, F was found higher starting from the Pt films (at each starting film thickness h) with respect to the Pd films. For each fixed metal and fluence, F was found to be higher decreasing the starting thickness of the deposited film. To explain the formation of the lumpy Pd and Pt nanoparticles and the behavior of F as a function of E and h both for Pd and Pt, the thermodynamic behavior of the Pd and Pt films and nanoparticles due to the interaction with the nanosecond laser is discussed. In particular, the

  1. Study and characterization of noble metal deposits on similar rusty surfaces to those of the reactor U-1 type BWR of nuclear power station of Laguna Verde

    International Nuclear Information System (INIS)

    Flores S, V. H.

    2011-01-01

    In the present investigation work, were determined the parameters to simulate the conditions of internal oxidation reactor circulation pipes of the nuclear power plant of Laguna Verde in Veracruz. We used 304l stainless steel cylinders with two faces prepared with abrasive paper of No. 600, with the finality to obtain similar surface to the internal circulation piping nuclear reactor. Oxides was formed within an autoclave (Autoclave MEX-02 unit B), which is a device that simulates the working conditions of the nuclear reactor, but without radiation generated by the fission reaction within the reactor. The oxidation conditions were a temperature of 280 C and pressure of 8 MPa, similar conditions to the reactor operating in nuclear power plant of Laguna Verde in Veracruz, Mexico (BWR conditions), with an average conductivity of 4.58 ms / cm and 2352 ppb oxygen to simulate normal water chemistry NWC. Were obtained deposits of noble metal oxides formed on 304l stainless steel samples, in a 250 ml autoclave at a temperature range of 180 to 200 C. The elements that were used to deposit platinum-rhodium (Pt-Rh) with aqueous Na 2 Pt (OH) 6 and Na 3 Rh (NO 2 ) 6 , Silver (Ag) with an aqueous solution of AgNO 3 , zirconium (Zr) with aqueous Zr O (NO 3 ) and ZrO 2 , and zinc (Zn) in aqueous solution of Zn (NO 3 ) 2 under conditions of normal water chemistry. Also there was the oxidation of 304l stainless steel specimens in normal water chemistry with a solution of Zinc (Zn) (NWC + Zn). Oxidation of the specimens in water chemistry with a solution of zinc (Zn + NWC) was prepared in two ways: within the MEX-02 autoclave unit A in a solution of zinc and a flask at constant temperature in zinc solution. The oxides formed and deposits were characterized by scanning electron microscopy, energy dispersive X-ray analysis, elemental field analysis and X-ray diffraction. By other hand was evaluated the electrochemical behavior of the oxides formed on the surface of 304l stainless steel

  2. THE INFLUENCE OF TRANSITION METALS ON THE ...

    African Journals Online (AJOL)

    Experimental results show that the addition of Zr, Mn, Co, and Cu promoters improved the activity of Pt Rh Pd/γ-Al2O3 catalyst remarkably for CO, CH and NOx conversion, respectively. The effective order of the promoters is CuO > ZrO2 > Co3O4 > MnO2. The addition of CuO improved the dispersion of the noble metal on ...

  3. Characterization of Irradiated Metal Waste from the Pyrometallurgical Treatment of Used EBR-II Fuel

    Energy Technology Data Exchange (ETDEWEB)

    B.R. Westphal; K.C. Marsden; W.M. McCartin; S.M. Frank; D.D. Keiser, Jr.; T.S. Yoo; D. Vaden; D.G. Cummings; K.J. Bateman; J. J. Giglio; T. P. O' Holleran; P. A. Hahn; M. N. Patterson

    2013-03-01

    As part of the pyrometallurgical treatment of used Experimental Breeder Reactor-II fuel, a metal waste stream is generated consisting primarily of cladding hulls laden with fission products noble to the electrorefining process. Consolidation by melting at high temperature [1873 K (1600 degrees C)] has been developed to sequester the noble metal fission products (Zr, Mo, Tc, Ru, Rh, Te, and Pd) which remain in the iron-based cladding hulls. Zirconium from the uranium fuel alloy (U-10Zr) is also deposited on the hulls and forms Fe-Zr intermetallics which incorporate the noble metals as well as residual actinides during processing. Hence, Zr has been chosen as the primary indicator for consistency of the metal waste. Recently, the first production-scale metal waste ingot was generated and sampled to monitor Zr content for Fe-Zr intermetallic phase formation and validation of processing conditions. Chemical assay of the metal waste ingot revealed a homogeneous distribution of the noble metal fission products as well as the primary fuel constituents U and Zr. Microstructural characterization of the ingot confirmed the immobilization of the noble metals in the Fe-Zr intermetallic phase.

  4. Shape-controlled synthesis of Pd polyhedron supported on polyethyleneimine-reduced graphene oxide for enhancing the efficiency of hydrogen evolution reaction

    Science.gov (United States)

    Li, Jing; Zhou, Panpan; Li, Feng; Ma, Jianxin; Liu, Yang; Zhang, Xueyao; Huo, Hongfei; Jin, Jun; Ma, Jiantai

    2016-01-01

    The catalytic activity of noble-metal nanoparticles (NPs) often has closely connection with their sizes and geometric shape. In the work, polyhedral NPs of palladium (Pd) with controlled sizes, shapes, and different proportions of {100} to {111} facets on the surface were prepared by a seed-mediated approach. Electrochemical experiment demonstrates that the catalytic performance of the Pd nanocubes (NCs) enclosed by {100} facets is more active than Pd octahedrons enclosed by {111} facets for the hydrogen evolution reaction (HER), which is consistent with density functional theory (DFT) calculation results. Meanwhile, with the assistance of a polyethyleneimine-reduced graphene oxide (PEI-rGO) support, the examined Pd cube/PEI-rGO50:1 (10 wt. %) electrocatalyst presents outstanding HER activity comparable with that of commercial Pt/C catalyst. This correlation between the HER catalytic activity and surface structure will contribute to the reasonable design of Pd catalysts for HER with high efficiency and low metal loading.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-07-01

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

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

    International Nuclear Information System (INIS)

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

    2003-01-01

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

  7. Atomically dispersed Pd catalysts in graphyne nanopore: formation and reactivity

    Science.gov (United States)

    Gu, Yongbing; Chen, Xianlang; Cao, Yongyong; Zhuang, Guilin; Zhong, Xing; Wang, Jianguo

    2017-07-01

    The formation of single-atom noble metal catalysts on carbon materials remains a challenge due to the weak interaction between metals and pristine carbon. By means of density functional theory (DFT) calculations, it is found that the atomically dispersed Pd in graphyne nanopore is much more stable than that of relative Pd clusters. The large diffusion barrier of Pd from the most stable hollow site to the bridge site confirms the kinetic stability of such structures. While CO adsorption causes the pulling of Pd from graphyne nanopore due to the low diffusion barrier, based on DFT calculations, which can be further confirmed by ab initio molecular dynamic simulations. Finally, CO oxidation on the reconstruction of Pd@graphyne exhibits an energy barrier of 0.62 eV in the rate-limiting step through the Langmuir-Hinshelwood mechanism. After the reaction, the catalyst can be restored to the original atomically dispersed state again. This study shows graphyne is an excellent support for an atomically dispersed or single-metal catalyst.

  8. Microstructure and mechanical properties of Pt-added and Pd-added Zr-20Nb alloys and their metal release in 1 mass% lactic acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, R.; Suyalatu,; Tsutsumi, Y. [Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, Chiyoda-ku, Tokyo 101-0062 (Japan); Doi, H., E-mail: doi.met@tmd.ac.jp [Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, Chiyoda-ku, Tokyo 101-0062 (Japan); Nomura, N. [Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, Chiyoda-ku, Tokyo 101-0062 (Japan); Hanawa, T. [Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, Chiyoda-ku, Tokyo 101-0062 (Japan); Graduate School of Engineering, University of Tokyo, Bunkyo-ku, Tokyo 113-8650 (Japan)

    2011-07-20

    The effects of Pt and Pd addition to a Zr-20Nb alloy on its microstructure and mechanical property, as well as the elution of metals from the alloys in lactic acid solution, were investigated. The microstructure was characterized with an X-ray diffractometer (XRD), an optical microscope (OM), and a transmission electron microscope (TEM). The mechanical properties were evaluated by a tensile test. The {beta} phase is dominantly observed in the Zr-20Nb as well as in the Pt-added and Pd-added Zr-20Nb alloys. Needle-like microstructures are observed in equiaxed grains in all alloys. Pd addition to the Zr-20Nb alloy suppresses {omega} phase formation more than Pt addition does. The 0.2% offset yield strength and the ultimate tensile strength of the Pt-added and Pd-added Zr-20Nb alloys increase with the Pt and Pd concentrations. XRD analysis revealed that the lattice parameter of {beta}-Zr in the Pt-added and Pd-added Zr-20Nb alloys decreases with the Pt and Pd concentrations. Pt and Pd solute in {beta}-Zr as a substitutional element and contribute to the increase in the strength by solid solution hardening. The addition of 2Pt and 2Pd to the Zr-20Nb alloy also improves metal elution from the alloys in lactic acid solution.

  9. Stable structures and potential energy surface of the metallic clusters: Ni, Cu, Ag, Au, Pd, and Pt

    Science.gov (United States)

    Wu, Xia; Sun, Yan

    2017-06-01

    Metallic clusters have been widely studied due to their special electrical, optical, and catalytic properties. The many-body Gupta potential is applied to describe the interatomic interaction of Ni, Cu, Ag, Au, Pd, and Pt clusters, and their global minimal structures within 100 atoms are optimized using dynamic lattice searching (DLS) method. The configurational distribution of global minima is analyzed, and the geometrical difference among these clusters is demonstrated. Results show that the dominant motif of Ni and Cu clusters is the icosahedron, and in Ag and Au clusters the number of decahedra is slightly larger than that of the icosahedra. However, more face-centered cubic (fcc), stacking fault fcc, and amorphous structures are formed in Au clusters than in Ag clusters. Furthermore, the main motif of Pd and Pt clusters is the decahedron. In particular, Ni98 adopts a Leary tetrahedral motif, and Pt54 is a central vacant icosahedron. The difference related to the potential parameters of these metallic clusters is further investigated by energy analysis. Moreover, the potential energy surfaces (PES) of 38-atom metallic clusters is characterized in terms of conformational analysis. It was found that the sequence of the number of local minima on the PES from large to low is Ni, Cu, Ag, Pt, Pd, and Au.

  10. Fast microwave-assisted solvothermal synthesis of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated MWCNTs: Pd-based bimetallic catalysts for ethanol oxidation in alkaline medium

    CSIR Research Space (South Africa)

    Ramulifho, T

    2012-01-01

    Full Text Available -MWCNT-Pd and its "mixed" bimetallic electrocatalysts (i.e., SF-MWCNT-PdSn mix and SF-MWCNT-PdNi) towards ethanol oxidation in alkaline medium was investigated. The result shows that the mixed Pd-based catalysts (obtained by simple ultrasonic...

  11. Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd.

    OpenAIRE

    Duguid, J.; Bloomfield, V. A.; Benevides, J.; Thomas, G. J.

    1993-01-01

    Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) ind...

  12. Corrosion resistance of amorphous and crystalline Pd40Ni40P20 alloys in aqueous solutions

    DEFF Research Database (Denmark)

    Wu, Y.F.; Chiang, Wen-Chi; Chu, J.

    2006-01-01

    The corrosion behaviors of amorphous and crystalline Pd40Ni40P20 alloys in various aqueous solutions are reported in this paper. The corrosion resistance of crystalline (annealed) Pd40Ni40P20 is better than that of amorphous Pd40Ni40P20 in various corrosive solutions, due to crystalline Pd40Ni40P20...... and mainly consists of inert Pd5P2, NI3P, Ni2Pd2P and noble Pd phases. These inert and noble properties result in a higher corrosion resistance in crystalline Pd40Ni40P20....

  13. Investigation of Supported Pd-Based Electrocatalysts for the Oxygen Reduction Reaction: Performance, Durability and Methanol Tolerance.

    Science.gov (United States)

    Lo Vecchio, Carmelo; Alegre, Cinthia; Sebastián, David; Stassi, Alessandro; Aricò, Antonino S; Baglio, Vincenzo

    2015-11-25

    Next generation cathode catalysts for direct methanol fuel cells (DMFCs) must have high catalytic activity for the oxygen reduction reaction (ORR), a lower cost than benchmark Pt catalysts, and high stability and high tolerance to permeated methanol. In this study, palladium catalysts supported on titanium suboxides (Pd/Ti n O 2 n -1 ) were prepared by the sulphite complex route. The aim was to improve methanol tolerance and lower the cost associated with the noble metal while enhancing the stability through the use of titanium-based support; 30% Pd/Ketjenblack (Pd/KB) and 30% Pd/Vulcan (Pd/Vul) were also synthesized for comparison, using the same methodology. The catalysts were ex-situ characterized by physico-chemical analysis and investigated for the ORR to evaluate their activity, stability, and methanol tolerance properties. The Pd/KB catalyst showed the highest activity towards the ORR in perchloric acid solution. All Pd-based catalysts showed suitable tolerance to methanol poisoning, leading to higher ORR activity than a benchmark Pt/C catalyst in the presence of low methanol concentration. Among them, the Pd/Ti n O 2 n -1 catalyst showed a very promising stability compared to carbon-supported Pd samples in an accelerated degradation test of 1000 potential cycles. These results indicate good perspectives for the application of Pd/Ti n O 2 n -1 catalysts in DMFC cathodes.

  14. Investigation of Supported Pd-Based Electrocatalysts for the Oxygen Reduction Reaction: Performance, Durability and Methanol Tolerance

    Directory of Open Access Journals (Sweden)

    Carmelo Lo Vecchio

    2015-11-01

    Full Text Available Next generation cathode catalysts for direct methanol fuel cells (DMFCs must have high catalytic activity for the oxygen reduction reaction (ORR, a lower cost than benchmark Pt catalysts, and high stability and high tolerance to permeated methanol. In this study, palladium catalysts supported on titanium suboxides (Pd/TinO2n–1 were prepared by the sulphite complex route. The aim was to improve methanol tolerance and lower the cost associated with the noble metal while enhancing the stability through the use of titanium-based support; 30% Pd/Ketjenblack (Pd/KB and 30% Pd/Vulcan (Pd/Vul were also synthesized for comparison, using the same methodology. The catalysts were ex-situ characterized by physico-chemical analysis and investigated for the ORR to evaluate their activity, stability, and methanol tolerance properties. The Pd/KB catalyst showed the highest activity towards the ORR in perchloric acid solution. All Pd-based catalysts showed suitable tolerance to methanol poisoning, leading to higher ORR activity than a benchmark Pt/C catalyst in the presence of low methanol concentration. Among them, the Pd/TinO2n–1 catalyst showed a very promising stability compared to carbon-supported Pd samples in an accelerated degradation test of 1000 potential cycles. These results indicate good perspectives for the application of Pd/TinO2n–1 catalysts in DMFC cathodes.

  15. Radon: Not so Noble

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 5; Issue 7. Radon: Not so Noble-Radon in the Environment and Associated Health Problems. Deepanjan Majumdar. General Article Volume 5 Issue 7 July 2000 pp 44-55. Fulltext. Click here to view fulltext PDF. Permanent link:

  16. Direct NO decomposition over stepped transition-metal surfaces

    DEFF Research Database (Denmark)

    Falsig, Hanne; Bligaard, Thomas; Christensen, Claus H.

    2007-01-01

    We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition-metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Bronsted-Evans-Polanyi (BEP) relations for the activation barriers of dissociation...... of diatomic molecules over stepped transition- and noble-metal surfaces. The potential energy diagram directly points to why Pd and Pt are the best direct NO decomposition catalysts among the 3d, 4d, and 5d metals. We analyze the NO decomposition reaction in terms of a Sabatier-Gibbs-type analysis, and we...... demonstrate that this type of analysis yields results that to within a surprisingly small margin of error are directly proportional to the measured direct NO decomposition over Ru, Rh, Pt, Pd, Ag, and An. We suggest that Pd, which is a better catalyst than Pt under the employed reaction conditions...

  17. The Self-Organized Critical Behavior in Pd-based Bulk Metallic Glass

    Directory of Open Access Journals (Sweden)

    Zhong Wang

    2015-07-01

    Full Text Available Bulk metallic glasses (BMGs deform irreversibly through shear banding manifested as serrated-flow behavior during compressive tests. The strain-rate-dependent plasticity under uniaxial compression at the strain rates of 2 × 10−2, 2 × 10−3, and 2 × 10−4·s−1 in a Pd-based BMG is investigated. The serrated flow behavior is not observed in the stress-strain curve at the strain rate of 2 × 10−2·s−1. However, the medial state occurs at the strain rates of 2 × 10−3·s−1, and eventually the self-organized critical (SOC behavior appears at the strain rate of 2 × 10−4·s−1. The distribution of the elastic energy density shows a power-law distribution with the power-law exponent of −2.76, suggesting that the SOC behavior appears. In addition, the cumulative probability is well approximated by a power-law distribution function with the power-law exponent of 0.22 at the strain rate of 2 × 10−4·s−1. The values of the goodness of fit are 0.95 and 0.99 at the strain rates of 2 × 10−3 and 2 × 10−4·s−1, respectively. The transition of the dynamic serrated flows of BMGs is from non-serrated flow to an intermediate state and finally to the SOC state with decreasing the strain rates.

  18. Structural behavior of Pd40Cu30Ni10P20 bulk metallic glass below and above the glass transition

    DEFF Research Database (Denmark)

    Mattern, N.; Hermann, H.; Roth, S.

    2003-01-01

    The thermal behavior of the structure of Pd40Cu30Ni10P20 bulk metallic glass has been investigated in situ through the glass transition by means of high-temperature x-ray synchrotron diffraction. The dependence of the x-ray structure factor S(q) of the Pd40Cu30Ni10P20 glass on temperature follows...... the Debye theory up to the glass transition with a Debye temperature theta=296 K. Above the glass transition temperature T-g, the temperature dependence of S(q) is altered, pointing to a continuous development of structural changes in the liquid with temperature. The atomic pair correlation functions g......(r) indicate changes in short-range-order parameters of the first and the second neighborhood with temperature. The temperature dependence of structural parameters is different in glass and in supercooled liquid, with a continuous behavior through the glass transition. The nearest-neighbor distance decreases...

  19. Interaction of Pd with α-Al2O3(0001): A case study of modeling the metal-oxide interface on complex substrates

    OpenAIRE

    Gomes, J. R. B.; Illas, Francesc; Cruz Hernández, Norge; Márquez Cruz, Antonio Marcial; Fernández Sanz, Javier

    2002-01-01

    The Pd/α-Al2O3(0001) interface at low Pd coverage has been studied by a variety of theoretical methods and models at this metal-oxide interface. All results are consistent and predict a noticeable interaction dominated by the metal polarization in response to the presence of the substrate. A significant contribution of the charge transfer from the transition metal to the surface is also observed. The periodic fully relaxed calculations show that the most favorable adsorption site for the inte...

  20. Study and characterization of noble metal deposits on similar rusty surfaces to those of the reactor U-1 type BWR of nuclear power station of Laguna Verde; Estudio y caracterizacion de depositos de metales nobles sobre superficies oxidadas similares a las del reactor de la Central de Laguna Verde (CNLV) U1 del tipo BWR

    Energy Technology Data Exchange (ETDEWEB)

    Flores S, V. H.

    2011-07-01

    In the present investigation work, were determined the parameters to simulate the conditions of internal oxidation reactor circulation pipes of the nuclear power plant of Laguna Verde in Veracruz. We used 304l stainless steel cylinders with two faces prepared with abrasive paper of No. 600, with the finality to obtain similar surface to the internal circulation piping nuclear reactor. Oxides was formed within an autoclave (Autoclave MEX-02 unit B), which is a device that simulates the working conditions of the nuclear reactor, but without radiation generated by the fission reaction within the reactor. The oxidation conditions were a temperature of 280 C and pressure of 8 MPa, similar conditions to the reactor operating in nuclear power plant of Laguna Verde in Veracruz, Mexico (BWR conditions), with an average conductivity of 4.58 ms / cm and 2352 ppb oxygen to simulate normal water chemistry NWC. Were obtained deposits of noble metal oxides formed on 304l stainless steel samples, in a 250 ml autoclave at a temperature range of 180 to 200 C. The elements that were used to deposit platinum-rhodium (Pt-Rh) with aqueous Na{sub 2}Pt (OH){sub 6} and Na{sub 3}Rh (NO{sub 2}){sub 6}, Silver (Ag) with an aqueous solution of AgNO{sub 3}, zirconium (Zr) with aqueous Zr O (NO{sub 3}) and ZrO{sub 2}, and zinc (Zn) in aqueous solution of Zn (NO{sub 3}){sub 2} under conditions of normal water chemistry. Also there was the oxidation of 304l stainless steel specimens in normal water chemistry with a solution of Zinc (Zn) (NWC + Zn). Oxidation of the specimens in water chemistry with a solution of zinc (Zn + NWC) was prepared in two ways: within the MEX-02 autoclave unit A in a solution of zinc and a flask at constant temperature in zinc solution. The oxides formed and deposits were characterized by scanning electron microscopy, energy dispersive X-ray analysis, elemental field analysis and X-ray diffraction. By other hand was evaluated the electrochemical behavior of the oxides

  1. Cu assisted synthesis of self-supported PdCu alloy nanowires with enhanced performances toward ethylene glycol electrooxidation

    Science.gov (United States)

    Yan, Bo; Xu, Hui; Zhang, Ke; Li, Shujin; Wang, Jin; Shi, Yuting; Du, Yukou

    2018-03-01

    Self-supported PdCu alloy nanowires fabricated by a facile one-pot method have been reported, which copper assists in the morphological transformation from graininess to nanowires. The copper incorporated with palladium to form alloy structures cannot only cut down the usage of noble metal but also enhance their catalytic performances. The catalysts with self-supported structure and proper ratio of palladium to copper show great activity and long-term stability for the electrooxidation of ethylene glycol in alkaline solution. Especially for Pd43Cu57, its mass activity reaches to 5570.83 mA mg-1, which is 3.12 times as high as commercial Pd/C. This study highlights an accessible strategy to prepare self-supported PdCu alloy nanowires and their potential applications in renewable energy fields.

  2. Noble Gas Detectors

    CERN Document Server

    Aprile, Elena; Bolozdynya, Alexander I; Doke, Tadayoshi

    2006-01-01

    This book discusses the physical properties of noble fluids, operational principles of detectors based on these media, and the best technical solutions to the design of these detectors. Essential attention is given to detector technology: purification methods and monitoring of purity, information readout methods, electronics, detection of hard ultra-violet light emission, selection of materials, cryogenics etc.The book is mostly addressed to physicists and graduate students involved in the preparation of fundamental next generation experiments, nuclear engineers developing instrumentation

  3. Multi-elemental ionic liquid-based solvent bar micro-extraction of priority and emerging trace metallic pollutants (Cd, Ag, Pd) in natural waters.

    Science.gov (United States)

    Herce-Sesa, Belén; López-López, José A; Moreno, Carlos

    2018-02-12

    Transition metals Cd, Pd and Ag are toxic even at very low concentration. Cd is considered a priority substance; while, Pd and Ag are emerging pollutants. Membrane technologies have been applied for their extraction; however, they require important amounts of reagents, time and energy. Additionally, effective reagents for metal extraction in saline natural waters are limited. In this case, hollow fiber liquid phase micro-extraction with a configuration of solvent bar (SBME) using the ionic liquid Cyphos® 101 as extractant is proposed. Optimized conditions for SBME of Cd, Ag and Pd were 50% Cyphos® 101 in the organic solution, extraction time 30 min and 800 rpm stirring rate. Leaching was in all cases lower than 0.1%. Metallic concentrations were measured by flame atomic absorption spectroscopy. The method was applied to the extraction of Ag, Cd and Pd in natural water samples. Except for waste water, Pd extraction was higher than 90% in all cases. Cd (≈100%) and Ag (93-95%) offered their best results for saline samples. Concluding, the proposed system is a low cost and green methodology that allows a simple and fast extraction of trace pollutants such as Ag, Cd and Pd in different natural waters, including highly saline samples. Copyright © 2018 Elsevier B.V. All rights reserved.

  4. Continuous syntheses of Pd@Pt and Cu@Ag core-shell nanoparticles using microwave-assisted core particle formation coupled with galvanic metal displacement.

    Science.gov (United States)

    Miyakawa, Masato; Hiyoshi, Norihito; Nishioka, Masateru; Koda, Hidekazu; Sato, Koichi; Miyazawa, Akira; Suzuki, Toshishige M

    2014-08-07

    Continuous synthesis of Pd@Pt and Cu@Ag core-shell nanoparticles was performed using flow processes including microwave-assisted Pd (or Cu) core-nanoparticle formation followed by galvanic displacement with a Pt (or Ag) shell. The core-shell structure and the nanoparticle size were confirmed using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observation and EDS elemental mapping. The Pd@Pt nanoparticles with a particle size of 6.5 ± 0.6 nm and a Pt shell thickness of ca. 0.25 nm were synthesized with appreciably high Pd concentration (Pd 100 mM). This shell thickness corresponds to one atomic layer thickness of Pt encapsulating the Pd core metal. The particle size of core Pd was controlled by tuning the initial concentrations of Na2[PdCl4] and PVP. Core-shell Cu@Ag nanoparticles with a particle size of 90 ± 35 nm and an Ag shell thickness of ca. 3.5 nm were obtained using similar sequential reactions. Oxidation of the Cu core was suppressed by the coating of Cu nanoparticles with the Ag shell.

  5. Can there be a multi-bond between noble gas and metal? A theoretical study of F2XeMoF2.

    Science.gov (United States)

    Gao, Kunqi; Sheng, Li

    2017-04-05

    A new noble gas compound containing a Xe-Mo double bond, F 2 XeMoF 2 , was theoretically constructed and studied based on DFT and ab initio calculations. The CCSD(T)-calculated Xe-Mo bond length of 2.518 Å was comparable to the standard value of 2.56 Å. The bonding energy (32.3 kcal mol -1 ) was even higher than that of the Xe-Au bond in the well-known XeAuF complex (24.1 kcal mol -1 ). The result of natural bond orbital (NBO) analysis indicates that there is a σ-bond and a π-bond between the Xe and Mo atoms in F 2 XeMoF 2 . The properties of the Xe-Mo double bond were also analyzed with the atoms in molecules (AIM) approach and natural resonance theory (NRT).

  6. Development of Ag-Pd-Au-Cu alloys for multiple dental applications. Part 2. Mechanical properties of experimental Ag-Pd-Au-Cu alloys containing Sn or Ga for ceramic-metal restorations.

    Science.gov (United States)

    Goto, S; Nakai, A; Miyagawa, Y; Ogura, H

    2001-06-01

    Eighteen Ag-Pd-Au-Cu alloys, consisting of nine Ag-Pd-Au-Cu mother compositions (Pd: 20, 30 or 40%, Au: 20%, Cu: 10, 15 or 20%, Ag: balance) containing either 5% Sn or 5% Ga as an additive metal, were experimentally prepared. Tensile strength, proof stress, elongation, elastic modulus, and Vickers hardness of these alloys were evaluated to clarify the potential of these alloys for use as ceramic-metal restorations as well as the effects of the Pd and Cu contents on their mechanical properties. The tensile strength, proof stress, elongation, elastic modulus and Vickers hardness of the 18 experimental alloys were in the range of 410.0-984.0 MPa, 289.7-774.3 MPa, 2.2-23.7%, 81.3-123.0 GPa and 135.7-332.3 HV1, respectively. Ten of the 18 experimental alloys can be used for ultra-low fusing ceramics based on their proof stress, elastic modulus, elongation and hardness. Between the Ga- and Sn-added alloys, differences in tensile strength, proof stress, elongation and hardness were found at several Ag-Pd-Au-Cu compositions.

  7. Thermal expansion of Pd-based metallic glasses by ab initio methods and high energy X-ray diffraction.

    Science.gov (United States)

    Evertz, Simon; Music, Denis; Schnabel, Volker; Bednarcik, Jozef; Schneider, Jochen M

    2017-11-16

    Metallic glasses are promising structural materials due to their unique properties. For structural applications and processing the coefficient of thermal expansion is an important design parameter. Here we demonstrate that predictions of the coefficient of thermal expansion for metallic glasses by density functional theory based ab initio calculations are efficient both with respect to time and resources. The coefficient of thermal expansion is predicted by an ab initio based method utilising the Debye-Grüneisen model for a Pd-based metallic glass, which exhibits a pronounced medium range order. The predictions are critically appraised by in situ synchrotron X-ray diffraction and excellent agreement is observed. Through this combined theoretical and experimental research strategy, we show the feasibility to predict the coefficient of thermal expansion from the ground state structure of a metallic glass until the onset of structural changes. Thereby, we provide a method to efficiently probe a potentially vast number of metallic glass alloying combinations regarding thermal expansion.

  8. Atomic Distribution in Catalytic Amorphous Metals

    Directory of Open Access Journals (Sweden)

    Sanghita Mridha

    2015-01-01

    Full Text Available The atomic distribution in catalytically active metallic glass alloys, Pd43Cu27Ni10P20 and Pt57.5Cu14.7Ni5.3P22.5, was investigated using three-dimensional atom probe microscopy. Atom probe analysis showed uniform distribution of constituent elements for both the starting amorphous alloys, with no phase separation. Both the crystallized alloys showed eutectic microstructure with a very sharp interface (~0.5 nm as determined from atom probe. The atomic distribution in the devitrified state is explained based on the “fragile liquid” behavior for these noble-metal glassy alloys.

  9. Deuterium-Labeling Study of the Hydrogenation of 2-Methylfuran and 2,5-Dimethylfuran over Carbon-Supported Noble Metal Catalysts.

    Science.gov (United States)

    Kang, Jungshik; Vonderheide, Anne; Guliants, Vadim V

    2015-09-21

    2-Methylfuran and 2,5-dimethylfuran were deuterated over Pd and Pt catalysts at 90-220 °C. Furan ring saturation over a Pd/C catalyst occurred at low reaction temperatures, which led to deuterated THFs, followed by progressive D exchange in the THF ring at higher temperatures. Finally, H/D exchange occurred in the methyl groups on the THF ring. Cleavage of the C-O bond also occurred over a Pd/C catalyst at elevated temperatures, which resulted in deuterated ketones, for which all H atoms were exchanged for D. Alcohols were produced over a Pt/C catalyst at low temperatures because they are more stable than the corresponding ketones. D replaced H on all carbon atoms of the furan ring and saturated the O and C atoms of the broken C-O bond in both deuterated 2-pentanol and 2-hexanol. At low temperatures (90-105 °C), all H atoms in the deuterated alcohols were exchanged for D except for the last two hydrogen atoms on the methyl groups. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Preparation of TiO₂ supported Au–Pd and Cu–Pd by the combined ...

    Indian Academy of Sciences (India)

    TiO₂ supported Au–Pd and Cu–Pd catalysts were prepared by strong electrostatic adsorption (SEA) of Pd followed by electroless deposition (ED) of a second metal with incremental surface coverages of Au or Cu. High dispersion of small Pd particles on the Pd/TiO2 prepared by SEA led to the high amount of second metal ...

  11. Fundamental mechanisms of oxidation of alkaline earth-bearing metal precursors: yttrium-barium-copper-silver-palladium and silver bariate

    Science.gov (United States)

    Sitaraman, Vilayannur R.

    Noble-metal-bearing metallic precursors can be selectively oxidized to yield oxide/noble metal composites. This processing method is investigated for producing 123/Ag-Pd laminates from a solid metallic Y-Ba-Cu-Ag-Pd precursor. A unique feature heretofore unnoticed is the external oxidation mechanism of Ba. The extent of external oxidation at 840C in a 3%H2-Ar atmosphere (PO2 ˜ 10-19 atm.) as measured by a segregation factor, is higher for Ba than for Y. Combined with the fact that Ba does not have significant solid solubility in Ag, Cu or Pd, this means that a short circuit transport path is possible for transport of Ba through such metals as described in chapter 1. Since diffusion through grain boundaries, is fast, the effective permeability of Ba can be relatively high even though its solubility is low. This proposed mechanism is proven using a model system, the Ag5Ba intermetallic compound. Both internal and external oxidation has been demonstrated in this material. Grain boundary diffusion is demonstrated using Ag clad Ag 5Ba. Due to a change in the mechanism from external to internal oxidation of Y in Y-Ba-Cu-Ag-Pd alloys, the imbalance in the surface stoichiometry caused by Ba segregation is not easily removed. A mechanism proposed by Meijering for copper oxide dissolution, Cu migration and Cu reoxidation at the outer surface is also consistent with the microstructural observations in oxidized Y-Ba-Cu-Ag-Pd specimens.

  12. Significance of a Noble Metal Nanolayer on the UV and Visible Light Photocatalytic Activity of Anatase TiO2 Thin Films Grown from a Scalable PECVD/PVD Approach.

    Science.gov (United States)

    Baba, Kamal; Bulou, Simon; Quesada-Gonzalez, Miguel; Bonot, Sébastien; Collard, Delphine; Boscher, Nicolas D; Choquet, Patrick

    2017-11-29

    UV and visible light photocatalytic composite Pt and Au-TiO 2 coatings have been deposited on silicon and glass substrates at low temperature using a hybrid ECWR-PECVD/MS-PVD process. Methylene blue, stearic acid, and sulfamethoxazole were used as dye, organic, and antibiotic model pollutants, respectively, to demonstrate the efficiency of these nanocomposite coatings for water decontamination or self-cleaning surfaces applications. Raman investigations revealed the formation of anatase polymorph of TiO 2 in all synthesized coatings with a shifting of the main vibrational mode peak to higher wavenumber in the case of Au-TiO 2 coating, indicating an increase number of crystalline defects within this coating. Because of the difference of the chemical potentials of each of the investigated noble metals, the sputtered metal layers exhibit different morphology. Pt sputtered atoms, with high surface adhesion, promote formation of a smooth 2D layer. On the other hand, Au sputtered atoms with higher cohesive forces promote the formation of 5-10 nm nanoparticles. As a result, the surface plasmon resonance phenomenon was observed in the Au-TiO 2 coatings. UV photoactivity of the nanocomposite coatings was enhanced 1.5-3 times and 1.3 times for methylene blue and stearic acid, respectively, thanks to the enhancement of electron trapping in the noble metal layer. This electron trapping phenomenon is higher in the Pt-TiO 2 coating because of its larger work function. On the other hand, the enhancement of the visible photoactivity was more pronounced (3 and 7 times for methylene blue and stearic acid, respectively) in the case of Au-TiO 2 thanks to the surface plasmon resonance. Finally, these nanocomposite TiO 2 coatings exhibited also a good ability for the degradation of antibiotics usually found in wastewater such as sulfamethoxazole. However, a complementary test have showed an increase of the toxicity of the liquid medium after photocatalysis, which could be due the

  13. Noble Gases in Lakes and Ground Waters

    OpenAIRE

    Kipfer, Rolf; Aeschbach-Hertig, Werner; Peeters, Frank; Stute, Marvin

    2002-01-01

    In contrast to most other fields of noble gas geochemistry that mostly regard atmospheric noble gases as 'contamination,' air-derived noble gases make up the far largest and hence most important contribution to the noble gas abundance in meteoric waters, such as lakes and ground waters. Atmospheric noble gases enter the meteoric water cycle by gas partitioning during air / water exchange with the atmosphere. In lakes and oceans noble gases are exchanged with the free atmosphere at the surface...

  14. Valence-Band Electronic Structures of High-Pressure-Phase PdF2-type Platinum-Group Metal Dioxides MO2 (M = Ru, Rh, Ir, and Pt)

    Science.gov (United States)

    Soda, Kazuo; Kobayashi, Daichi; Mizui, Tatsuya; Kato, Masahiko; Shirako, Yuichi; Niwa, Ken; Hasegawa, Masashi; Akaogi, Masaki; Kojitani, Hiroshi; Ikenaga, Eiji; Muro, Takayuki

    2018-04-01

    The valence-band electronic structures of high-pressure-phase PdF2-type (HP-PdF2-type) platinum-group metal dioxides MO2 (M = Ru, Rh, Ir, and Pt) were studied by synchrotron radiation photoelectron spectroscopy and first-principles calculations. The obtained photoelectron spectra for HP-PdF2-type RuO2, RhO2, and IrO2 agree well with the calculated valence-band densities of states (DOSs) for these compounds, indicating their metallic properties, whereas the DOS of HP-PdF2-type PtO2 (calculated in the presence and absence of spin-orbit interactions) predicts that this material may be metallic or semimetallic, which is inconsistent with the electric conductivity reported to date and the charging effect observed in current photoelectron measurements. Compared with the calculated results, the valence-band spectrum of PtO2 appears to have shifted toward the high-binding-energy side and reveals a gradual intensity decrease toward the Fermi energy EF, implying a semiconductor-like electronic structure. Spin-dependent calculations predict a ferromagnetic ground state with a magnetization of 0.475 μB per formula unit for HP-PdF2-type RhO2.

  15. Development of casting investment preventing blackening of noble metal alloys part 3. Effect of reducing agent addition on the strength and expansion of the investments.

    Science.gov (United States)

    Meng, Yukun; Nakai, Akira; Ogura, Hideo

    2004-06-01

    Different reducing agents (B, Al, Si and Ti) were individually added to two gypsum-bonded investments to prepare investments preventing surface blackening of some noble cast alloys. The effect of different additive contents on green-body and burnout compressive strength, setting and thermal expansion of the investments were evaluated. The strength and expansion of the investments were changed by the additives. The compressive strength of Al-, Si- and Ti-added investments decreased with the increase of additive contents. The burnout strength of B-added investments significantly increased while green-body strength remained unchanged. The setting expansion of the B-added investments increased while those of the Al-, Si- and Ti-added investments decreased with the increase of additive contents. The thermal expansion of the Si- and Ti-added investments decreased, and that of the Al- and B-added investments remained unchanged. Further study is necessary to evaluate the effects of these additives on the accuracy of dental castings.

  16. Strain field due to transition metal impurities in Ni and Pd

    Indian Academy of Sciences (India)

    1 2. 28 1 π. ¯h2r3 2. dH mr5. (44). In eqs (41) to (44), ∆φFE(r), ∆φc(r) and ∆φb(r) are impurity induced changes in the po- tential due to free electron, s–d hybridization and d-bandwidth contributions respectively. 3. Calculations and results. The above formalism is used to calculate the atomic displacements in Ni and Pd dilute.

  17. Determination of Compton profiles in the metal-hydrogen systems VHx, VDx and PdHx

    International Nuclear Information System (INIS)

    Laesser, R.

    1978-02-01

    Compton profiles for polycrystalline PdH(0.72), VD(0.77), VH(0.71), Pd and V have been determined by Compton scattering of 159 keV photons from a Te-123sup(m) source. The difference in profiles before and after hydrogen loading is compared to different models for the electronic structure of the hydrides. It is shown that the Compton profile is a sensitive test of the accuracy of various model wave functions for the hydrides. In both palladium- and vanadium hydride (deuteride) the anionic model (where it is assumed that the hydrogen forms a negative ion H - in the hydride) does not describe the experimental results. The best agreement with the experimental data for PdH(0.72), VD(0.77) and VH(0.71) is obtained for a model which is based on band structure calculations for these hydrides and which takes into account that hydrogen-palladium or hydrogen-vanadium bonding states are created below the Fermi level by the introduction of hydrogen in the host lattice. (orig.) [de

  18. Comparative Analysis of Cobalt Oxide Nanoisland Stability and Edge Structures on Three Related Noble Metal Surfaces: Au (111), Pt (111) and Ag (111)

    DEFF Research Database (Denmark)

    Fester, Jakob; Bajdich, Michal; Walton, Alexander

    2017-01-01

    Metal oxide nanostructures and thin films grown on metallic substrates have attracted strong attention as model catalysts and as interesting inverse catalyst systems in their own right. In this study, we investigate the role of metal support in the growth and stabilization of cobalt oxide...... nanostructures on the three related (111) surfaces of Au, Pt and Ag, as investigated by means of high-resolution scanning tunneling microscopy and DFT calculations. All three substrates promote the growth of crystalline CoOx (x = 1−2) islands under oxidative conditions, but we find several noteworthy differences...

  19. Branched Pd@Rh core@shell nanocrystals with exposed Rh {100} facets: an effective electrocatalyst for hydrazine electro-oxidation.

    Science.gov (United States)

    Wang, Guojing; Jing, Shengchang; Tan, Yiwei

    2017-11-28

    Shape control of noble metal (NM) nanocrystals (NCs) is of great importance for improving their electrocatalytic performance. In this report, branched Pd@Rh core@shell NCs that have right square prism-like arms with preferential exposure of Rh {100} facets (denoted as b-Pd@Rh-NCs thereafter) are synthesized and utilized as an electrocatalyst for the hydrazine electrooxidation (HEO) in acidic and alkaline electrolytes. The b-Pd@Rh-NCs are obtained by the heteroepitaxial growth of Rh on the pre-formed branched Pd NCs (denoted as b-Pd-NCs thereafter) core in the presence of poly(vinyl pyrrolidone) (PVP) and bromide ions. A comparative analysis of the voltammetric data for the HEO shows a higher activity on the b-Pd@Rh-NCs exposed with Rh {100} faces than on Rh black, the b-Pd-NCs, and Pd black in acid and alkaline solutions, indicating a structure sensitivity of the reaction. Analysis of the products from the b-Pd@Rh-NCs catalysed HEO reveals a very high hydrazine fuel efficiency, as determined by on-line differential electrochemical mass spectrometry (DEMS).

  20. The influence of the pure metal components of four different casting alloys on the electrochemical properties of the alloys.

    Science.gov (United States)

    Tuna, Süleyman H; Pekmez, Nuran Ozçiçek; Keyf, Filiz; Canli, Fulya

    2009-09-01

    The aim of this study was to investigate the influence of the pure metal components of the four different casting alloys on the corrosion behaviors of these alloys tested. Potentiodynamic polarization tests were carried out on four different types of casting alloys and their pure metals at 37 degrees C in an artificial saliva solution. The ions released from the alloys into the solutions during the polarization test were also determined quantitatively using inductively coupled plasma-mass spectrometry (ICP-MS). Ni-Cr (M1) and Co-Cr (M2) alloys had a more homogenous structure than palladium based (M3) and gold based (M4) alloys in terms of the pitting potentials of the casting alloys and those of the pure metals composing the alloys. The total ion concentration released from M3 and M4 was less than from M1 and M2. This may be because M3 and M4 alloys contained noble metals. It was also found that the noble metals in the M3 and M4 samples decreased the current density in the anodic branch of the potentiodynamic polarization curves. In other words, noble metals contributed positively to dental materials. Corrosion resistance of the casting alloys can be affected by the pure metals they are composed of. Au and Pd based noble alloys dissolved less than Ni-Cr and Co-Cr based alloys.

  1. Nanoindentation study on the characteristic of shear transformation zone in a Pd-based bulk metallic glass during serrated flow

    Science.gov (United States)

    Liao, G. K.; Long, Z. L.; Zhao, M. S. Z.; Peng, L.; Chai, W.; Ping, Z. H.

    2018-04-01

    This paper presents the research on the evolution of shear transformation zone (STZ) in a Pd-based bulk metallic glass (BMG) during serrated flow under nanoindentation. A novel method of estimating the STZ volume through statistical analysis of the serrated flow behavior was proposed for the first time. Based on the proposed method, the STZ volume of the studied BMG at various peak loads have been systematically investigated. The results indicate that the measured STZ volumes are in good agreement with that documented in literature, and the STZ size exhibits an increasing trend during indentation. Moreover, the correlation between the serrated flow dynamics and the STZ activation has also been evaluated. It is found that the STZ activation can promote the formation of self-organized critical (SOC) state during serrated flow.

  2. Ultrasound-induced crystallization around the glass transition temperature for Pd40Ni40P20 metallic glass

    International Nuclear Information System (INIS)

    Ichitsubo, Tetsu; Matsubara, Eiichiro; Kai, Satoshi; Hirao, Masahiko

    2004-01-01

    We have found that crystallization of a Pd 40 Ni 40 P 20 bulk metallic glass is accelerated in the vicinity of the glass transition temperature T g when it is subjected to sub/low-MHz frequency ultrasonic vibration. Resonance frequencies and internal frictions have been measured with the electromagnetic acoustic resonance (EMAR) technique. In the initial heating process of an as-cast glassy sample, the resonance frequencies jump up just above T g under ultrasonic excitation, which is attributed to nano-crystallization that is confirmed by the X-ray diffraction profile. However, such a notable change is not observed without ultrasonic vibration. The irregular Λ-shaped internal-friction peaks are also observed prior to the abrupt crystallization. This rapid crystallization is considered to be caused by a stochastic resonance, in which the jump frequency of atoms matches the frequency of the interatomic-potential change by the ultrasonic vibration

  3. Selective noble gases monitoring

    International Nuclear Information System (INIS)

    Janecka, S.; Jancik, O.; Kapisovsky, V.; Kubik, I.; Sevecka, S.

    1995-01-01

    The monitoring of leak releases from ventilation stack of NPP requires a system by several orders more sensitive then currently used radiometer Kalina, designed to cover the range up to a design-based accident. To reach this goal a noble gases monitor with a germanium detector (MPVG) has been developed. It enables nuclide selective monitoring of current value of volume activity of particular nuclides in ventilation stack and daily releases of noble gases (balancing). MPVG can be viewed as a system build of three levels of subsystem: measuring level; control level; presentation level. Measuring level consists of gamma-spectroscopy system and operational parameters monitoring unit (flow rate, temperature, humidity). Control level provides communication between presentation and measuring level, acquisition of operational parameters and power supply. The presentation level of MPVG enables: 1) the measured data storage in predetermined time intervals; 2) the presentation of measured and evaluated values of radiation characteristics. The monitored radionuclides - default set: argon-41, krypton-85m, krypton-87, krypton-88, krypton-89, xenon-131m, xenon-133, xenon-133m, xenon-135, xenon-135m, xenon-137 and xenon-138. The values of volume activities observed at maximum releases have been approximately ten times higher. In that case in balancing some other nuclides exceed corresponding detection limits: 88 Kr(67; 22) Bq/m 3 ; 85m Kr(17; 7) Bq/m 3 ; 135m Xe(7.1; 0.5) Bq/m 3 ; 138 Xe(5.9; 0.9) Bq/m 3 . (J.K.)

  4. Effect of additive metals, Sn, Ga, and In in Ag-Pd-Au-Cu alloys on initial bond strength of 4-META adhesive cement to these alloys.

    Science.gov (United States)

    Goto, Shin-ichi; Churnjitapirom, Pornkiat; Miyagawa, Yukio; Ogura, Hideo

    2008-09-01

    The purpose of this study was to investigate the effects of three additives, Sn, Ga, and In, as well as the main constituents, Pd and Cu, of Ag-Pd-Au-Cu alloys on the initial bond strength of 4-META adhesive cement to these alloys. The Ag-Pd-Au-Cu alloys consisted of 20%, 30% or 40% Pd, and 10%, 15% or 20% Cu, 20% Au, and Ag as balance. Besides, additive metals (Sn, Ga, and In) of 2% and 4% were added to these compositions. The addition of three additives, in general, increased the initial bond strength of the cement in comparison to the mother compositions (0% additives), although the degrees of effectiveness of the three additives were different and varied with their contents. Among these additives, a remarkable increase in bond strength was observed with the addition of In. The increase in Cu content, in many cases, resulted in an increase in bond strength at high Pd contents (30% and 40%), but a decrease at low Pd content (20%) in some cases. The positive effects of the three additives and Cu could be due to the formation of a suitable oxide layer for strong bonding with 4-META.

  5. Positron scattering from noble gases future prospects

    Energy Technology Data Exchange (ETDEWEB)

    Jones, A C L; Caradonna, P; Makochekanwa, C; Slaughter, D S; Sullivan, J P; Buckman, S J [Centre for Antimatter-Matter Studies, Research School of Physics and Engineering, Australian National University, Canberra, ACT (Australia); Mitroy, J, E-mail: acj107@rsphysse.anu.edu.a [Faculty of Education Health and Science, Charles Darwin University, NT (Australia)

    2009-11-01

    Recent results for positron scattering from noble gases over an energy range from 0.5 to 60eV are presented. Measurements include the grand total ({sigma}{sub GT}), Ps formation ({sigma}{sub Ps}) and Grand total - Ps formation (({sigma}{sub GT}-P{sub s}) cross sections. Some preliminary DCS results will also be presented. Work on a formulation of modified effective range theory (MERT) is being undertaken to determine the value of the scattering length which may be useful for identifying a bound state. Plans for experiments on metal atoms will be outlined.

  6. Leaching characteristics of the metal waste form from the electrometallurgical treatment process: Product consistency testing

    International Nuclear Information System (INIS)

    Johnson, S. G.; Keiser, D. D.; Frank, S. M.; DiSanto, T.; Noy, M.

    1999-01-01

    Argonne National Laboratory is developing an electrometallurgical treatment for spent fuel from the experimental breeder reactor II. A product of this treatment process is a metal waste form that incorporates the stainless steel cladding hulls, zirconium from the fuel and the fission products that are noble to the process, i.e., Tc, Ru, Nb, Pd, Rh, Ag. The nominal composition of this waste form is stainless steel/15 wt% zirconium/1--4 wt% noble metal fission products/1--2 wt % U. Leaching results are presented from several tests and sample types: (1) 2 week monolithic immersion tests on actual metal waste forms produced from irradiated cladding hulls, (2) long term (>2 years) pulsed flow tests on samples containing technetium and uranium and (3) crushed sample immersion tests on cold simulated metal waste form samples. The test results will be compared and their relevance for waste form product consistency testing discussed

  7. Noble gases solubility in water

    International Nuclear Information System (INIS)

    Crovetto, Rosa; Fernandez Prini, Roberto.

    1980-07-01

    The available experimental data of solubility of noble gases in water for temperatures smaller than 330 0 C have been critically surveyed. Due to the unique structure of the solvent, the solubility of noble gases in water decreases with temperature passing through a temperature of minimum solubility which is different for each gas, and then increases at higher temperatures. As aresult of the analysis of the experimental data and of the features of the solute-solvent interaction, a generalized equation is proposed which enables thecalculation of Henry's coefficient at different temperatures for all noble gases. (author) [es

  8. EIS-assisted performance analysis of non-noble metal electrocatalyst (Fe-N/C)-based PEM fuel cells in the temperature range of 23-80 deg. C

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Jianlu; Zhang Lei [Institute for Fuel Cell Innovation, National Research Council of Canada, Vancouver, BC, V6T 1W5 (Canada); Bezerra, Cicero W.B. [Institute for Fuel Cell Innovation, National Research Council of Canada, Vancouver, BC, V6T 1W5 (Canada); Department of Chemistry, Universidade Federal do Maranhao, Av. dos Portugueses, S/N 65.080-040 Sao Luis, MA (Brazil); Li Hui; Xia Zetao [Institute for Fuel Cell Innovation, National Research Council of Canada, Vancouver, BC, V6T 1W5 (Canada); Zhang Jiujun [Institute for Fuel Cell Innovation, National Research Council of Canada, Vancouver, BC, V6T 1W5 (Canada)], E-mail: jiujun.zhang@nrc.gc.ca; Marques, Aldalea L.B.; Marques, Edmar P. [Department of Chemistry, Universidade Federal do Maranhao, Av. dos Portugueses, S/N 65.080-040 Sao Luis, MA (Brazil)

    2009-02-15

    A carbon-supported non-noble metal catalyst, Fe-N/C, was used as the cathode catalyst to construct membrane electrolyte assemblies (MEAs) for a proton exchange membrane (PEM) fuel cell. The performance of such a fuel cell was then tested and diagnosed using electrochemical impedance spectroscopy (EIS) in the temperature range of 23-80 deg. C. Based on the EIS measurements, individual resistances, such as charger transfer resistance and membrane resistance, were obtained and used to simulate polarization curves (current-voltage (I-V) curves). A close agreement between the simulated I-V curves and the measured curves demonstrates consistency between the polarization and EIS data. The temperature-dependent parameters obtained via EIS, such as apparent exchange current densities and electrolyte membrane conductivities, were also used to acquire activation energies for both the oxygen reduction reaction (ORR) catalyzed by an Fe-N/C catalyst and the proton transport process across the electrolyte membrane. In addition, the maximum power densities for such a fuel cell were also analyzed.

  9. Electron microscopy of X7R and Y5V type barium titanate multilayer ceramic capacitors with noble and base metal electrodes

    Science.gov (United States)

    Feng, Qiquan

    Two types of multilayer ceramic capacitors (MLCCs), Y5V with Ni electrodes and X7R with Ag/Pd electrodes, were characterized by transmission electron microscopy (TEM) and showed quite different microstructures which determined their dielectric behaviors. In X7R-type MLCCs, core-shell structures were observed. The flat dielectric constant-temperature curves obtained from these materials can be interpreted in terms of the internal stress states in individual grains. The stress states were observed using weak beam dark field (WBDF) microscopy. The strain contours observed were formed by distorted crystal planes and were dependent on the stress state of the crystal instead of crystal symmetry. The stress distribution in individual grains was determined by both the thickness ratio of shell and core and the geometrical relationship of the core and the shell. (111) lamella twins and dislocation loops in the paraelectric phases of BaTiO3 doped with Bi2O3 were analyzed by TEM under two-beam conditions. Y5V-type MLCCs based on re-oxidized Ba(Ti 0.88,Zr0.12)O3 (BTZ) materials exhibited frequency relaxation effects. Multi-domain structures coexisting in one grain were observed at dynamical diffraction conditions. Uneven distribution of internal stress and coexistence of multi-phases and multi-domains in individual grains were considered to be responsible for the frequency relaxor behavior observed in these materials. The compatibility of electrodes and dielectrics in cofired MLCCs with both Ni and Ag/Pd electrodes was characterized by TEM using tripod polished samples. NiO lamellae and P-rich intermediate layers were found in highly accelerated life tested (HALT) MLCCs with Ni electrodes. It is believed that Mn ions were reduced by the Ni electrodes, as P-rich and Mn-rich segregated layers were observed in the virginal non-life tested MLCCs. No silver diffusion was found in either the BaTiO3 based perovskite lattices or the flux phases in air-fired X7R type MLCCs.

  10. Growth and photoemission spectroscopic studies of ultrathin noble ...

    Indian Academy of Sciences (India)

    2015-05-24

    May 24, 2015 ... ness towards most of the residual gases inside ultrahigh vacuum (UHV) chamber [12]. The van der Waals' surface of graphite cleaves very nicely leaving the surface extremely flat with large terraces. Low interdiffusion for most of the noble metals, makes it an ideal substrate material for the growth of thin ...

  11. Comparing Ullmann Coupling on Noble Metal Surfaces: On-Surface Polymerization of 1,3,6,8-Tetrabromopyrene on Cu(111) and Au(111)

    DEFF Research Database (Denmark)

    Pham, Tuan Anh; Song, Fei; Nguyen, Manh-Thuong

    2016-01-01

    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...

  12. Non-noble metal Bi deposition by utilizing Bi{sub 2}WO{sub 6} as the self-sacrificing template for enhancing visible light photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Shixin [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Zhang, Yihe, E-mail: zyh@cugb.edu.cn [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Li, Min [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Du, Xin [Research Center for Bioengineering and Sensing Technology, Department of Chemistry& Biological Engineering, University of Science & Technology Beijing, Beijing 100083 (China); Huang, Hongwei, E-mail: hhw@cugb.edu.cn [Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China)

    2017-01-01

    Highlights: • Bi metal deposited Bi{sub 2}WO{sub 6} photocatalyst is synthesized via an in-situ reduction. • The light absorption of Bi{sub 2}WO{sub 6} is enhanced by Bi metal. • Charge separation efficiency of Bi{sub 2}WO{sub 6} is increased by Bi metal. • Bi-Bi{sub 2}WO{sub 6} shows highly promoted photocatalytic activity for phenol degradation. - Abstract: Bi metal deposited on Bi{sub 2}WO{sub 6} composite photocatalysts have been successfully synthesized via a simple in-situ reduction method at room temperature with using Bi{sub 2}WO{sub 6} as self-sacrificing template and NaBH{sub 4} as reducing agent. The reduction extent can be easily modulated by controlling the concentration of NaBH{sub 4} solution. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FTIR) spectra, N{sub 2} adsorption-desorption isotherms, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), diffuse reflection spectroscopy (DRS) and photoelectrochemical measurements were carried out to analyze the phase, morphology, optical property and photoelectrochemical property of the as-prepared samples. The photocatalytic activity is surveyed by degradation of phenol under visible light (λ > 420 nm), which showed that the BWO-0.2 photocatalyst exhibited the highest efficiency, which was over 3 times as high as pure Bi{sub 2}WO{sub 6}. The enhanced photocatalytic activity should be attributed to strengthened photoabsorption and charge separation efficiency derived from the surface plasmon resonance (SPR) of Bi metal.

  13. Oxidation catalysts comprising metal exchanged hexaaluminate wherein the metal is Sr, Pd, La, and/or Mn

    Science.gov (United States)

    Wickham, David [Boulder, CO; Cook, Ronald [Lakewood, CO

    2008-10-28

    The present invention provides metal-exchanged hexaaluminate catalysts that exhibit good catalytic activity and/or stability at high temperatures for extended periods with retention of activity as combustion catalysts, and more generally as oxidation catalysts, that make them eminently suitable for use in methane combustion, particularly for use in natural gas fired gas turbines. The hexaaluminate catalysts of this invention are of particular interest for methane combustion processes for minimization of the generation of undesired levels (less than about 10 ppm) of NOx species. Metal exchanged hexaaluminate oxidation catalysts are also useful for oxidation of volatile organic compounds (VOC), particularly hydrocarbons. Metal exchanged hexaaluminate oxidation catalysts are further useful for partial oxidation, particularly at high temperatures, of reduced species, particularly hydrocarbons (alkanes and alkenes).

  14. Multi-metallic Nanomaterials From Ni, Ag, Pd With Pt's Catalytic Activity

    KAUST Repository

    Huang, Kuo-Wei

    2015-06-04

    A trimetallic catalyst that is a combination of nickel, silver and palladium metal is described. The trimetallic catalyst can be used to produce hydrogen and is useful as a replacement for platinum in hydrogenation reactions.

  15. Carbonates-based noble metal-free lean NOx trap catalysts MOx-K2CO3/K2Ti8O17 (M = Ce, Fe, Cu, Co) with superior catalytic performance

    Science.gov (United States)

    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.

  16. Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra.

    Science.gov (United States)

    Gilroy, Kyle D; Elnabawy, Ahmed O; Yang, Tung-Han; Roling, Luke T; Howe, Jane; Mavrikakis, Manos; Xia, Younan

    2017-06-14

    Despite the remarkable success in controlling the synthesis of metal nanocrystals, it still remains a grand challenge to stabilize and preserve the shapes or internal structures of metastable kinetic products. In this work, we address this issue by systematically investigating the surface and bulk reconstructions experienced by a Pd concave icosahedron when subjected to heating up to 600 °C in vacuum. We used in situ high-resolution transmission electron microscopy to identify the equilibration pathways of this far-from-equilibrium structure. We were able to capture key structural transformations occurring during the thermal annealing process, which were mechanistically rationalized by implementing self-consistent plane-wave density functional theory (DFT) calculations. Specifically, the concave icosahedron was found to evolve into a regular icosahedron via surface reconstruction in the range of 200-400 °C, and then transform into a pseudospherical crystalline structure through bulk reconstruction when further heated to 600 °C. The mechanistic understanding may lead to the development of strategies for enhancing the thermal stability of metal nanocrystals.

  17. Ultrafine and Ligand-Free Precious Metal (Ru, Ag, Au, Rh and Pd) Nanoclusters Supported on Phosphorus-Doped Carbon.

    Science.gov (United States)

    Liu, Ben; Jin, Lei; Zhong, Wei; Lopes, Aaron; Suib, Steven L; He, Jie

    2018-02-21

    We report the use of phosphorus-doped carbon (P-C) as support to grow ultrasmall (1-3 nm) and ligand-free precious metal nanocrystals (PMNCs) via chemical reduction. We show that the valence states of surface phosphorus species are critical in tuning the affinity between the carbon support and metal precursors, which rationally controls the loading size and uniformity of resultant PMNCs. Five kinds of PMNCs, including Ru, Ag, Au, Rh, and Pd, were grown in situ to demonstrate the key role of surface phosphorus sites on the P-C support. As a proof-of-concept application, Ru nanocatalysts with an average diameter of 1.0±0.2 nm supported on P-C were examined for the electrocatalytic hydrogen evolution reaction (HER). Ultrasmall and ligand-free Ru nanocatalysts exhibited superior HER activity and stability compared to its counterparts with surface agents or larger sizes. An overpotential of 27.6 mV (vs. reversible hydrogen electrode) for Ru nanocatalysts was achieved at a current density of 10 mA cm -2 . This novel method opens a new avenue to immobilize ligand-free and well-dispersed PMNCs on carbon; and, more importantly, it provides a new library of supported PMNCs with high catalytic activity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Quantum-chemical investigation of the nature of metal-carbene and metal-olefin bonds in complexes [ClnM(C2H4)]- (M=Mo,Pd)

    International Nuclear Information System (INIS)

    Gritsenko, O.V.; Mitkov, M.I.; Bagatur'yants, A.A.; Kamalov, G.L.; Kazanskij, V.B.; AN Ukrainskoj SSR, Odessa. Fiziko-Khimicheskij Inst.)

    1986-01-01

    On the basis of electron structure calculation using Huckel method comparative investigation of the nature of metal-ethylidene and metal-ethylene bonds in complexes [Cl 5 Mo(C 2 H 4 )] - and [Cl 3 Pd(C 2 H 4 )] - , and also carbene complex stability regarding olefine izomerization is carried out. It is shown that metal-ethylidene bond in the above complexes is stronger than metal-ethylene one, and Mo(4)-ethylidene bond is stronger than Pd(2)-ethylidene one. It is supposed that relative stability of alkylidene structures may be one of the reasons of catalytic activity of Mo(4) compounds in olefine metathesis and oligomerization reactions in which carbene complex is considered as an intermediate

  19. Understanding the Adsorption of CuPc and ZnPc on Noble Metal Surfaces by Combining Quantum-Mechanical Modelling and Photoelectron Spectroscopy

    Directory of Open Access Journals (Sweden)

    Yu Li Huang

    2014-03-01

    Full Text Available 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.

  20. Review: gas-phase ion chemistry of the noble gases: recent advances and future perspectives.

    Science.gov (United States)

    Grandinetti, Felice

    2011-01-01

    This review article surveys recent experimental and theoretical advances in the gas-phase ion chemistry of the noble gases. Covered issues include the interaction of the noble gases with metal and non-metal cations, the conceivable existence of covalent noble-gas anions, the occurrence of ion-molecule reactions involving singly-charged xenon cations, and the occurrence of bond-forming reactions involving doubly-charged cations. Research themes are also highlighted, that are expected to attract further interest in the future.

  1. Gallium-rich Pd-Ga phases as supported liquid metal catalysts

    Science.gov (United States)

    Taccardi, N.; Grabau, M.; Debuschewitz, J.; Distaso, M.; Brandl, M.; Hock, R.; Maier, F.; Papp, C.; Erhard, J.; Neiss, C.; Peukert, W.; Görling, A.; Steinrück, H.-P.; Wasserscheid, P.

    2017-09-01

    A strategy to develop improved catalysts is to create systems that merge the advantages of heterogeneous and molecular catalysis. One such system involves supported liquid-phase catalysts, which feature a molecularly defined, catalytically active liquid film/droplet layer adsorbed on a porous solid support. In the past decade, this concept has also been extended to supported ionic liquid-phase catalysts. Here we develop this idea further and describe supported catalytically active liquid metal solutions (SCALMS). We report a liquid mixture of gallium and palladium deposited on porous glass that forms an active catalyst for alkane dehydrogenation that is resistant to coke formation and is thus highly stable. X-ray diffraction and X-ray photoelectron spectroscopy, supported by theoretical calculations, confirm the liquid state of the catalytic phase under the reaction conditions. Unlike traditional heterogeneous catalysts, the supported liquid metal reported here is highly dynamic and catalysis does not proceed at the surface of the metal nanoparticles, but presumably at homogeneously distributed metal atoms at the surface of a liquid metallic phase.

  2. Preparation of supported Au–Pd and Cu–Pd by the combined strong ...

    Indian Academy of Sciences (India)

    BOONTIDA PONGTHAWORNSAKUN

    2017-10-25

    Oct 25, 2017 ... Abstract. TiO2 supported Au–Pd and Cu–Pd catalysts were prepared by strong electrostatic adsorption (SEA) of Pd followed by electroless deposition (ED) of a second metal with incremental surface coverages of Au or. Cu. High dispersion of small Pd particles on the Pd/TiO2 prepared by SEA led to the ...

  3. Formation of Mixed-Ligand Complexes of Pd2+ with Nucleoside 5'-Monophosphates and Some Metal-Ion-Binding Nucleoside Surrogates

    Directory of Open Access Journals (Sweden)

    Oleg Golubev

    2014-10-01

    Full Text Available Formation of mixed-ligand Pd2+ complexes between canonical nucleoside 5'-monophosphates and five metal-ion-binding nucleoside analogs has been studied by 1H-NMR spectroscopy to test the ability of these nucleoside surrogates to discriminate between unmodified nucleobases by Pd2+-mediated base pairing. The nucleoside analogs studied included 2,6-bis(3,5-dimethylpyrazol-1-yl-, 2,6-bis(1-methylhydrazinyl- and 6-(3,5-dimethylpyrazol-1-yl-substituted 9-(β-d-ribofuranosylpurines 1–3, and 2,4-bis(3,5-dimethylpyrazol-1-yl- and 2,4-bis(1-methylhydrazinyl-substituted 5-(β-d-ribofuranosyl-pyrimidines 4–5. Among these, the purine derivatives 1-3 bound Pd2+ much more tightly than the pyrimidine derivatives 4, 5 despite apparently similar structures of the potential coordination sites. Compounds 1 and 2 formed markedly stable mixed-ligand Pd2+ complexes with UMP and GMP, UMP binding favored by 1 and GMP by 2. With 3, formation of mixed-ligand complexes was retarded by binding of two molecules of 3 to Pd2+.

  4. Synthesis of nanocrystals with variable high-index Pd facets through the controlled heteroepitaxial growth of trisoctahedral Au templates.

    Science.gov (United States)

    Yu, Yue; Zhang, Qingbo; Liu, Bo; Lee, Jim Yang

    2010-12-29

    The shape-controlled synthesis of noble metal nanocrystals (NCs) bounded by high-index facets is a current research interest because the products have the potential of significantly improving the catalytic performance of NCs in industrially important reactions. This study reports a versatile method for synthesizing polyhedral NCs enclosed by a variety of high-index Pd facets. The method is based on the heteroepitaxial growth of Pd layers on concave trisoctahedral (TOH) gold NC seeds under careful control of the growth kinetics. Polyhedral Au@Pd NCs with three different classes of high-index facets, including concave TOH NCs with {hhl} facets, concave hexoctahedral (HOH) NCs with {hkl} facets, and tetrahexahedral (THH) NCs with {hk0} facets, can be formed in high yield. The Miller indices of NCs are also modifiable, and we have used the THH NCs as a demonstrative example. The catalytic activities of these NCs were evaluated by the structure-sensitive reaction of formic acid electro-oxidation. The results showed that the high-index facets are generally more active than the low-index facets. In summary, a seeded growth process based on concave high-index faceted monometallic TOH NC templates and careful control of the growth kinetics is a simple and effective strategy for the synthesis of noble metal NCs with high-index facets. It also offers tailorability of the surface structure in shape-controlled synthesis.

  5. Accurate description of the bonding of C6H6 at noble metal surfaces, using a local exchange-correlation correction scheme

    Science.gov (United States)

    McNellis, Erik; Reuter, Karsten; Scheffler, Matthias

    2008-03-01

    The adsorption of benzene (C6H6) at the Cu(111) surface is a much studied model system for the interaction of larger π-conjugated molecules with solid surfaces. At first glance a simple system, the suspected predominantly van der Waals type bonding at the extended metal surface poses a severe challenge for accurate first-principles calculations. Density-Functional Theory (DFT) with local and semi-local exchange-correlation (xc) functionals is uncertain to properly account for this type of bonding, while the system sizes required to correctly grasp the metallic band structure are computationally untractable with correlated wave function techniques. We overcome these limitations with a recently introduced ``local xc correction'' scheme [1], correcting the adsorption energetics from present-day DFT xc functionals with hybrid functional and Møller-Plesset perturbation theory calculations for small clusters. From the obtained convergence of the xc correction with cluster size we can disentangle short-range and dispersion type contributions to the bonding of the molecule at different heights above the surface. This enables us to qualify the role played by the two contributions in determining the binding energetics and geometry. [1] Q.-M. Hu, K. Reuter, and M. Scheffler, PRL 98, 176103 (2007) and 99, 169903 (2007); C. Tuma and J. Sauer, CPL 387, 388 (2004).

  6. Non-noble metal Bi deposition by utilizing Bi2WO6 as the self-sacrificing template for enhancing visible light photocatalytic activity

    Science.gov (United States)

    Yu, Shixin; Zhang, Yihe; Li, Min; Du, Xin; Huang, Hongwei

    2017-01-01

    Bi metal deposited on Bi2WO6 composite photocatalysts have been successfully synthesized via a simple in-situ reduction method at room temperature with using Bi2WO6 as self-sacrificing template and NaBH4 as reducing agent. The reduction extent can be easily modulated by controlling the concentration of NaBH4 solution. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FTIR) spectra, N2 adsorption-desorption isotherms, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), diffuse reflection spectroscopy (DRS) and photoelectrochemical measurements were carried out to analyze the phase, morphology, optical property and photoelectrochemical property of the as-prepared samples. The photocatalytic activity is surveyed by degradation of phenol under visible light (λ > 420 nm), which showed that the BWO-0.2 photocatalyst exhibited the highest efficiency, which was over 3 times as high as pure Bi2WO6. The enhanced photocatalytic activity should be attributed to strengthened photoabsorption and charge separation efficiency derived from the surface plasmon resonance (SPR) of Bi metal.

  7. Structures of metal nanoparticles adsorbed on MgO(001).II. Pt and Pd

    Czech Academy of Sciences Publication Activity Database

    Goniakowski, J.; Jelea, A.; Mottet, Ch.; Barcaro, G.; Fortunelli, A.; Kuntová, Zdeňka; Nita, F.; Levi, A. C.; Rossi, G.; Ferrando, R.

    2009-01-01

    Roč. 130, č. 17 (2009), 174703/1-174703/9 ISSN 0021-9606 Institutional research plan: CEZ:AV0Z10100521 Keywords : adsorbed layers * epitaxial layers * metal clusters * nanoparticles surface phase transformations Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.093, year: 2009

  8. Role of reactive metals in Ge/Pd/GaAs contact structures

    Czech Academy of Sciences Publication Activity Database

    Macháč, P.; Peřina, Vratislav

    2003-01-01

    Roč. 65, č. 3 (2003), s. 335-343 ISSN 0167-9317 Institutional research plan: CEZ:AV0Z1048901 Keywords : gallium arsenide * ohmic contact * reactive metal Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.229, year: 2003

  9. Fractionation of rhenium from osmium during noble metal alloy formation in association with sulfides: Implications for the interpretation of model ages in alloy-bearing magmatic rocks

    Science.gov (United States)

    Fonseca, Raúl O. C.; Brückel, Karoline; Bragagni, Alessandro; Leitzke, Felipe P.; Speelmanns, Iris M.; Wainwright, Ashlea N.

    2017-11-01

    Although Earth's continental crust is thought to derive from melting of the Earth's mantle, how the crust has formed and the timing of its formation are not well understood. The main difficulty in understanding how the crust was extracted from the Earth's mantle is that most isotope systems recorded in mantle rocks have been disturbed by crustal recycling, metasomatic activity and dilution of the signal by mantle convection. In this regard, important age constraints can be obtained from Re-Os model ages in platinum group minerals (PGM), as Re-poor and Os-rich PGM show evidence of melting events up to 4.1 Ga. To constrain the origin of the Re-Os fractionation and Os isotope systematics of natural PGM, we have investigated the linkage between sulfide and PGM grains of variable composition via a series of high-temperature experiments carried out at 1 bar. We show that with the exception of laurite, all experimentally-produced PGM, in particular Pt3Fe (isoferroplatinum) and Pt-Ir metal grains, are systematically richer in Re than their sulfide precursors and will develop radiogenic 187Os /188Os signatures over time relative to their host base metal sulfides. Cooling of an PGM-saturated sulfide assemblage shows a tendency to amplify the extent of Re-Os fractionation between PGM and the different sulfide phases present during cooling. Conversely, laurite grains (RuS2) are shown to accept little to no Re in them and their Os isotope composition changes little over time as a result. Laurite is therefore the PGM that provides the most robust Re-depletion ages in mantle lithologies. Our results are broadly consistent with observations made on natural PGM, where laurites are systematically less radiogenic than Pt-rich PGM. These experimental results highlight the need for the acquisition of large datasets for both mantle materials and ophiolite-derived detrital grains that include measurements of the Os isotope composition of minerals rich in highly siderophile elements at

  10. Noble-metal-free g-C3N4/Ni(dmgH)2 composite for efficient photocatalytic hydrogen evolution under visible light irradiation

    Science.gov (United States)

    Cao, Shao-Wen; Yuan, Yu-Peng; Barber, James; Loo, Say Chye Joachim; Xue, Can

    2014-11-01

    We report an economic photocatalytic H2 generation system consisting of earth-abundant elements only by coupling graphitic carbon nitride (g-C3N4) with Ni(dmgH)2 sub-microwires that serve as effective co-catalysts for H2 evolution. This composite photocatalyst exhibits efficient hydrogen evolution under visible-light irradiation in the presence of triethanolamine as electron donor. The optimal coupling of 3.5 wt% Ni(dmgH)2 to g-C3N4 (5 mg composite) allows for a steady H2 generation rate of 1.18 μmol/h with excellent stability. This study demonstrates that the combination of polymeric g-C3N4 semiconductor and small proportion of transition-metal-based co-catalyst could serve as a stable, earth-abundant and low-cost system for solar-to-hydrogen conversion.

  11. On the mechanisms of cation injection in conducting bridge memories: The case of HfO2 in contact with noble metal anodes (Au, Cu, Ag)

    International Nuclear Information System (INIS)

    Saadi, M.; Gonon, P.; Vallée, C.; Mannequin, C.; Bsiesy, A.; Grampeix, H.; Jalaguier, E.; Jomni, F.

    2016-01-01

    Resistance switching is studied in HfO 2 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 HfO 2 /anode interface. If oxygen ion mobility is low in the interfacial oxide, a negative space charge builds-up at the HfO 2 /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).

  12. Tungsten-coated nano-boron carbide as a non-noble metal bifunctional electrocatalyst for oxygen evolution and hydrogen evolution reactions in alkaline media.

    Science.gov (United States)

    Zhang, Yan; Wang, Yanhui; Han, Chan; Jia, Shaopei; Zhou, Shuyu; Zang, Jianbing

    2017-12-14

    Herein, tungsten-coated nano-boron carbide (W-WB 4 -WC x /B 4 C) particles were prepared by heating a mixture of B 4 C and W powder using a spark plasma coating (SPC) method. During the discharge treatment process, metal W in the mixture is activated and reacts with B 4 C to form WC x , WB 4 , and graphite nanoribbons. The oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance of W-WB 4 -WC x /B 4 C is tested in an alkaline solution, and the results show that the W-WB 4 -WC x /B 4 C composite electrocatalyst exhibits a low overpotential of 0.36 V at 10 mA cm -2 for the OER, a small overpotential of -0.19 V (j = 10 mA cm -2 ) for the HER, as well as good stability. The significantly enhanced electrocatalytic performance of the W-WB 4 -WC x /B 4 C composites is attributed to their unique structure, in which WC x and WB 4 not only improve the catalytic activity for the OER and HER, but also effectively anchor the W coating on the substrate.

  13. Nitrogen-Doped Hollow Carbon Spheres with Embedded Co Nanoparticles as Active Non-Noble-Metal Electrocatalysts for the Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Ruohao Xing

    2018-02-01

    Full Text Available Transition metal (Fe, Co, Ni complexes on carbon nanomaterials are promising candidates as electrocatalysts towards the oxygen reduction reaction (ORR. In this paper, nitrogen-doped hollow carbon spheres with embedded Co nanoparticles were successfully prepared via a controllable synthesis strategy. The morphology characterization shows that the hollow carbon spheres possess an average diameter of ~150 nm with a narrow size distribution and a shell thickness of ~14.5 nm. The content of N doping ranges from 2.1 to 6.6 at.% depending on the calcination temperature from 900 to 1050 °C. Compared with commercial Pt/C, the Co-containing nitrogen-doped hollow carbon spheres prepared at 900 °C (CoNHCS-900 as an ORR electrocatalyst shows a half-wave potential shift of only ∆E1/2 = 55 mV, but a superior stability of about 90.2% maintenance after 20,000 s in the O2-saturated 0.1 M KOH at a rotating speed of 1600 rpm. This could be ascribed to the synergistic effects of N-containing moieties, Co-Nx species, and Co nanoparticles, which significantly increase the density of active sites and promote the charge transfer during the ORR process.

  14. Compression-compression fatigue of Pd43Ni10Cu27P20 metallic glass foam

    Science.gov (United States)

    Wang, Gongyao; Demetriou, Marios D.; Schramm, Joseph P.; Liaw, Peter K.; Johnson, William L.

    2010-07-01

    Compression-compression fatigue testing of metallic-glass foam is performed. A stress-life curve is constructed, which reveals an endurance limit at a fatigue ratio of about 0.1. The origin of fatigue resistance of this foam is identified to be the tendency of intracellular struts to undergo elastic and reversible buckling, while the fatigue process is understood to advance by anelastic strut buckling leading to localized plasticity (shear banding) and ultimate strut fracture. Curves of peak and valley strain versus number of cycles coupled with plots of hysteresis loops and estimates of energy dissipation at various loading cycles confirm the four stages of foam-fatigue.

  15. Noble metal recycling. Project 2: Optimization of discontinuous thermal processes (emission reduction). Final report; Edelmetallrecycling. Teilvorhaben 2: Weiterentwicklung der Verfahrenstechnik bei diskontinuierlichen thermischen Prozessen (Emissionsminderung). Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Baumbach, G.; Berger, R.

    2000-10-01

    A batch operated incineration process, used for the recycling of precious metals is described in the report. The development of a new combined pyrolysis/oxidation Process is the main focus of the work. This new process has several remarkable advantages compared to traditionally used techniques. The optimisation of the process with a modern fuzzy based control technique is described in detail. The emissions of the process were reduced considerably applying the new process and the innovative control technique. Furthermore the layout of several components of the new process can be reduced in the future. The developed techniques can also be applied in other thermal processes, especially batch processes. Additionally the application of catalysts for PCDD/PCDF reduction in the flue gas upstream and downstream of the filter was investigated. Whereas the catalyst performed well, as expected, downstream of the filter, no acceptable operation was possible upstream of the filter. As the reheating downstream the filter is economically not feasible the application of catalysts is not applicable for the describe process. (orig.) [German] Die Arbeit beschreibt einen diskontinuierlichen thermischen Prozess, der zur Rueckgewinnung von Edelmetallen eingesetzt wird. Der Schwerpunkt der Arbeit liegt auf der Entwicklung eines neuartigen kombinierten Pyrolyse/Oxidations-Prozesses, der gegenueber den traditionell eingesetzten Anlagen grosse Vorteile aufweist. Die Optimierung dieses Prozesses mit Hilfe modernster Fuzzy-Regelungstechnik wird detailliert beschrieben. Mit dem neuen Verfahren und den innovativen Regelungstechniken konnten die Emissionen des Prozesses merklich gesenkt werden, ohne den Energiebedarf negativ zu beeinflussen. Ausserdem koennen zukuenftige Anlagen kleiner ausgelegt werden. Die entwickelten Verfahren koennen auch auf andere thermische Prozesse uebertragen werden. Weiterhin wurde der Einsatz von Katalysatoren zur PCDD/PCDF-Minderung im Rein- und Rohgas untersucht

  16. Mechanism of NO Photocatalytic Oxidationon g-C3N4 Was Changed by Pd-QDs Modification

    Directory of Open Access Journals (Sweden)

    Yuhan Li

    2015-12-01

    Full Text Available Quantum dot (QD sensitization can increase the light absorption and electronic transmission of photocatalysts. However, limited studies have been conducted on the photocatalytic activity of photocatalysts after modification by noble metal QDs. In this study, we developed a simple method for fabricating Pd-QD-modified g-C3N4. Results showed that the modification of Pd-QDs can improve the NO photocatalytic oxidation activity of g-C3N4. Moreover, Pd-QD modification changed the NO oxidation mechanism from the synergistic action of h+ and O2− to the single action of ·OH. We found that the main reason for the mechanism change was that Pd-QD modification changed the molecular oxygen activation pathway from single-electron reduction to two-electron reduction. This study can not only develop a novel strategy for modifying Pd-QDs on the surface of photocatalysts, but also provides insight into the relationship between Pd-QD modification and the NO photocatalytic oxidation activity of semiconductor photocatalysts.

  17. A facile one-pot solvothermal method for synthesis of magnetically recoverable Pd-Fe3O4 hybrid nanocatalysts for the Mizoroki-Heck reaction

    Science.gov (United States)

    Zhen, Fangchen; Ran, Maofei; Chu, Wei; Jiang, Chengfa; Sun, Wenjing

    2018-03-01

    Pd-Fe3O4 hybrid nanostructures were prepared using a simple one-pot hydrothermal method. The prepared materials were characterized by Fourier transform-infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma, N2 adsorption-desorption, and vibrating sample magnetometry. This self-assembled nanosystem acted as an efficient magnetically recyclable noble metal-based multi-functional nanocatalyst. It showed excellent catalytic activity and stability for the Heck reaction of iodobenzene and styrene under mild conditions. The methods used to prepare the Pd-Fe3O4 catalysts were simple and low-cost, which will be useful for the large-scale development and application of a magnetically recoverable Pd catalyst.

  18. Structural stability of Pd40Cu30Ni10P20 metallic glass in supercooled liquid region

    International Nuclear Information System (INIS)

    Jiang, J.Z.; Saksl, K.

    2004-01-01

    Phase separation of bulk and ribbon Pd 40 Cu 30 Ni 10 P 20 glasses, annealed in the supercooled liquid region at ambient pressure and high pressures, has been studied by means of differential scanning calorimetry (DSC) and X-ray diffraction techniques. DSC measurements show only one glass transition event in all annealed samples, indicating that no phase separation occurs in the alloy annealed in the supercooled liquid region. Phase analyses reveal at least six crystalline phases in the crystallized sample: monoclinic, tetragonal Cu 3 Pd-like, rhombohedral, fcc-Ni 2 Pd 2 P, fcc-(Ni, Pd) solid solution, and body-centered tetragonal (bct) Ni 3 P-like phases. Annealing treatments under external pressures in the vicinity of the glass transition temperature neither induce phase separation nor alter the glass transition temperature of the Pd 40 Cu 30 Ni 10 P 20 bulk glass

  19. Isolation and Structural Characterization of a Mackay 55-Metal-Atom Two-Shell Icosahedron of Pseudo-Ih Symmetry, Pd55L12(μ3-CO)20 (L = PR3, R = Isopropyl): Comparative Analysis with Interior Two-Shell Icosahedral Geometries in Capped Three-Shell Pd145, Pt-Centered Four-Shell Pd-Pt M165, and Four-Shell Au133 Nanoclusters.

    Science.gov (United States)

    Erickson, Jeremiah D; Mednikov, Evgueni G; Ivanov, Sergei A; Dahl, Lawrence F

    2016-02-10

    We present the first successful isolation and crystallographic characterization of a Mackay 55-metal-atom two-shell icosahedron, Pd55L12(μ3-CO)20 (L = PPr(i)3) (1). Its two-shell icosahedron of pseudo-Ih symmetry (without isopropyl substituents) enables a structural/bonding comparison with interior 55-metal-atom two-shell icosahedral geometries observed within the multi-shell capped 145-metal-atom three-shell Pd145(CO)72(PEt3)30 and 165-metal-atom four-shell Pt-centered (μ12-Pt)Pd164-xPtx(CO)72(PPh3)20 (x ≈ 7) nanoclusters, and within the recently reported four-shell Au133(SC6H4-p-Bu(t))52 nanocluster. DFT calculations carried out on a Pd55(CO)20(PH3)12 model analogue, with triisopropyl phosphine substituents replaced by H atoms, revealed a positive +0.84 e charge for the entire Pd55 core, with a highly positive second-shell Pd42 surface of +1.93 e.

  20. The Inert and the Noble

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 4; Issue 3. The Inert and the Noble. A G Samuelson. Article-in-a-Box Volume 4 Issue 3 March 1999 pp 3-5 ... Author Affiliations. A G Samuelson1. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, India.

  1. Effect of an in-plane ligand on the electronic structures of bromo-bridged nano-wire Ni-Pd mixed-metal complexes, [Ni(1-x)Pd(x)(bn)2Br]Br2 (bn = 2S,3S-diaminobutane).

    Science.gov (United States)

    Sasaki, Mari; Wu, Hashen; Kawakami, Daisuke; Takaishi, Shinya; Kajiwara, Takashi; Miyasaka, Hitoshi; Breedlove, Brian K; Yamashita, Masahiro; Kishida, Hideo; Matsuzaki, Hiroyuki; Okamoto, Hiroshi; Tanaka, Hisaaki; Kuroda, Shinichi

    2009-08-03

    Single crystals of quasi-one-dimensional bromo-bridged Ni-Pd mixed-metal complexes with 2S,3S-diaminobutane (bn) as an in-plane ligand, [Ni(1-x)Pd(x)(bn)(2)Br]Br(2), were obtained by using an electrochemical oxidation method involving mixed methanol/2-propanol (1:1) solutions containing different ratios of [Ni(II)(bn)(2)]Br(2) and [Pd(II)(bn)(2)]Br(2). To investigate the competition between the electron-correlation of the Ni(III) states, or Mott-Hubbard states (MH), and the electron-phonon interaction of the Pd(II)-Pd(IV) mixed valence states, or charge-density-wave states (CDW), in the Ni-Pd mixed-metal compounds, X-ray structure analyses, X-ray oscillation photograph, and Raman, IR, ESR, and single-crystal reflectance spectra were analyzed. In addition, the local electronic structures of Ni-Pd mixed-metal single crystals were directly investigated by using scanning tunneling microscopy (STM) at room temperature and ambient pressure. The oxidation states of [Ni(1-x)Pd(x)(bn)(2)Br]Br(2) changed from a M(II)-M(IV) mixed valence state to a M(III) MH state at a critical mixing ratio (x(c)) of approximately 0.8, which is lower than that of [Ni(1-x)Pd(x)(chxn)(2)Br]Br(2) (chxn = 1R,2R-diaminocyclohexane) (x(c) approximately 0.9) reported previously. The lower value of x(c) for [Ni(1-x)Pd(x)(bn)(2)Br]Br(2) can be explained by the difference in their CDW dimensionalities because the three-dimensional CDW ordering in [Pd(bn)(2)Br]Br(2) observed by using X-ray diffuse scattering stabilizes the Pd(II)-Pd(IV) mixed valence state more than two-dimensional CDW ordering in [Pd(chxn)(2)Br]Br(2) does, which has been reported previously.

  2. The hierarchy of 1D-, 2D- and 3D-dimensional LPS in Cu-Pd and Ag-Pd: A first-principles study

    Science.gov (United States)

    Bärthlein, S.; Winning, E.; Müller, S.; Hart, G. L. W.; Zunger, A.

    2006-03-01

    Throughout many decades the marvelous variety of so-called long-periodic superlattices (LPS) - being constructed from stacks of L12 with a certain period M after which an anti-phase boundary is introduced - has been a matter of interest for binary compounds consisting of Pd and noble metals such like Cu, Ag and Au. Whereas Au0.75Pd0.75 puts forth the D023 (i.e. M=2) structure as ground state [1], Cu0.75Pd0.75 and Ag0.75Pd0.75 exhibit LPS3 (i.e. M=3) as T=0K ground state. Moreover, the formation enthalpies for a whole class of superlattices are almost degenerated. In order to control the energetical hierarchies of all LPS in question the usual 1D-LPS configuration space must be overcome. We therefore demonstrate how for each system a set of suitable interactions can be constructed by first principles means. Questions concerning a complete description and exhaustive predictive power will be asked and answered by a mixed-space cluster expansion that allows us to handle 1D-LPS with average M, 2D- and 3D-LPS with arbitrary integer M and to predict their energies in order to investigate their abilities to serve as ground state candidates. [1] S. Barabash et al., submitted to Phys. Rev. B

  3. Novel Metal Nanomaterials and Their Catalytic Applications

    Directory of Open Access Journals (Sweden)

    Jiaqing Wang

    2015-09-01

    Full Text Available In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe2O3 nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts and their new catalytic applications in our group, to establish heterogeneous catalytic system in “green” environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials’ development that leads to new opportunities in nanocatalysis.

  4. Synthesis of 4H/fcc Noble Multimetallic Nanoribbons for Electrocatalytic Hydrogen Evolution Reaction.

    Science.gov (United States)

    Fan, Zhanxi; Luo, Zhimin; Huang, Xiao; Li, Bing; Chen, Ye; Wang, Jie; Hu, Yanling; Zhang, Hua

    2016-02-03

    Noble multimetallic nanomaterials, if only consisting of Au, Ag, Pt, and Pd, typically adopt the high-symmetry face-centered cubic (fcc) structure. Here for the first time, by using the 4H/fcc Au@Ag nanoribbons (NRBs) as seeds, we report the synthesis of 4H/fcc trimetallic Au@PdAg core-shell NRBs via the galvanic reaction method under ambient conditions. Moreover, this strategy can also be used to synthesize 4H/fcc trimetallic Au@PtAg and quatermetallic Au@PtPdAg core-shell NRBs. Impressively, for the first time, these alloy shells, i.e., PdAg, PtAg, and PtPdAg, epitaxially grown on the 4H/fcc Au core with novel 4H hexagonal phase were successfully synthesized. Remarkably, the obtained 4H/fcc Au@PdAg NRBs exhibit excellent electrocatalytic activity toward the hydrogen evolution reaction, which is even quite close to that of the commercial Pt black. We believe that our findings here may provide a novel strategy for the crystal-structure-controlled synthesis of advanced functional noble multimetallic nanomaterials with various promising applications.

  5. Toward hybrid Au nanorods @ M (Au, Ag, Pd and Pt) core-shell heterostructures for ultrasensitive SERS probes

    Science.gov (United States)

    Xie, Xiaobin; Gao, Guanhui; Kang, Shendong; Lei, Yanhua; Pan, Zhengyin; Shibayama, Tamaki; Cai, Lintao

    2017-06-01

    Being able to precisely control the morphologies of noble metallic nanostructures is of essential significance for promoting the surface-enhanced Raman scattering (SERS) effect. Herein, we demonstrate an overgrowth strategy for synthesizing Au @ M (M = Au, Ag, Pd, Pt) core-shell heterogeneous nanocrystals with an orientated structural evolution and highly improved properties by using Au nanorods as seeds. With the same reaction condition system applied, we obtain four well-designed heterostructures with diverse shapes, including Au concave nanocuboids (Au CNs), Au @ Ag crystalizing face central cube nanopeanuts, Au @ Pd porous nanocuboids and Au @ Pt nanotrepangs. Subsequently, the exact overgrowth mechanism of the above heterostructural building blocks is further analysed via the systematic optimiziation of a series of fabrications. Remarkably, the well-defined Au CNs and Au @ Ag nanopeanuts both exhibit highly promoted SERS activity. We expect to be able to supply a facile strategy for the fabrication of multimetallic heterogeneous nanostructures, exploring the high SERS effect and catalytic activities.

  6. Effects of single metal atom (Pt, Pd, Rh and Ru) adsorption on the photocatalytic properties of anatase TiO2

    Science.gov (United States)

    Jin, Cui; Dai, Ying; Wei, Wei; Ma, Xiangchao; Li, Mengmeng; Huang, Baibiao

    2017-12-01

    The effects of single metal atom (Pt, Pd, Rh and Ru) adsorption on the photocatalytic properties of anatase TiO2 are investigated by means of the first-principles calculations based on density functional theory (DFT). Our results show that the most stable adsorption site for single metal atom on anatase TiO2 (101) surface is the bridge site formed by two twofold coordinated oxygen (O2c) atoms at the step edge. Due to the charge transfer from metal atoms to anatase TiO2 (101) surface, the work function of adsorbed surface is significantly smaller than the clean one, indicating enhanced surface activity. Fukui functions are highly localized around the isolated metal atoms, indicating that single metal atoms on anatase TiO2 (101) surface serve as the active reduction and oxidation sites in the photocatalytic process. Photo-induced electrons in the electronically excited TiO2 photocatalyst can be transferred to target species through the deposited single atoms. The band structures of host TiO2 are almost unchanged upon the adsorption, and the metal induced states are located in the band gap of the host. Remarkably, due to the metal atoms adsorption, the upward shift of conduction band edge will improve the reducing capacity of anatase TiO2. Moreover, when single metal atoms are adsorbed, potential energy of topmost surface Ti atoms turns to get close to the vacuum level, which significantly facilitates the electron transfer for hydrogen evolution. Results in this work provide new insights into improving the photocatalytic performance by single metal atoms adsorption.

  7. Effect of different surface treatments and retainer designs on the retention of posterior Pd-Ag porcelain-fused-to-metal resin-bonded fixed partial dentures.

    Science.gov (United States)

    Chen, Xiwen; Zhang, Yixin; Zhou, Jinru; Chen, Chenfeng; Zhu, Zhimin; Li, Lei

    2018-02-01

    The aim of this study was to investigate the adhesive property of palladium-silver alloy (Pd-Ag) and the simulated clinical performance of Pd-Ag porcelain-fused-to-metal (PFM), resin-bonded, fixed partial dentures (RBFPDs). A total of 40 Pd-Ag discs (diameter=5 mm) were prepared and divided into the following four groups (n=10): a) No sandblasting, used as a control; and b, 50 µm; c, 110 µm; and d, 250 µm aluminum oxide (Al 2 O 3 ) particles, respectively. Another 50 discs were pre-sandblasted and divided into five groups (n=10) subjected to different treatments: e) Sandblasting, used as a control; f) silane; g) alloy primer; h) silica coating + silane and i) silica coating + alloy primer. All 90 discs were bonded to enamel with Panavia F 2.0 and then subjected to shear bond strength (SBS) testing. The fracture surfaces were examined by scanning electron microscopy. Next, 40 missing maxillary second premolar models were restored with one of the four following RBFPD designs (n=10): I) A premolar occlusal bar combined with molar double rests (MDR); II) both occlusal bars with a wing (OBB); III) a premolar occlusal bar combined with a molar dental band (MDB); and IV) two single rests adjacent to the edentulous space with a wing (SRB) used as a control. All specimens were aged with thermal cycling and mechanical loading. Subsequently, they were loaded until broken. The data were analyzed by one-way analysis of variance. Al 2 O 3 (250 µm) abrasion provided the highest SBS (P<0.05). The alloy primer and silica + silane exhibited increased SBS. Furthermore, fracture analysis revealed that the failure mode varied among the different treatments. Whereas MDB exhibited the highest retention (P<0.05), that of OBB was greater than that of MDR (P<0.05), and the control exhibited the lowest retention. Abrasion with Al 2 O 3 (250 µm) effectively increased the adhesive property of Pd-Ag. Additionally, treatment with the alloy primer and silica coating + silane was able to

  8. Role of Hydrogen and Oxygen Activation over Pt and Pd-Doped Composites for Catalytic Hydrogen Combustion.

    Science.gov (United States)

    Singh, Satyapaul A; Vishwanath, Karan; Madras, Giridhar

    2017-06-14

    Removal of excess amount of hydrogen in a catalytic route is a safety measure to be implemented in fuel cell technologies and in nuclear power plants. Hydrogen and oxygen activation are crucial steps for hydrogen combustion that can be achieved by modifying supports with suitable noble metals. In the present study, Pt- and Pd-substituted Co 3 O 4 -ZrO 2 (CZ) were synthesized using PEG-assisted sonochemical synthesis. Ionic states of Pt and Pd in CZ supports were analyzed by X-ray photoelectron spectroscopy. Pd and Pt improved H 2 and O 2 activation extensively, which reduced the temperature of 50% conversion (T 50% ) to 33 °C compared with the support (CZ). The activation energy of PdCZ catalyst was decreased by more than 2 folds (13.4 ± 1.2 kJ mol -1 ) compared with CZ (34.3 ± 2.3 kJ mol -1 ). The effect of oxygen vacancies in the reaction mechanism is found to be insignificant with Pt- and Pd-substituted CZ supports. However, oxygen vacancies play an important role when CZ alone was used as catalyst. The importance of hydrogen and oxygen activation as well as the oxygen vacancies in mechanism was studied by H 2 -TPD, H 2 -TPR, and in situ FTIR spectroscopy.

  9. A Synthetic Pseudo-Rh: NOx Reduction Activity and Electronic Structure of Pd-Ru Solid-solution Alloy Nanoparticles.

    Science.gov (United States)

    Sato, Katsutoshi; Tomonaga, Hiroyuki; Yamamoto, Tomokazu; Matsumura, Syo; Zulkifli, Nor Diana Binti; Ishimoto, Takayoshi; Koyama, Michihisa; Kusada, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Nagaoka, Katsutoshi

    2016-06-24

    Rh is one of the most important noble metals for industrial applications. A major fraction of Rh is used as a catalyst for emission control in automotive catalytic converters because of its unparalleled activity toward NOx reduction. However, Rh is a rare and extremely expensive element; thus, the development of Rh alternative composed of abundant elements is desirable. Pd and Ru are located at the right and left of Rh in the periodic table, respectively, nevertheless this combination of elements is immiscible in the bulk state. Here, we report a Pd-Ru solid-solution-alloy nanoparticle (PdxRu1-x NP) catalyst exhibiting better NOx reduction activity than Rh. Theoretical calculations show that the electronic structure of Pd0.5Ru0.5 is similar to that of Rh, indicating that Pd0.5Ru0.5 can be regarded as a pseudo-Rh. Pd0.5Ru0.5 exhibits better activity than natural Rh, which implies promising applications not only for exhaust-gas cleaning but also for various chemical reactions.

  10. Synthesis of Pd/Au bimetallic nanoparticle-loaded ultrathin graphitic carbon nitride nanosheets for highly efficientcatalytic reduction of p-nitrophenol.

    Science.gov (United States)

    Fang, Wei; Deng, Yaocheng; Tang, Lin; Zeng, Guangming; Zhou, Yaoyu; Xie, Xia; Wang, Jingjing; Wang, Yang; Wang, Jiajia

    2017-03-15

    Noble metal nanoparticles (NPs) applied in heterogeneous catalysis have attracted considerable attention due to their highly efficient catalytic performance. Pd/Au bimetallic NPs were successfully decorated on the ultrathin graphitic carbon nitride nanosheets (g-C 3 N 4 -N) by a facile one-pot deposition reduction method. The obtained results show that Pd/Au NPs with average diameter around 8nm are homogeneously dispersed on the surface of unmodified g-C 3 N 4 -N. The obtained materials were characterized via transmission electron microscopy (TEM), high-resolution TEM, energy-dispersive X-ray spectroscopy, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). In addition, considering the large surface area and special π-bonded planar structure, the unique ultrathin g-C 3 N 4 -N behave as an excellent carrier and stabilizer in this synthesis. The as-synthesized Pd/Au bimetallic nanohybrids show superior catalytic performance and stability for reduction of p-nitrophenol (p-NP), which is better than either of pure Pd or Au nanohybrids. Besides, the catalytic activities of Pd/Au@g-C 3 N 4 -N nanohybrids were found to be controlled by altering the Pd versus Au mass ratio in the preparation process. Copyright © 2016 Elsevier Inc. All rights reserved.

  11. Multiple crossovers between positive and negative magnetoresistance versus field due to fragile spin structure in metallic GdPd3

    Science.gov (United States)

    Pandey, Abhishek; Mazumdar, Chandan; Ranganathan, R.; Johnston, D. C.

    2017-01-01

    Studies on the phenomenon of magnetoresistance (MR) have produced intriguing and application-oriented outcomes for decades–colossal MR, giant MR and recently discovered extremely large MR of millions of percents in semimetals can be taken as examples. We report here the discovery of novel multiple sign changes versus applied magnetic field of the MR in the cubic intermetallic compound GdPd3. Our study shows that a very strong correlation between magnetic, electrical and magnetotransport properties is present in this compound. The magnetic structure in GdPd3 is highly fragile since applied magnetic fields of moderate strength significantly alter the spin arrangement within the system–a behavior that manifests itself in the oscillating MR. Intriguing magnetotransport characteristics of GdPd3 are appealing for field-sensitive device applications, especially if the MR oscillation could materialize at higher temperature by manipulating the magnetic interaction through perturbations caused by chemical substitutions. PMID:28211520

  12. Noble metals nanoparticles on titanium dioxide nanostructured films and the influence of their photocatalytic activity; Atividade fotocatalitica de filmes nanoestruturados de dioxido de titanio incorporados com nanoparticulas de metais nobres

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, Liana Key Okada

    2012-07-01

    Currently, nanoscience and nanotechnology are considered an emerging field and continuously breaking the barrier among various disciplines. The main focus of study involves controlling structures at molecular level, arranging the atoms in order to achieve an understanding and controlling the fundamental properties of matter. In this study, molecular changes on the basis of morphology, optical and crystalline properties of TiO{sub 2}hin films in order to increase their photon efficiency were proposed. The TiO{sub 2} thin films were prepared by sol gel process evaluating the influence of different acids and templates to obtain the nano structured arrangements. Then, metal nanoparticles like Au, Ag, Pd and Pt were incorporated on TiO{sub 2} thin films. This incorporation might minimize the electron-hole recombination, so it could improve the photon efficiency. From the several routes studied, the TiO{sub 2} thin films prepared with acetic acid showed the best performance by the reason of low agglomeration of TiO{sub 2} grains, which favors the exposure of the photoactive sites. The presence of template in the formulation had a slightly effect on photon efficiency, possible due to the higher agglomeration of the grains on the TiO{sub 2} thin films. The addition of Pt and Au nanoparticles on TiO{sub 2} thin films showed superior photon efficiency. The TiO{sub 2} thin films with hexamine and metallic nanoparticles did not show the improvement on photon efficiency except for Pt and Au nanoparticles. On these situations, the improvement on photon efficiency is might be due to a possible decrease at the electron-hole recombination's velocity. Thus, the present work demonstrates the great influence of preparation conditions on the optical, morphological properties and the photon efficiency. In the future, with greater understanding of the mechanism of this influence, the properties of TiO{sub 2} thin films will be able tailoring depending on the application. (author)

  13. Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd.

    Science.gov (United States)

    Duguid, J; Bloomfield, V A; Benevides, J; Thomas, G J

    1993-11-01

    Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) induce the greatest structural changes in B-DNA. The Raman (vibrational) band differences are extensive and indicate partial disordering of the B-form backbone, reduction in base stacking, reduction in base pairing, and specific metal interaction with acceptor sites on the purine (N7) and pyrimidine (N3) rings. Many of the observed spectral changes parallel those accompanying thermal denaturation of B-DNA and suggest that the metals link the bases of denatured DNA. While exocyclic carbonyls of dT, dG, and dC may stabilize metal ligation, correlation plots show that perturbations of the carbonyls are mainly a consequence of metal-induced denaturation of the double helix. Transition metal interactions with the DNA phosphates are weak in comparison to interactions with the bases, except in the case of Cu2+, which strongly perturbs both base and phosphate group vibrations. On the other hand, the Raman signature of B-DNA is largely unperturbed by Mg2+, Ca2+, Sr2+, and Ba2+, suggesting much weaker interactions of the alkaline earth metals with both base and phosphate sites. A notable exception is a moderate perturbation by alkaline earths of purine N7 sites in 160-base pair DNA, with Ca2+ causing the greatest effect. Correlation plots demonstrate a strong interrelationship between perturbations of Raman bands assigned to ring vibrations of the bases and those of bands assigned to exocyclic carbonyls and backbone phosphodiester groups. However, strong correlations do not occur between

  14. Growth of Pd{sub 4}S, PdS and PdS{sub 2} films by controlled sulfurization of sputtered Pd on native oxide of Si

    Energy Technology Data Exchange (ETDEWEB)

    Bhatt, R., E-mail: rbhatt@barc.gov.in [Technical Physics Division, Bhabha Atomic Research Center, Mumbai–400 085 (India); Bhattacharya, S.; Basu, R.; Singh, A. [Technical Physics Division, Bhabha Atomic Research Center, Mumbai–400 085 (India); Deshpande, U. [UGC–DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore–452017 (India); Surger, C. [Karlsruhe Institute of Technology, Physikalisches Institut and DFG Center for Functional Nanostructures, P.O. Box 6980, D–76049 Karlsruhe (Germany); Basu, S. [Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai-400 085 (India); Aswal, D.K.; Gupta, S.K. [Technical Physics Division, Bhabha Atomic Research Center, Mumbai–400 085 (India)

    2013-07-31

    Thin films of different Pd–S phase, namely Pd{sub 4}S, PdS and PdS{sub 2}, have been reproducibly grown by the sulfurization of Pd films deposited on native oxide of (111) Si substrates by radio frequency sputtering method. In order to achieve controlled sulfurization, a three-stage sulfurization setup consisting of evaporation chamber, activation chamber and sulfurization chamber has been developed. The sulfurization of Pd films (kept at a constant temperature of 500 °C) was carried out using sulfur vapors activated to different temperature between 550 and 700 °C. The results of X-ray diffraction and X-ray photoelectron spectroscopy measurements show that formation of Pd{sub 4}S, PdS and PdS{sub 2} phases takes place for the activation temperatures of 550, 600 and 700 °C, respectively. The room temperature resistivity of Pd, Pd{sub 4}S, PdS and PdS{sub 2} were found to be respectively 0.1, 15.9, 15,000 and 20,000 μΩ cm. The temperature-dependent electrical resistivity measurements showed metallic conduction for Pd and Pd{sub 4}S films. The Seebeck coefficient measured at 300 K for these Pd–S phases showed their n-type conducting behavior. - Highlights: • Multichamber sulfurization setup designed for preparing thin films of Pd–S. • S vapor activated at 550, 600 and 700 °C results in Pd{sub 4}S, PdS and PdS{sub 2} phases. • The Seebeck coefficient of Pd–S phases shows their n-type conducting behavior. • Transport properties of Pd{sub 4}S phase show that it is a metallic phase. • High resistivity and thermopower of PdS and PdS{sub 2} show semiconducting nature.

  15. O{sub 2} adsorption and dissociation on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Li, Sha; Yang, Yongpeng; Huang, Shiping, E-mail: huangsp@mail.buct.edu.cn

    2017-07-15

    Highlights: • O{sub 2} adsorption and dissociation on Pd{sub 13-n}Ni{sub n}@Pt{sub 42} NPs are performed by DFT. • Adsorption energies of O{sub 2} and O are strongly affected by the coordination number. • Adsorption energy and d-band center displays the opposite change tendency. • Ni{sub 13}@Pt{sub 42} is the most active catalyst among Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) NPs. - Abstract: Density functional theory calculations are performed to investigate O{sub 2} adsorption and dissociation on the icosahedral Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles. The parallel adsorption of O{sub 2} on Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) is stronger than the vertical adsorption. The adsorption of O{sub 2} on the bridge site (B1) is favorable in the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) nanoparticles, while the adsorption of O atom on the hollow site (H1) is preferred. The adsorption energies of O{sub 2} and O are strongly affected by the coordination number. Low coordination site shows strong adsorption of O{sub 2} and O on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) nanoparticles. The adsorption energies of O{sub 2} and O atoms are found to be correlated well with the d-band center of surface Pt. For the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and13) nanoparticles catalysts, the ORR activity follows the order of Ni{sub 13}@Pt{sub 42} > Pd{sub 13}@Pt{sub 42} > Pd{sub 12}Ni{sub 1}@Pt{sub 42} > Pd{sub 1}Ni{sub 12}@Pt{sub 42}, illustrating that the Ni{sub 13}@Pt{sub 42} is the strongest ORR activity among the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and13) nanoparticles catalysts. Our results have important significance to understand the mechanism of O{sub 2} dissociation on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles.

  16. A Phenomenological Study on the Synergistic Role of Precious Metals in the Steam Reforming of Logistic Fuels on Bimetal-Supported Catalysts

    Directory of Open Access Journals (Sweden)

    Abdul-Majeed Azad

    2011-01-01

    Full Text Available Fuel processors are required to convert sulfur-laden logistic fuels into hydrogen-rich reformate and deliver to the fuel cell stack with little or no sulfur. Since sulfur poisons and deactivates the reforming catalyst, robust sulfur-tolerant catalysts ought to be developed. In this paper, the development, characterization and evaluation of a series of reforming catalysts containing two noble metals (with total metal loading not exceeding 1 weight percent supported on nanoscale ceria for the steam-reforming of kerosene is reported. Due to inherent synergy, a bimetallic catalyst is superior to its monometallic analog, for the same level of loading. The choice of noble metal combination in the bimetallic formulations plays a vital and meaningful role in their performance. Presence of ruthenium and/or rhodium in formulations containing palladium showed improved sulfur tolerance and significant enhancement in their catalytic activity and stability. Rhodium was responsible for higher hydrogen yields in the logistic fuel reformate. Duration of steady hydrogen production was higher in the case of RhPd (75 h than for RuPd (68 h; hydrogen generation was stable over the longest period (88 h with RuRh containing no Pd. A mechanistic correlation between the characteristic role of precious metals in the presence of each other is discussed.

  17. Selective hydrogenation of maleic anhydride over Pd/Al2O3 ...

    Indian Academy of Sciences (India)

    The results showed that the activity of the Pd/Al2O3 catalysts was excellent due to its high active surface area. ... avoid the high cost of separating the solvent from the reaction mixture, solvent-free hydrogenation of MA ... loss of reaction activity was observed after 120 h.3. Noble catalysts, especially Pd-based catalysts, have.

  18. Laser cool and trap trace noble atoms

    Science.gov (United States)

    Wang, Mingdong; Hong, Yanji; Feng, Gaoping

    2016-01-01

    Laser can be used to cool and manipulate neutron atoms via momentum exchange between photons and atoms. Laser cooling and trapping is well established on alkali, alkali earth, and noble gas elements. Noble gases, with stable physical and chemical properties, no reactions with other elements, have great potential uses in cold collision, spectroscopy measurement, photo-association, atom optics, etc. However, trapping noble gas atoms is generally more difficult because of the lack of suitable UV lasers. Some of these problems will be overcome with future advances in UV laser technology. Excited by electron collisions, noble gas can reach the long life metastable state for the use of laser decelerating, focusing and trapping. In this paper some main methods which are used to achieve cooling and trapping metastable noble gas atoms are discussed.

  19. Heteronuclear transition metal diatomics - The bonding and electronic structure of ScNi, YNi, ScPd, and YPd

    Science.gov (United States)

    Faegri, Knut, Jr.; Bauschlicher, Charles W., Jr.

    1991-01-01

    High quality ab initio calculations show that ScNi, YNi, ScPd, and YPd all have 2Sigma(+) ground states in agreement with electron spin resonance experiments. For ScNi and YNi, this is expected based on the lowest atomic asymptote. For ScPd and YPd, the lowest atomic asymptote would give the order of stability 2Delta greater than 2Pi equal to about 2Sigma(+), but the calculations show that mixing in of the excited asymptotes preferentially lowers the 2Sigma(+) state. The calculations show that the quartet states are about 20-30 kcal/mol above the ground state, and therefore probably do not contribute significantly to the unexpected g(vertical) values found in experiment. Calculations of excited states for YPd reveal some strong transitions that should be amenable to spectroscopic studies.

  20. Noble Gases Trace Earth's Subducted Water Flux

    Science.gov (United States)

    Smye, A.; Jackson, C.; Konrad-Schmolke, M.; Parman, S. W.; Ballentine, C. J.

    2016-12-01

    Volatile elements are transported from Earth's surface reservoirs back into the mantle during subduction of oceanic lithosphere [e.g. 1]. Here, we investigate the degree to which the fate of slab-bound noble gases and water are linked through the subduction process. Both water and noble gases are soluble in ring-structured minerals, such as amphibole, that are common constituents of subducted oceanic lithosphere. Heating and burial during subduction liberates noble gases and water from minerals through a combination of diffusion and dissolution. Combining a kinetic model, parameterized for noble gas fractionation in amphibole [2], with thermodynamic phase equilibria calculations, we quantify the effect of subduction dehydration on the elemental composition of slab-bound noble gases. Results show that post-arc slab water and noble gas fluxes are highly correlated. Hot subduction zones, which likely dominate over geologic history, efficiently remove noble gases and water from the down-going slab; furthermore, kinetic fractionation of noble gases is predicted to occur beneath the forearc. Conversely, hydrated portions of slab mantle in cold subduction zones transport noble gases and water to depths exceeding 200 km. Preservation of seawater-like abundances of Ar, Kr and Xe in the convecting mantle [1] implies that recycling of noble gases and water occurred during cold subduction and that the subduction efficiency of these volatile elements has increased over geological time, driven by secular cooling of the mantle. [1] Holland, G. and Ballentine, C. (2006). Nature 441, 186-191. [2] Jackson et al. (2013). Nat.Geosci. 6, 562-565.

  1. O efeito da desativação térmica nas propriedades oxirredutoras e na atividade catalítica de catalisadores CZ e Pd-CZ

    Directory of Open Access Journals (Sweden)

    Daniela Cruz Damasceno da Silva

    2012-01-01

    Full Text Available Automotive catalyst, using in Brazil since 1992, is a essential technology for vehicular emissions control. Noble metals are the active phase of these catalysts, and cerium zirconium mixed oxides (CZ, responsibles for the oxygen storage capacity (OSC, one of the most important aspect for the operational performance of the catalyst. In this context, the oxireduction properties analysis of CZ and Pd/CZ (palladium supported in CZ system are the objective of this study, as well as, the impact of the thermal aging in the OSC. Aging consisted of treatments at 900 or 1200 °C, for 12 or 36 h, in oxidizing condition.

  2. Deactivation of Pd Catalysts by Water during Low Temperature Methane Oxidation Relevant to Natural Gas Vehicle Converters

    Directory of Open Access Journals (Sweden)

    Rahman Gholami

    2015-03-01

    Full Text Available Effects of H2O on the activity and deactivation of Pd catalysts used for the oxidation of unburned CH4 present in the exhaust gas of natural-gas vehicles (NGVs are reviewed. CH4 oxidation in a catalytic converter is limited by low exhaust gas temperatures (500–550 °C and low concentrations of CH4 (400–1500 ppmv that must be reacted in the presence of large quantities of H2O (10–15% and CO2 (15%, under transient exhaust gas flows, temperatures, and compositions. Although Pd catalysts have the highest known activity for CH4 oxidation, water-induced sintering and reaction inhibition by H2O deactivate these catalysts. Recent studies have shown the reversible inhibition by H2O adsorption causes a significant drop in catalyst activity at lower reaction temperatures (below 450 °C, but its effect decreases (water adsorption becomes more reversible with increasing reaction temperature. Thus above 500 °C H2O inhibition is negligible, while Pd sintering and occlusion by support species become more important. H2O inhibition is postulated to occur by either formation of relatively stable Pd(OH2 and/or partial blocking by OH groups of the O exchange between the support and Pd active sites thereby suppressing catalytic activity. Evidence from FTIR and isotopic labeling favors the latter route. Pd catalyst design, including incorporation of a second noble metal (Rh or Pt and supports high O mobility (e.g., CeO2 are known to improve catalyst activity and stability. Kinetic studies of CH4 oxidation at conditions relevant to natural gas vehicles have quantified the thermodynamics and kinetics of competitive H2O adsorption and Pd(OH2 formation, but none have addressed effects of H2O on O mobility.

  3. The electrochemical reduction of PdCl42- and PdCl62- in polyaniline: Influence of Pd deposit morphology on methanol oxidation in alkaline solution

    International Nuclear Information System (INIS)

    Hatchett, David W.; Millick, Nicole M.; Kinyanjui, John M.; Pookpanratana, Sujitra; Baer, Marcus; Hofmann, Timo; Luinetti, Alessio; Heske, Clemens

    2011-01-01

    Graphical abstract: Display Omitted Highlights: → The synthesis of PANI/Pd composites using PdCl 4 2- and PdCl 6 2- is achieved. → Conductivity of PANI/Pd composites is observed in alkaline solution (pH ∼ 14). → Oxidation of methanol at PANI/Pd is influenced to be the Pd surface morphology. → Surface poisoning is minimized for PANI/Pd produced using PdCl 4 2- . → The Pd metal acts as a solid state dopant in PANI. - Abstract: The controlled uptake and electrochemical reduction of metal precursors PdCl 4 2- and PdCl 6 2- in polyaniline (PANI) is demonstrated. The formation of PANI/Pd composites is achieved with a reduction in proton doping and an increase in the oxidation of the polymer with Pd deposits physically blocking the nitrogen groups. High surface area filaments (PdCl 4 2- ) or a rough encapsulation (PdCl 6 2- ) of Pd metal on PANI are obtained. The structural differences highlight the influence of the metal precursor oxidation state on the morphology of the Pd deposits in PANI. Thermal gravimetric analysis provides an estimate of the Pd content for each composite of ∼40%. X-ray Photoelectron Spectroscopy and X-ray-excited Auger Electron Spectroscopy analyses confirm the deposition of Pd metal. The catalytic oxidation of methanol was demonstrated for both PANI/Pd composites in alkaline solutions that prohibit proton doping of the polymer. The data indicates that Pd metal acts as a solid-state dopant that may delocalize the charge on the polymer backbone to maintain conductivity. Methanol oxidation at PANI/Pd composites produced using PdCl 4 2- was enhanced relative to the composite produced using PdCl 6 2- and a planar Pd electrode. Comparison of PANI/Pd composite produced using PdCl 4 2- with other Pd catalysts from the literature indicates surface poisoning is reduced when Pd is coupled with the polymer. The composite is robust and stable in alkaline solution with the charge density decreasing by 5% on the positive scan and 13% on the

  4. New experimental set-up and procedure for analyzing the dynamics of permeation of H2(g) across Pd-based metallic membranes

    International Nuclear Information System (INIS)

    Decaux, C.; Millet, P.; Decaux, C.

    2006-01-01

    . Impedances of the sorbing (permeating) membrane materials are then calculated using the theory of linear and time-invariant systems, by numerically Fourier-transforming the discretely sampled pressure signals. Using appropriate initial and boundary conditions, it is shown that the rate constants of the two major steps of the sorption (permeation) mechanisms can be separately accessed, i.e. surface resistances related to hydrogen dissociation (upstream side) and recombination (downstream side) processes, and bulk diffusion impedance. This experimental equipment and this treatment procedure therefore provide a new tool for analyzing the dynamics of hydrogen permeation across metallic membranes. This tool can be used for diagnosis purposes and for optimizing the structure and composition of permeation membranes. Results obtained with Pd and Pd 77 Ag 23 foils are presented and discussed. (authors)

  5. Subsurface Noble Gas Sampling Manual

    Energy Technology Data Exchange (ETDEWEB)

    Carrigan, C. R. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Sun, Y. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2017-09-18

    The intent of this document is to provide information about best available approaches for performing subsurface soil gas sampling during an On Site Inspection or OSI. This information is based on field sampling experiments, computer simulations and data from the NA-22 Noble Gas Signature Experiment Test Bed at the Nevada Nuclear Security Site (NNSS). The approaches should optimize the gas concentration from the subsurface cavity or chimney regime while simultaneously minimizing the potential for atmospheric radioxenon and near-surface Argon-37 contamination. Where possible, we quantitatively assess differences in sampling practices for the same sets of environmental conditions. We recognize that all sampling scenarios cannot be addressed. However, if this document helps to inform the intuition of the reader about addressing the challenges resulting from the inevitable deviations from the scenario assumed here, it will have achieved its goal.

  6. CHARACTERIZATION OF PD IMPURITIES AND TWIN BOUNDARY DEFECTS IN DETECTOR GRADE CDZNTE CRYSTALS

    Energy Technology Data Exchange (ETDEWEB)

    Duff, M.

    2011-06-22

    Synthetic CdZnTe or ''CZT'' crystals are highly suitable for {gamma}-spectrometers operating at the room temperature. Secondary phases (SP) in CZT are known to inhibit detector performance, particularly when they are present in large numbers or dimensions. These SP may exist as voids or composites of non-cubic phase metallic Te layers with bodies of polycrystalline and amorphous CZT material and voids. Defects associated with crystal twining may also influence detector performance in CZT. Using transmission electron microscopy, we identify two types of defects that are on the nano scale. The first defect consists of 40 nm diameter metallic Pd/Te bodies on the grain boundaries of Te-rich composites. Although the nano-Pd/Te bodies around these composites may be unique to the growth source of this CZT material, noble metal impurities like these may contribute to SP formation in CZT. The second defect type consists of atom-scale grain boundary dislocations. Specifically, these involve inclined ''finite-sized'' planar defects or interfaces between layers of atoms that are associated with twins. Finite-sized twins may be responsible for the subtle but observable striations that can be seen with optical birefringence imaging and synchrotron X-ray topographic imaging.

  7. A Novel Ultraviolet Irradiation Technique for Fabrication of Polyacrylamide-metal (M = Au, Pd) Nanocomposites at Room Temperature

    International Nuclear Information System (INIS)

    Zhou, Y.; Hao, L.Y.; Zhu, Y.R.; Hu, Y.; Chen, Z.Y.

    2001-01-01

    Polyacrylamide (PAM)-metal (M = gold, palladium) nanocomposites with metal nanoparticles homogeneously dispersed in the polymer matrix have been prepared via a novel ultraviolet irradiation technique at room temperature, which is based on the simultaneous occurrence of photo-reduction formation of the colloidal metal particles and photo-polymerization of the acrylamide (AM) monomer. The UV-vis absorption spectra and TEM were employed to characterize the M-PAM nanocomposites by different irradiation times. The average sizes of the colloidal gold and palladium particles dispersed in the nanocomposites were calculated by XRD patterns and TEM images. The present method may be extended to prepare other metal-polymer hybrid nanocomposite materials

  8. Mechanistic insight into the enhanced photocatalytic activity of single-atom Pt, Pd or Au-embedded g-C3N4

    Science.gov (United States)

    Tong, Tong; Zhu, Bicheng; Jiang, Chuanjia; Cheng, Bei; Yu, Jiaguo

    2018-03-01

    Single atoms of platinum (Pt), palladium (Pd) or gold (Au) trapped by two-dimensional graphitic carbon nitride (g-C3N4) exhibit superior photocatalytic performance. However, the underlying mechanism of single-atom noble metal/g-C3N4 photocatalytic system is still unclear. Herein, the structural, electronic and optical properties of single-atom Pt, Pd and Au loaded on bilayer g-C3N4 (BL-g-C3N4) substrate were investigated by density functional theory (DFT) simulations. The results indicate that single-atom Pt/Pd/Au loading can significantly narrow the band gap of g-C3N4 and thus increase its light absorption in the visible-light region. Rather than being adsorbed on the surface, Pt and Pd atoms tend to be embedded into g-C3N4 interlayer and act as bridges to facilitate the interlayer charge carrier transfer due to the effects of conduction band offset. In particular, an internal electric field is generated in Pt/BL-g-C3N4, which is further beneficial for separating charge carrier of photoexcited g-C3N4. By contrast, Au can only be adsorbed on the g-C3N4 surface (in the six-fold cavity) and deliver a limited amount of charge carrier excited in the N-conjugated aromatic pore of g-C3N4 surface. Our finding is conducive to understanding the interactive relationship between single-atom noble metal co-catalysts and g-C3N4 and to the design of high-efficiency photocatalyst.

  9. Improvement on the electrical characteristics of Pd/HfO{sub 2}/6H-SiC MIS capacitors using post deposition annealing and post metallization annealing

    Energy Technology Data Exchange (ETDEWEB)

    Esakky, Papanasam, E-mail: papanasamte@gmail.com; Kailath, Binsu J

    2017-08-15

    Highlights: • Post deposition annealing (PDA) and post metallization annealing (PMA) on the electrical characteristics of Pd/HfO{sub 2}/6H-SiC MIS capacitors. • Post deposition N{sub 2}O plasma annealing inhibits crystallization of HfO{sub 2} during high temperature annealing. • Plasma annealing followed by RTA in N{sub 2} results in formation of hafnium silicate at the HfO{sub 2}-SiC interface. • PDA reduces interface state density (D{sub it}) and gate leakage current density (J{sub g}) by order. • PMA in forming gas for 40 min results in better passivation and reduces D{sub it} by two orders and J{sub g} by thrice. - Abstract: HfO{sub 2} as a gate dielectric enables high electric field operation of SiC MIS structure and as gas sensor HfO{sub 2}/SiC capacitors offer higher sensitivity than SiO{sub 2}/SiC capacitors. The issue of higher density of oxygen vacancies and associated higher leakage current necessitates better passivation of HfO{sub 2}/SiC interface. Effect of post deposition annealing in N{sub 2}O plasma and post metallization annealing in forming gas on the structural and electrical characteristics of Pd/HfO{sub 2}/SiC MIS capacitors are reported in this work. N{sub 2}O plasma annealing suppresses crystallization during high temperature annealing thereby improving the thermal stability and plasma annealing followed by rapid thermal annealing in N{sub 2} result in formation of Hf silicate at the HfO{sub 2}/SiC interface resulting in order of magnitude lower density of interface states and gate leakage current. Post metallization annealing in forming gas for 40 min reduces interface state density by two orders while gate leakage current density is reduced by thrice. Post deposition annealing in N{sub 2}O plasma and post metallization annealing in forming gas are observed to be effective passivation techniques improving the electrical characteristics of HfO{sub 2}/SiC capacitors.

  10. Rare metal fission products in nuclear spent fuel as catalysts for hydrogen production by water electrolysis

    International Nuclear Information System (INIS)

    Ozawa, Masaki

    2004-01-01

    Separation and utilization of rare metal fission products (RMFP) in nuclear spent fuel were studied to apply them as a catalyst for hydrogen generation by water electrolysis. The RMFP, namely Pd, Ru, Rh and Tc, etc, are abundant, more than ca. 30kg per metric ton of a typical fast reactor spent fuel. The RMFP can be selectively separated from high level liquid waste (HLLW) by catalytic electrolytic extraction (CEE) method. Specific metallic cations such as Pd 2+ , which originate in the solutions, may act as promoters (i.e., Pd adatom ) or mediators, thereby accelerating electrochemical deposition of RuNO 3+ , Rh 3+ and ReO 4 - (simulator TcO 4 - ). In utilizing CEE method, electrodeposited electrodes were prepared, and successively dedicated to the water (alkaline or artificial sea water) electrolysis tests. Among the RMFP deposited electrodes, maximum potential shifting for hydrogen evolution to noble side was observed for the quaternary, Pd-Ru-Rh-Re (3.5:4:1:1), deposit Pt electrode, with suggesting the highest cathodic currents for hydrogen evolution both in alkaline solution and artificial sea water. The electro analytic activity of quaternary, Pd-Ru-Rh-Re (3.5:4:1:1), deposit Pt electrode exceeded that of Pt electrode by ca. twice both in alkaline solution and artificial sea water. The paper conclusively proposes RMFP generated by nuclear fission to utilize as an alternative material for hydrogen production with a novel vision to bridge nuclear and hydrogen energy systems. (author)

  11. Green Synthesis of Ag and Pd Nanospheres, Nanowires, and Nanorods Using Vitamin B2: Catalytic Polymerisation of Aniline and Pyrrole

    Directory of Open Access Journals (Sweden)

    Mallikarjuna N. Nadagouda

    2008-01-01

    Full Text Available For the first time, we report green chemistry approach using vitamin B2 in the synthesis of silver (Ag and palladium (Pd, nanospheres, nanowires, and nanorods at room temperature without using any harmful reducing agents, such as sodium borohydride (NaBH4 or hydroxylamine hydrochloride and any special capping or dispersing agent. Vitamin B2 was used as reducing agent as well as capping agent due to its high-water solubility, biodegradability, and low-toxicity compared with other reducing agents. The average particle size of nanoprticle was found to be Ag (average size 6.1±0.1 nm and Pd (average size 4.1±0.1 nm nanoparticles in ethylene glycol and Ag (average size 5.9±0.1 nm, and average size 6.1±0.1 nanoparticles in acetic acid and NMP, respectively. The formation of noble multiple shape nanostructures and their self assembly were dependent on the solvent employed for the preparation. When water was used as solvent media, Ag and Pd nanoparticles started to self-assemble into rod-like structures and in isopropanol Ag and Pd nanoparticles yielded wire-like structures with a thickness in the range of 10 to 20 nm and several hundred microns in length. In acetone and acetonitrile medium, the Ag and Pd nanoparticles are self-assembled into a regular pattern making nanorod structures with thicknesses ranging from 100 to 200 nm and lengths of a few microns. The so-synthesized nanostructures were characterized using scanning electron microscopy (SEM, transmission electron microscopy (TEM, energy dispersive X-ray (EDX analysis, and UV spectroscopy. The ensuing Ag and Pd nanoparticles catalyzed the reactions of aniline and pyrrole to generate polyaniline and polypyrrole nanofibers and may find various technological and biological applications. This single-step greener approach is general and can be extended to other noble metals and transition metal oxides.

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

    Science.gov (United States)

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

    2016-01-01

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

  13. Interaction of NO2 with model NSR catalysts: metal-oxide interaction controls initial NOx storage mechanism.

    Science.gov (United States)

    Desikusumastuti, Aine; Staudt, Thorsten; Qin, Zhihui; Happel, Markus; Laurin, Mathias; Lykhach, Yaroslava; Shaikhutdinov, Shamil; Rohr, Friedemann; Libuda, Jörg

    2008-10-24

    Using scanning tunneling microscopy (STM), molecular-beam (MB) methods and time-resolved infrared reflection absorption spectroscopy (TR-IRAS), we investigate the mechanism of initial NO(x) uptake on a model nitrogen storage and reduction (NSR) catalyst. The model system is prepared by co-deposition of Pd metal particles and Ba-containing oxide particles onto an ordered alumina film on NiAl(110). We show that the metal-oxide interaction between the active noble metal particles and the NO(x) storage compound in NSR model catalysts plays an important role in the reaction mechanism. We suggest that strong interaction facilitates reverse spillover of activated oxygen species from the NO(x) storage compound to the metal. This process leads to partial oxidation of the metal nanoparticles and simultaneous stabilization of the surface nitrite intermediate.

  14. Hydroconversion of n-hexane using Pt/H-MOR and Pt/H-BEA catalysts with various Pt contents and bimetallic PtPd/H-MOR, PtPd/H-BEA, PtIr/H-MOR and PtIr/H-BEA catalysts with various secondary metal contents

    Energy Technology Data Exchange (ETDEWEB)

    Aboul-Gheit, A.K.; Abdel-Hamid, S.M.; Awadallah, A.E. [Process Development Div., Egyptian Petroleum Research Inst., Nasr City, Cairo (Egypt)

    2004-03-01

    Monometallic catalysts containing 0.35 up to 0.50 wt%Pt on H-MOR or H-BEA zeolites, as well as bimetallic catalysts containing Pd or Ir of 0.05 up to 0.20-0.25 wt% combined with a fixed Pt content of 0.35 wt% also supported on H-MOR or H-BEA were prepared and tested for n-hexane hydroconversion in a hydrogen flow using pulsed reactor system. The reaction products were gas chromatographically analysed and the catalysts were characterised for acid sites strength distribution via ammonia temperature programmed desorption (TPD) and for metal(s) dispersion in the support via pulsed hydrogen chemisorption. Increased Pt content in either zeolites decreased its dispersion. The addition of Pd to Pt increased the metals dispersion in both zeolites up to a certain content, whereas Ir addition, principally, decreased dispersion. Maximum isohexanes production behaved parallel to the metals dispersion in the PtPd containing catalysts (structure sensitive). Hydrocracking was more active on the H-MOR supported catalysts, compared to those supported on H-BEA due to higher acid sites number and strength in the former zeolite. Benzene production via dehydrocyclisation of n-hexane was relatively more active on the H-BEA containing catalysts than on those containing H-MOR, due to the less effective diffusion resistance in the BEA channels. (orig.)

  15. Tunable reactivity of supported single metal atoms by impurity engineering of the MgO(001) support.

    Science.gov (United States)

    Pašti, Igor A; Johansson, Börje; Skorodumova, Natalia V

    2018-02-28

    Development of novel materials may often require a rational use of high price components, like noble metals, in combination with the possibility to tune their properties in a desirable way. Here we present a theoretical DFT study of Au and Pd single atoms supported by doped MgO(001). By introducing B, C and N impurities into the MgO(001) surface, the interaction between the surface and the supported metal adatoms can be adjusted. Impurity atoms act as strong binding sites for Au and Pd adatoms and can help to produce highly dispersed metal particles. The reactivity of metal atoms supported by doped MgO(001), as probed by CO, is altered compared to their counterparts on pristine MgO(001). We find that Pd atoms on doped MgO(001) are less reactive than on perfect MgO(001). In contrast, Au adatoms bind CO much more strongly when placed on doped MgO(001). In the case of Au on N-doped MgO(001) we find that charge redistribution between the metal atom and impurity takes place even when not in direct contact, which enhances the interaction of Au with CO. The presented results suggest possible ways for optimizing the reactivity of oxide supported metal catalysts through impurity engineering.

  16. Distribution trends and influence of 4d transition metal elements (Ru, Rh and Pd) doping on mechanical properties and martensitic transformation temperature of B2-ZrCu phase

    Science.gov (United States)

    Guo, Fuda; Zhan, Yongzhong

    2017-12-01

    The prediction for distribution trends and effect of three 4d transition metal elements (Ru, Rh and Pd) on mechanical properties and martensitic transformation temperature of B2-ZrCu phase were investigated by first-principles calculations. The convex surface of formation energy suggests that the alloying elements prefer to occupy the Cu sites in B2-ZrCu phase and the dopants studied in present are able to strengthen the phase stability. The calculated results of substitutional formation energy suggest that the distribution trend of dopants in B2-ZrCu phase is Ru > Rh > Pd below the dopant concentration 9 at. %, and the distribution trend is Rh > Pd > Ru from 9 at. % to 12.5 at. %. The elastic constants and mechanical properties including bulk modulus and shear modulus were calculated and discussed. The brittleness/ductility characteristic was investigated using the B/G ratio, Poisson's ratio v and Cauchy pressure Cp. The martensitic transformation temperature (Ms) and melting point (Tm) were predicted by using two cubic elastic moduli (C‧ and C44). The prediction results suggest that only the Ms of Zr8Cu7Pd is higher than the parent. The martensitic transformation temperatures of other compounds decrease with the addition of 4d transition metal dopants. Finally, the electronic structures and electron density different were discussed to reveal the bonding characteristics.

  17. Facile Synthesis of Pt-/Pd-MODIFIED NiTi Electrode with Superior Electro-Catalytic Activities Toward Methanol, Ethanol and Ethylene Glycol Oxidation

    Science.gov (United States)

    He, Yongwei; Wang, Mei; Ma, Zizai; Li, Ruixue; Kundu, Manab; Ma, Guanshui; Lin, Naiming; Tang, Bin; Wang, Xiaoguang

    2016-11-01

    Surface functional modification of NiTi electrode with noble Pt and Pd metal has been successfully carried out by simple and cost effective electro-spark deposition technique (ESD). Thin-film X-ray diffraction (TF-XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and cyclic voltammetry (CV) have been carried out in order to investigate the structure, morphology, chemical composition and electrochemical behavior of the modified electrode surface. The modified Pt/NiTi and Pd/NiTi electrode surface exhibit a circular splash pattern with a tiny amount of Pt (˜5.30 at.% Pt) and Pd (˜5.71 at.% Pd) existence. The electrochemical results demonstrate that the Pt/NiTi and Pd/NiTi electrode possess an improved electro-catalytic activities toward methanol (MeOH), ethanol (EtOH) and ethylene glycol (EG) oxidation in alkaline media in comparison with the bare NiTi electrode. In acidic environments, the Pt/NiTi electrode exhibits even much better catalytic activities than the pure Pt sheet electrode due to the bi-functional mechanism. In the same way, the electro-catalytic activity of the modified Pd/NiTi electrode is also slightly larger than that of the pure Pd sheet electrode in alkaline environment. The electro-spark surface modification approach is rapid and environmentally-benign, being attractive to widen the application of traditional surface modification technique in the field of material surface/interface design and functionalization.

  18. Parity nonconservation in 106Pd and 108Pd neutron resonances

    International Nuclear Information System (INIS)

    Crawford, B.E.; Roberson, N.R.; Bowman, J.D.; Knudson, J.N.; Penttilae, S.I.; Seestrom, S.J.; Yuan, V.W.; Delheij, P.P.; Haseyama, T.; Masaike, A.; Matsuda, Y.; Lowie, L.Y.; Mitchell, G.E.; Stephenson, S.L.; Postma, H.; Sharapov, E.I.

    1999-01-01

    Parity nonconservation (PNC) has been studied in the neutron p-wave resonances of 106 Pd and 108 Pd in the energy range of 20 to 2000 eV. Longitudinal asymmetries in p-wave capture cross sections are measured using longitudinally polarized neutrons incident on ∼20-g metal-powder targets at LANSCE. A CsI γ-ray detector array measures capture cross section asymmetries as a function of neutron energy which is determined by the neutron time-of-flight method. A total of 21 p-wave resonances in 106 Pd and 21 p-wave resonances in 108 Pd were studied. One statistically significant PNC effect was observed in 106 Pd, and no effects were observed in 108 Pd. For 106 Pd a weak spreading width of Γ w =34 -28 +47 x10 -7 eV was obtained. For 108 Pd an upper limit on the weak spreading width of Γ w -7 eV was determined at the 68% confidence level. copyright 1999 The American Physical Society

  19. Noble gas systematics of the Skaergaard intrusion

    Science.gov (United States)

    Horton, F.; Farley, K. A.; Taylor, H. P.

    2017-12-01

    The noble gas isotopic compositions of olivines from the Skaergaard layered mafic intrusion in Greenland reveal that magmas readily exchange noble gases with their environment after emplacement. Although Skaergaard magmas are thought to have derived from the upper mantle, all of the olivine separates we analyzed have 3He/4He ratios less than that of the upper mantle ( 8 Ra, where Ra = 3He/4He of the atmosphere, 1.39 x 10-6). This suggests that crustal and/or atmospheric noble gases have contaminated all Skaergaard magmas to some extent. We obtained the highest 3He/4He ratios ( 2 Ra) from olivines found in the lowermost exposed layers of the intrusion away from the margins. Excess radiogenic 4He (indicated by Raatmospheric isotopic compositions, but higher relative helium abundances than the atmosphere. We suggest that post-crystallization hydrothermal circulation introduced atmosphere-derived noble gases into uppermost layers of the intrusion. Such high temperature exchanges of volatiles between plutons and their immediate surroundings may help explain why so few mantle-derived rocks retain mantle-like noble gas signatures.

  20. Steady-State Spectroscopic Analysis of Proton-Dependent Electron Transfer on Pyrazine-Appended Metal Dithiolenes [Ni(pdt)2], [Pd(pdt)2], and [Pt(pdt)2] (pdt = 2,3-Pyrazinedithiol).

    Science.gov (United States)

    Kennedy, Steven R; Kozar, Morgan N; Yennawar, Hemant P; Lear, Benjamin J

    2016-09-06

    We report the structural, electronic, and acid/base properties of a series of ML2 metal dithiolene complexes, where M = Ni, Pd, Pt and L = 2,3-pyrazinedithiol. These complexes are non-innocent and possess strong electronic coupling between ligands across the metal center. The electronic coupling can be readily quantified in the monoanionic mixed valence state using Marcus-Hush theory. Analysis of the intervalence charge transfer (IVCT) band reveals that that electronic coupling in the mixed valence state is 5800, 4500, and 5700 cm(-1) for the Ni, Pd, and Pt complexes, respectively. We then focus on their response to acid titration in the mixed valence state, which generates the asymmetrically protonated mixed valence mixed protonated state. For all three complexes, protonation results in severe attenuation of the electronic coupling, as measured by the IVCT band. We find nearly 5-fold decreases in electronic coupling for both Ni and Pt, while, for the Pd complex, the electronic coupling is reduced to the point that the IVCT band is no longer observable. We ascribe the reduction in electronic coupling to charge pinning induced by asymmetric protonation. The more severe reduction in coupling for the Pd complex is a result of greater energetic mismatch between ligand and metal orbitals, reflected in the smaller electronic coupling for the pure mixed valence state. This work demonstrates that the bridging metal center can be used to tune the electronic coupling in both the mixed valence and mixed valence mixed protonated states, as well as the magnitude of change of the electronic coupling that accompanies changes in protonation state.

  1. ACCUMULATION OF SOME HEAVY METALS (PD, CD AND CR IN MILK OF GRAZING SHEEP IN NORTH-EAST HUNGARY

    Directory of Open Access Journals (Sweden)

    Péter Póti

    2012-08-01

    Full Text Available Food safety and traceability control in the production of agricultural primary products becomes more important criteria for the consumers because of the novel requirements of foods as tools for disease prevention and health. The objective of this study was to investigate the accumulation of lead, cadmium and chromium in milk of ewes during pasture condition. In present study, the amounts of the heavy metals in grass samples were lower than the highest acceptable limits according the regulations. Moreover, lead, cadmium and chromium concentrations were 0.023 mg, 0.012 mg and 0.290 mg/wet weight kg in milk samples, respectively. 50% and 40% of the milk samples the lead and cadmium values were out of the permissible limit. However, the amount of the heavy metals in grass and other forages samples were lower than the highest acceptable limits, concentration of Pb and Cd in milk samples were higher than the maximum acceptable limits of the EU regulation. These results suggested that necessary control the heavy metal contents of primary food products for food safety.

  2. Formation of amorphous alloys by mechanical alloying for platinum group metal-M(M=Zr or Al) system; Mechanical alloying ni yoru kikinzoku (Pd,Pt) to M(Zr aruiwa Al) tono kongo funmatsu no hishoshitsuka

    Energy Technology Data Exchange (ETDEWEB)

    Tsuzuki, T.; Arakawa, T. [Kinki Univ., Higashi-Osaka, Osaka (Japan)

    1998-08-15

    The intermetallic compounds containing precious metals such as platinum white gold are widely used in chemistry or industry as catalysts. These alloy catalysts are mainly used in grinding the materials prepared by solidifying liquids. The authors of the paper attempt to prepare alloy powders of precious metal with Zr or Al by mechanical alloying (MA). As an object of applying them on a catalyst, alloy powders of precious metals (Pd and Pt) and M (Zr or Al) are regulated by the mechanical alloying reaction, and the results show that the Pd and Pt show different MA reaction while using Al as the M, the former generates an intermetallic compound as PdAl during the halfway point of the MA reaction, but the later generates amorphous powders. But, each of them generates amorphous alloys only while using Zr and the M. As a result of differential thermal analysis and electrical resistivity measurement investigating the crystalline process of the obtained amorphous alloys, it is clarified that the Pt-Al base alloy shows higher crystalline temperature compared with the other alloys. 8 refs., 6 figs.

  3. Reducing-Agent-Free Instant Synthesis of Carbon-Supported Pd Catalysts in a Green Leidenfrost Droplet Reactor and Catalytic Activity in Formic Acid Dehydrogenation

    Science.gov (United States)

    Lee, Dong-Wook; Jin, Min-Ho; Lee, Young-Joo; Park, Ju-Hyoung; Lee, Chun-Boo; Park, Jong-Soo

    2016-05-01

    The development of green synthesis methods for supported noble metal catalysts remains important challenges to improve their sustainability. Here we first synthesized carbon-supported Pd catalysts in a green Leidenfrost droplet reactor without reducing agents, high-temperature calcination and reduction procedures. When the aqueous solution containing Pd nitrate precursor, carbon support, and water is dripped on a hot plate, vapor layer is formed between a solution droplet and hot surface, which allow the solution droplet to be levitated on the hot surface (Leidenfrost phenomena). Subsequently, Pd nanoparticles can be prepared without reducing agents in a weakly basic droplet reactor created by the Leidenfrost phenomena, and then the as-prepared Pd nanoparticles are loaded on carbon supports during boiling down the droplet on hot surface. Compared to conventional incipient wetness and chemical synthetic methods, the Leidenfrost droplet reactor does not need energy-consuming, time-consuming, and environmentally unfriendly procedures, which leads to much shorter synthesis time, lower carbon dioxide emission, and more ecofriendly process in comparison with conventional synthesis methods. Moreover, the catalysts synthesized in the Leidenfrost droplet reactor provided much better catalytic activity for room-temperature formic acid decomposition than those prepared by the incipient wetness method.

  4. Quality management for noble gas trace analysis

    International Nuclear Information System (INIS)

    Schmid, S.; Konrad, M.; Kumberg, T.; Schlosser, C.; Gohla, H.

    2014-01-01

    The Federal Office for Radiation Protection operates measurement systems to determine the activity concentrations of Krypton-85 and Xenon-133 in air samples since the early 70s. Certified standards with stable noble gas admixtures are still missing for quality assurance (certified activity concentrations). The Comprehensive Nuclear-Test-Ban Treaty Organization (CTBTO) is currently establishing a global noble gas monitoring network for the verification of compliance with the Treaty. In cooperation with CTBTO the BfS currently develops concepts of quality assurance for noble gas measurements. Opportunities for quality assurance without using certified standards are discussed by comparisons between individual laboratories and internal audits. The results from the first CTBTO laboratory intercomparison with synthetic radioxenon samples look very promising.

  5. In vitro corrosion and biocompatibility screening of sputtered Ti40Cu36Pd14Zr10 thin film metallic glasses on steels.

    Science.gov (United States)

    Subramanian, B

    2015-02-01

    The growth of multi-component thin film metallic glasses (TFMGs) of Ti40Cu36Pd14Zr10 (at.%) alloys fabricated using magnetron sputtering on bioimplantable 316 L stainless steel substrates has been investigated. The vapor-solid quenching during sputtering enables the amorphous phases to be formed. The amorphous films consist of a single glassy phase, as evidenced by a broad hump and no detectable crystalline peaks as observed from XRD and selective area electron diffraction (SAED) patterns. The average surface roughness (Ra) of the coated film as observed from AFM was 0.3 nm. Nanohardness of about 7.7 GPa and Young's modulus of 110 GPa were measured from nanoindentation analysis. The potentiodynamic polarization and impedance measurements showed that coated stainless steel substrates have higher corrosion resistance compared to uncoated SS substrate in simulated body fluid (SBF) solution. The cytotoxicity studies using L929 fibroblast cells showed that these coatings were non-cytotoxic in nature. The interactions between the coated surface and bacteria were investigated by agar diffusion method, solution suspension and wet interfacial contact methods. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Ni-free Zr-Cu-Al-Nb-Pd bulk metallic glasses with different Zr/Cu ratios for biomedical applications.

    Science.gov (United States)

    Huang, Lu; Yokoyama, Yoshihiko; Wu, Wei; Liaw, Peter K; Pang, Shujie; Inoue, Akihisa; Zhang, Tao; He, Wei

    2012-08-01

    Zr-based bulk metallic glasses (BMGs) possess attractive properties for prospective biomedical applications. The present study designs Ni-free Zr-Cu-Al-Nb-Pd BMGs and investigates their in vitro biocompatibility by studying mechanical properties, bio-corrosion resistance, and cellular responses. The Ti-6Al-4V alloy is used as a reference material. It is found that the Zr-based BMGs exhibit good mechanical properties, including high strengths above 1600 MPa, high hardness over 4700 MPa, and low elastic moduli of 85-90 GPa. The Zr-based BMGs are corrosion resistant in a simulated body environment, as revealed by wide passive regions, low passive current densities, and high pitting overpotentials. The formation of ZrO(2)-rich surface passive films of the Zr-based BMGs contributes to their high corrosion resistance, whereas their pitting corrosion in the phosphate buffered saline solution can be attributed to the sensitivity of the ZrO(2) films to the chloride ion. The general biosafety of the Zr-based BMGs is revealed by normal cell adhesions and cell morphologies. Moreover, the Zr/Cu content ratio in the alloy composition affects the biocompatibility of the Zr-based BMGs, by increasing their corrosion resistance and surface wettability with the increase of the Zr/Cu ratio. Effects of Zr/Cu ratios can be used to guide the future design of biocompatible Zr-based BMGs. Copyright © 2012 Wiley Periodicals, Inc.

  7. Metallic glassy Zr70Ni20Pd10 powders for improving the hydrogenation/dehydrogenation behavior of MgH2

    Science.gov (United States)

    El-Eskandarany, M. Sherif

    2016-01-01

    Because of its low density, storage of hydrogen in the gaseous and liquids states possess technical and economic challenges. One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides. Magnesium hydride (MgH2) remains the best hydrogen storage material due to its high hydrogen capacity and low cost of production. Due to its high activation energy and poor hydrogen sorption/desorption kinetics at moderate temperatures, the pure form of MgH2 is usually mechanically treated by high-energy ball mills and catalyzed with different types of catalysts. These steps are necessary for destabilizing MgH2 to enhance its kinetics behaviors. In the present work, we used a small mole fractions (5 wt.%) of metallic glassy of Zr70Ni20Pd10 powders as a new enhancement agent to improve its hydrogenation/dehydrogenation behaviors of MgH2. This short-range ordered material led to lower the decomposition temperature of MgH2 and its activation energy by about 121 °C and 51 kJ/mol, respectively. Complete hydrogenation/dehydrogenation processes were successfully achieved to charge/discharge about 6 wt.%H2 at 100 °C/200 °C within 1.18 min/3.8 min, respectively. In addition, this new nanocomposite system shows high performance of achieving continuous 100 hydrogen charging/discharging cycles without degradation. PMID:27220994

  8. On the Potential of Bulk Metallic Glasses for Dental Implantology: Case Study on Ti40Zr10Cu36Pd14

    Directory of Open Access Journals (Sweden)

    Alethea Liens

    2018-02-01

    Full Text Available Ti40Zr10Cu36Pd14 Bulk Metallic Glass (BMG appears very attractive for future biomedical applications thanks to its high glass forming ability, the absence of toxic elements such as Ni, Al or Be and its good mechanical properties. For the first time, a complete and exhaustive characterization of a unique batch of this glassy alloy was performed, together with ISO standard mechanical tests on machined implant-abutment assemblies. The results were compared to the benchmark Ti-6Al-4V ELI (Extra-Low-Interstitial to assess its potential in dental implantology. The thermal stability, corrosion and sterilization resistance, cytocompatibility and mechanical properties were measured on samples with a simple geometry, but also on implant-abutment assemblies’ prototypes. Results show that the glassy alloy exhibits a quite high thermal stability, with a temperature range of 38 °C between the glass transition and crystallization, a compressive strength of 2 GPa, a certain plastic deformation (0.7%, a hardness of 5.5 GPa and a toughness of 56 MPa.√m. Moreover, the alloy shows a relatively lower Young’s modulus (96 GPa than the Ti-6Al-4V alloy (110–115 GPa, which is beneficial to limit bone stress shielding. The BMG shows a satisfactory cytocompatibility, a high resistance to sterilization and a good corrosion resistance (corrosion potential of −0.07 V/SCE and corrosion current density of 6.0 nA/cm2, which may ensure its use as a biomaterial. Tests on dental implants reveal a load to failure 1.5-times higher than that of Ti-6Al-4V and a comparable fatigue limit. Moreover, implants could be machined and sandblasted by methods usually conducted for titanium implants, without significant degradation of their amorphous nature. All these properties place this metallic glass among a promising class of materials for mechanically-challenging applications such as dental implants.

  9. Catalyst System for Hydrogenation Catalysis Based on Multiarm Hyperbranched Polymer Templated Metal (Au, Pt, Pd, Cu Nanoparticles

    Directory of Open Access Journals (Sweden)

    Yunfeng Shi

    2017-09-01

    Full Text Available With a hyperbranched poly(amidoamine core and many water-soluble poly(ethylene glycol monomethyl ether arms connected by pH-sensitive acylhydrazone bonds, multiarm hyperbranched polymer was used as nanoreactor and reductant to prepare metal nanoparticles endowed with intelligence and biocompatibility. The multiarm hyperbranched polymer encapsulated nanoparticles (NPs showed excellent catalytic activity for hydrogenation, thus an excellent catalyst system for hydrogenation was established. The rate constants could reach as high as 3.48 L·s−1·m−2, which can be attributed to the lack of surface passivation afforded by the multiarm hyperbranched polymer.

  10. Noble Gas signatures of Enhanced Oil Recovery

    Science.gov (United States)

    Barry, P. H.; Kulongoski, J. T.; Tyne, R. L.; Hillegonds, D.; Byrne, D. J.; Landon, M. K.; Ballentine, C. J.

    2017-12-01

    Noble gases are powerful tracers of fluids from various oil and gas production activities in hydrocarbon reservoirs and nearby groundwater. Non-radiogenic noble gases are introduced into undisturbed oil and natural gas reservoirs through exchange with formation waters [1-3]. Reservoirs with extensive hydraulic fracturing, injection for enhanced oil recovery (EOR), and/or waste disposal also show evidence for a component of noble gases introduced from air [4]. Isotopic and elemental ratios of noble gases can be used to 1) assess the migration history of the injected and formation fluids, and 2) determine the extent of exchange between multiphase fluids in different reservoirs. We present noble gas isotope and abundance data from casing, separator and injectate gases of the Lost Hills and Fruitvale oil fields in the San Joaquin basin, California. Samples were collected as part of the California State Water Resource Control Board's Oil and Gas Regional Groundwater Monitoring Program. Lost Hills (n=7) and Fruitvale (n=2) gases are geochemically distinct and duplicate samples are highly reproducible. Lost Hills casing gas samples were collected from areas where EOR and hydraulic fracturing has occurred in the past several years, and from areas where EOR is absent. The Fruitvale samples were collected from a re-injection port. All samples are radiogenic in their He isotopes, typical of a crustal environment, and show enrichments in heavy noble gases, resulting from preferential adsorption on sediments. Fruitvale samples reflect air-like surface conditions, with higher air-derived noble gas concentrations. Lost Hills gases show a gradation from pristine crustal signatures - indicative of closed-system exchange with formation fluids - to strongly air-contaminated signatures in the EOR region. Pristine samples can be used to determine the extent of hydrocarbon exchange with fluids, whereas samples with excess air can be used to quantify the extent of EOR. Determining noble

  11. Clinical Evaluation and Patient Satisfaction of Single Zirconia-Based and High-Noble Alloy Porcelain-Fused-to-Metal Crowns in the Esthetic Area: A Retrospective Cohort Study.

    Science.gov (United States)

    Shi, Jun-Yu; Li, Xin; Ni, Jie; Zhu, Zi-Yuan

    2016-10-01

    The aim of this study was to assess clinical survival, complications, and patient satisfaction with single zirconia-based crowns (ZC) or high-noble alloy PFM crowns (HC) in esthetic areas. The study was a retrospective cohort study with up to 3.8 years follow-up (mean 2.5 years). Patients who met the inclusion criteria were reviewed. Survival rates, complications, satisfaction rates (color and form), and overall satisfaction (visual analogue scale, VAS) were evaluated by follow-up examination. Chi-square test (survival, complication, and satisfaction rate) and unpaired t-test (overall satisfaction: VAS) were used to test the difference between the ZC and HC groups. Survival rates and complications were assessed both at subject-level (patient as statistical unit) and at tooth-level (tooth as statistical unit). One hundred and thirteen patients met the inclusion criteria; 95 patients (ZC: 45, HC: 50) with 132 crowns (ZC: 61, HC: 71) were enrolled in the study. The overall survival rate was 93.3% for ZC crowns and 96.0% for HC crowns at subject-level and 93.4% for ZC crowns and 97.2% for HC crowns at tooth-level (p = 0.56 and 0.30, respectively). Veneer chipping was the most frequently seen complication. One HC crown lost retention because of poor cementation. One patient in the ZC group showed progression of periodontal disease. No significant difference of complications was found between the two groups at subject-level and tooth-level (p = 0.37 and 0.34, respectively). The overall satisfaction (VAS) was 8.18 for ZC crowns and 8.46 for HC crowns (p = 0.34). The results of the study showed that a high survival rate could be achieved in both ZC and HC groups. Chipping of the veneering porcelain was the most frequently seen event that led to short-term (less than 3 years) failure and complications. The patients' rating of ZC crowns was not superior to HC crowns. Well-designed studies with high evidence level and large sample size are still needed to further explore the

  12. Exploring the metal coordination properties of the pyrimidine part of purine nucleobases: isomerization reactions in heteronuclear Pt(II)/Pd(II) of 9-methyladenine.

    Science.gov (United States)

    Ibáñez, Susana; Albertí, Francisca M; Sanz Miguel, Pablo J; Lippert, Bernhard

    2011-10-17

    The synthesis and characterization of three heteronuclear Pt(2)Pd(2) (4, 5) and PtPd(2) (6) complexes of the model nucleobase 9-methyladenine (9-MeA) is reported. The compounds were prepared by reacting [Pt(NH(3))(3)(9-MeA-N7)](ClO(4))(2) (1) with [Pd(en)(H(2)O)(2)](ClO(4))(2) at different ratios r between Pt and Pd, with the goal to probe Pd(II) binding to any of the three available nitrogen atoms, N1, N3, N6 or combinations thereof. Pd(II) coordination occurs at N1 and at the deprotonated N6 positions, yet not at N3. 4 and 5 are isomers of [{(en)Pd}(2){N1,N6-9-MeA(-)-N7)Pt(NH(3))(3)}(2)](ClO(4))(6)·nH(2)O, with a head-head orientation of the two bridging 9-MeA(-) ligands in 4 and a head-tail orientation in 5. 6 is [{(en)Pd}(2)(OH)(N1,N6-9MeA(-)-N7)Pt(NH(3))(3)](ClO(4))(4)·4H(2)O, hence a condensation product between [Pt(NH(3))(3)(9-MeA-N7)](2+) and a μ-OH bridged dinuclear (en)Pd-OH-Pd(en) unit, which connects the N1 and N6 positions of 9-MeA(-) in an intramolecular fashion. 4 and 5, which slowly interconvert in aqueous solution, display distinct structural differences such as significantly different intramolecular Pd···Pd contacts (3.124 0(16) Å in 4; 2.986 6(14) Å in 5), among others. Binding of (en)Pd(II) to the exocyclic N6 atom in 4 and 5 is accompanied by a large movement of Pd(II) out of the 9-MeA(-) plane and a trend to a further shortening of the C6-N6 bond as compared to free 9-MeA. The packing patterns of 4 and 5 reveal substantial anion-π interactions.

  13. Encapsulation of noble gas in zeolites

    International Nuclear Information System (INIS)

    Dorea, A.

    1987-04-01

    The noble gases neon, argon, krypton and xenon were encapsulated hydrothermally as pure gases as well as in the form of mixtures in type A zeolite of various cationic compositions. As opposed to the starting material the encapsulates are X-ray amorphous and posess a very small specific surface area. Irrespective of the thermal pretreatment of the zeolites the optimal loading occured within a certain temperature window. The amount of gas trapped was essentially a function of the fixation pressure. Within the pressure range 50-2200 bar the obtained loading was independent from the type of noble gas. When mixtures of noble gases were encapsulated a small enrichment of the heavier noble gas, caused by kinetic and thermodynamic effects, was observed. The thermal stability of the encapsulates was found to be very high. Even at temperatures as high as 750 0 C a recrystallization to anorthite was only observed after practically all the trapped gas had been released. Experiments destined to clarify the mechanism of gas leckage at temperatures below 750 0 C suggest a diffusion controlled mechanism described by a √t law. Even at loadings of 45 ml/(STP) Kr/g the leckage predicted under conditions as expected during longterm storage of Kr-85 is extremely small. Kinetic data demonstrate that the gas is not trapped in the form of agglomerates but rather exists homogeneously distributed within the encapsulate. This result is substantiated by electron beam microanalysis. (orig./RB) [de

  14. Noble gases as cardioprotectants - translatability and mechanism

    NARCIS (Netherlands)

    Smit, Kirsten F.; Weber, Nina C.; Hollmann, Markus W.; Preckel, Benedikt

    2015-01-01

    Several noble gases, although classified as inert substances, exert a tissue-protective effect in different experimental models when applied before organ ischaemia as an early or late preconditioning stimulus, after ischaemia as a post-conditioning stimulus or when given in combination before,

  15. Natural Death and the Noble Savage.

    Science.gov (United States)

    Walter, Tony

    1995-01-01

    The belief that dying and grieving are natural processes is widely held in modern bereavement care. Examines four assumption often made in this connection: (1) most primitive cultures deal with death in an accepting way; (2) this way is different than our own; (3) it is a good and noble way; and (4) traditional societies see death as natural. (JBJ)

  16. Organ protection by the noble gas helium

    NARCIS (Netherlands)

    Smit, K.F.

    2017-01-01

    The aims of this thesis were to investigate whether helium induces preconditioning in humans, and to elucidate the mechanisms behind this possible protection. First, we collected data regarding organ protective effects of noble gases in general, and of helium in particular (chapters 1-3). In chapter

  17. Cold and trapped metastable noble gases

    NARCIS (Netherlands)

    Vassen, W.; Cohen-Tannoudji, C.; Leduc, M.; Boiron, D.; Westbrook, C.I.; Truscott, A.; Baldwin, K.; Birkl, G.; Cancio, P.; Trippenbach, M.

    2012-01-01

    Experimental work on cold, trapped metastable noble gases is reviewed. The aspects which distinguish work with these atoms from the large body of work on cold, trapped atoms in general is emphasized. These aspects include detection techniques and collision processes unique to metastable atoms.

  18. Synthesis of Pt, Pd, Pt/Ag and Pd/Ag nanoparticles by microwave ...

    Indian Academy of Sciences (India)

    Unknown

    ved considerable attention. It has been shown that the colour of noble metal nanoparticles ... process favours the complete reduction of latter into monometallic clusters before the other ions can be reduced at their ... attracted significant attention due to their specific catalytic activity and selectivity in hydrogenation and visible ...

  19. Therapeutic Potential of Noble Nanoparticles for Wound Repair

    Directory of Open Access Journals (Sweden)