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Sample records for ag pd pt

  1. Bimetallic Pt-Ag and Pd-Ag nanoparticles

    SciTech Connect

    Lahiri, Debdutta; Bunker, Bruce; Mishra, Bhoopesh; Zhang, Zhenyuan; Meisel, Dan; Doudna, C.M.; Bertino, M. F.; Blum, Frank D.; Tokuhiro, A.T.; Chattopadhyay, Soma; Shibata, Tomohiro; Terry, Jeff

    2005-05-01

    We report studies of bimetallic nanoparticles with 15%-16% atomic crystal parameters size mismatch. The degree of alloying was probed in a 2-nm Pt core (smallest attainable core size) of Pt-Ag nanoparticles (completely immiscible in bulk) and 20-nm-diameter Pd-Ag nanowires (completely miscible in bulk). Particles were synthesized radiolytically, and depending on the initial parameters, they assume spherical or cylindrical (nanowire) morphologies. In all cases, the metals are seen to follow their bulk alloying characteristics. Pt and Ag segregate in both spherical and wire forms, which indicates that strain due to crystallographic mismatch overcomes the excess surface free energy in the small particles. The Pd-Ag nanowires alloy similar to previously reported spherical Pd-Ag particles of similar diameter and composition.

  2. Bimetallic Pt-Ag and Pd-Ag nanoparticles

    SciTech Connect

    Lahiri, Debdutta; Bunker, Bruce; Mishra, Bhoopesh; Zhang, Zhenyuan; Meisel, Dan; Doudna, C. M.; Bertino, M. F.; Blum, Frank D.; Tokuhiro, A. T.; Chattopadhyay, Soma; Shibata, Tomohiro; Terry, Jeff

    2005-04-19

    We report studies of bimetallic nanoparticles with 15%–16% atomic crystal parameters size mismatch. The degree of alloying was also probed in a 2-nm Pt core ssmallest attainable core sized of Pt–Ag nanoparticles scompletely immiscible in bulkd and 20-nm-diameter Pd–Ag nanowires scompletely miscible in bulkd. Particles were synthesized radiolytically, and depending on the initial parameters, they assume spherical or cylindrical snanowired morphologies. In all cases, the metals are seen to follow their bulk alloying characteristics. Also, Pt and Ag segregate in both spherical and wire forms, which indicates that strain due to crystallographic mismatch overcomes the excess surface free energy in the small particles. The Pd–Ag nanowires alloy similar to previously reported spherical Pd–Ag particles of similar diameter and composition

  3. EXAFS Studies of Bimetallic Ag-Pt and Ag-Pd Nanorods

    SciTech Connect

    Lahiri, D.; Chattopadhyay, S.; Bunker, B.A.; Doudna, C.M.; Bertino, M.F.; Blum, F.; Tokuhiro, A.; Terry, J.

    2008-10-30

    Nanoparticles of Ag-Pt and Ag-Pd with high aspect ratios were synthesized using a radiolysis method. Gamma rays at dose rates below 0.5 kGy/h were used for irradiation. The nanoparticles were characterized by transmission electron microscopy (TEM), optical absorption spectroscopy and x-ray Absorption Fine Structure (XAFS) spectroscopy. Bright field micrographs show that Ag-Pt nanowires are composed of large particles with diameters ranging from 20-30 nm and joined by filaments of diameter between 2-5 nm. The Ag-Pd nanowires have diameters of 20-25 nm and lengths of 1.5 {micro}m. For XAFS measurements, the Pt L3 edge (11.564 keV), Ag K-edge (25.514 keV) and Pd K-edge (24.350 keV) were excited to determine the local structure around the respective atoms in the cluster. The Ag-Pt particles were found to possess a distinct core-shell structure with Pt in the core surrounded by Ag shell, with no indication of alloy formation. However, nanorods of Ag-Pd have formed an alloy for all the alloy compositions.

  4. Genetic Pd, Pt, Au, Ag, and Rh mineralogy in Noril'sk sulfide ores

    NASA Astrophysics Data System (ADS)

    Spiridonov, E. M.; Kulagov, E. A.; Serova, A. A.; Kulikova, I. M.; Korotaeva, N. N.; Sereda, E. V.; Tushentsova, I. N.; Belyakov, S. N.; Zhukov, N. N.

    2015-09-01

    The undeformed ore-bearing intrusions of the Noril'sk ore field (NOF) cut through volcanic rocks of the Late Permian-Early Triassic trap association folded in brachysynclines. Due to the nonuniform load on the roof of intrusive bodies, most sulfide melts were squeezed, up to the tops of ore-bearing intrusions; readily fusible Ni-Fe-Cu sulfide melts were almost completely squeezed. In our opinion, not only one but two stages of mineralization developed at the Noril'sk deposits: (i) syntrap magmatic and (ii) epigenetic post-trap metamorphic-hydrothermal. All platinum-group minerals (PGM) and minerals of gold are metasomatic in the Noril'sk ores. They replaced sulfide solid solutions and exsolution structures. All types of PGM and Au minerals occur in the ores, varying in composition from pyrrhotite to chalcopyrite, talnakhite, mooihoekite, and rich in galena; they are localized in the inner and outer contact zones and differ only in the quantitative proportions of ore minerals. The aureoles of PGM and Au-Ag minerals are wider than the contours of sulfide bodies and coincide with halos of fluid impact on orebodies and adjacent host rocks. The pneumatolytic PGM and Au-Ag minerals are correlated in abundance with the dimensions of sulfide bodies. Their amounts are maximal in veins of late fusible ore composed of eutectic PbS ss and iss intergrowths, as well as at their contacts. The Pd and Pt contents in eutectic sulfide ores of NOF are the world's highest. In the process of noble-metal mineral formation, the fluids supply Pd, Pt, Au, As, Sb, Sn, Bi, and a part of Te, whereas Fe, Ni, Cu, Pb, Ag, Rh, a part of Te and Pd are leached from the replaced sulfide minerals. The pneumatolytic PGM of the early stage comprises Pd and Pt intermetallic compounds enriched in Au along with Pd-Pt-Fe-Ni-Cu-Sn-Pb(As) and (Pd,Pt,Au)(Sn,Sb,Bi,Te,As) solid solutions. Pneumatolytic PGM and Au minerals of the middle stage are products of solid-phase transformation and recrystallization of

  5. Nanocatalyst superior to Pt for oxygen reduction reactions: the case of core/shell Ag(Au)/CuPd nanoparticles.

    PubMed

    Guo, Shaojun; Zhang, Xu; Zhu, Wenlei; He, Kai; Su, Dong; Mendoza-Garcia, Adriana; Ho, Sally Fae; Lu, Gang; Sun, Shouheng

    2014-10-22

    Controlling the electronic structure and surface strain of a nanoparticle catalyst has become an important strategy to tune and to optimize its catalytic efficiency for a chemical reaction. Using density functional theory (DFT) calculations, we predicted that core/shell M/CuPd (M = Ag, Au) NPs with a 0.8 or 1.2 nm CuPd2 shell have similar but optimal surface strain and composition and may surpass Pt in catalyzing oxygen reduction reactions. We synthesized monodisperse M/CuPd NPs by the coreduction of palladium acetylacetonate and copper acetylacetonate in the presence of Ag (or Au) nanoparticles with controlled shell thicknesses of 0.4, 0.75, and 1.1 nm and CuPd compositions and evaluated their catalysis for the oxygen reduction reaction in 0.1 M KOH solution. As predicted, our Ag/Cu37Pd63 and Au/Cu40Pd60 catalysts with 0.75 and 1.1 nm shells were more efficient catalysts than the commercial Pt catalyst (Fuel Cells Store), with their mass activity reaching 0.20 A/mg of noble metal at -0.1 V vs Ag/AgCl (4 M KCl); this was over 3 times higher than that (0.06 A/mg Pt) from the commercial Pt. These Ag(Au)/CuPd nanoparticles are promising non-Pt catalysts for oxygen reduction reactions. PMID:25279704

  6. Trimetallic nanostructures: the case of AgPd/Pt multiply twinned nanoparticles

    PubMed Central

    Khanal, Subarna; Bhattarai, Nabraj; Velázquez-Salazar, J. Jesús; Bahena, Daniel; Soldano, German; Ponce, Arturo; Mariscal, Marcelo M.; Mejía-Rosales, Sergio; José-Yacamán, Miguel

    2013-01-01

    We report the synthesis, structural characterization, and atomistic simulations of AgPd/Pt trimetallic (TM) nanoparticles. Two types of structure were synthesized using a relatively facile chemical method: multiply twinned core-shell, and hollow particles. The nanoparticles were small in size, with an average diameter of 11 nm and a narrow distribution, and their characterization by aberration corrected scanning transmission electron microscopy allowed us to probe the structure of the particles at atomistic level. In some nanoparticles, the formation of a hollow structure was also observed, that facilitates the alloying of Ag and Pt in the shell region and the segregation of Ag atoms in the surface, affecting the catalytic activity and stability. We also investigated the growth mechanism of the nanoparticles using grand canonical Monte Carlo simulations, and we have found that Pt regions grow at overpotentials on the AgPd nanoalloys, forming 3D islands at the early stages of the deposition process. We found very good agreement between the simulated structures and those observed experimentally. PMID:24165796

  7. Beet juice utilization: Expeditious green synthesis of nobel metal nanoparticles (Ag, Au, Pt, and Pd) using microwaves

    EPA Science Inventory

    Metal nanoparticles of Ag, Au, Pt, and Pd were prepared in aqueous solutions via a rapid microwave-assisted green method using beet juice, an abundant sugar-rich agricultural produce, served as both a reducing and a capping reagent. The Ag nanoparticles with capping prepared by b...

  8. Effect of Ag addition to L1{sub 0} FePt and L1{sub 0} FePd films grown by molecular beam epitaxy

    SciTech Connect

    Tokuoka, Y.; Seto, Y.; Kato, T.; Iwata, S.

    2014-05-07

    L1{sub 0} ordered FePt-Ag (5 nm) and FePd-Ag (5 nm) films were grown on MgO (001) substrate at temperatures of 250–400 °C by using molecular beam epitaxy method, and their crystal and surface structures, perpendicular magnetic anisotropies and Curie temperatures were investigated. In the case of FePt-Ag, Ag addition with the amount of 10–20 at. % was effective to promote L1{sub 0} ordering and granular growth, resulting in the increase of the perpendicular magnetic anisotropy and coercivity of the FePt-Ag films. On the other hand, in the case of FePd-Ag, Ag addition changed the surface morphology from island to continuous film associated with the reductions of its coercivity and perpendicular anisotropy. The variations of lattice constants and Curie temperature with Ag addition were significantly different between FePt-Ag and FePd-Ag. For FePd-Ag, the c and a axes lattice spacings and Curie temperature gradually changed with increasing Ag content, while they unchanged for FePt-Ag. These results suggest the possibility of the formation of FePdAg alloy in FePd-Ag, while Ag segregation in FePt-Ag.

  9. Tarnish resistance evaluation of experimental Pd-free Ag-Au-Pt-Cu dental alloys.

    PubMed

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

    2010-05-01

    This study evaluated the tarnish resistance of eight experimental Pd-free Ag-Au-Pt-Cu dental alloys in a 0.1% Na(2)S aqueous solution at 37 degrees C. Color measurements of the plate samples were made using a computerized spectrophotometer before and after immersion in the test solution for up to 72 hours. Tarnish discoloration was evaluated using the color difference vector, DeltaE*, in the CIELAB color space. Microstructural observation of each sample through an optical microscope revealed the matrix phase as the major constituent and second-phase small grains in the matrix phase. Selective tarnish discoloration occurred in the matrix, and fractional area of the matrix to the whole surface area was influenced by the sum of Au and Ag concentrations. The DeltaE* value significantly decreased with increasing Au/(Au+Ag) atomic ratio. In conclusion, the Au/(Au+Ag) ratio in an alloy and the fractional area of the matrix were found to be primary and auxiliary factors affecting the tarnish resistance of the experimental alloys. PMID:20495286

  10. Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 1

    NASA Astrophysics Data System (ADS)

    Pech-Pech, I. E.; Gervasio, Dominic F.; Godínez-Garcia, A.; Solorza-Feria, O.; Pérez-Robles, J. F.

    2015-02-01

    Silver (Ag) nanoparticles enriched with platinum (Pt) and palladium (Pd) on their surfaces (Ag@Pt0.1Pd0.1) are supported on Vulcan XC-72 carbon (C) to form a new catalyst (Ag@Pt0.1Pd0.1/C) for the oxygen reduction reaction (ORR) in acid electrolytes. This catalyst is prepared in one pot by reducing Ag and then Pt and Pd metal salts with sodium borohydride in the presence of trisodium citrate then adding XC-72 while applying intense ultrasound. The metallic Ag@Pt0.1Pd0.1 nanoparticles contain 2 weight percent of Pt, are spherical and have an average size less than 10 nm as determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). At the ORR potentials, Ag nanoparticles on carbon (Ag/C) rapidly lose Ag by dissolution and show no more catalytic activity for the ORR than the carbon support, whereas Ag@Pt0.1Pd0.1/C is a stable catalyst and exhibits 1.4 and 1.6 fold greater specific activity, also 3.6 and 2.8 fold greater mass activity for ORR in 0.5 M H2SO4 solution than comparable Pt/C and Pt0.5Pd0.5/C catalysts with the same Pt loading as determined for thin-films of these catalysts on a rotating-disk electrode (TF-RDE). Using silver nanoparticles increases Pt utilization and therefore decreases Pt-loading and cost of a catalyst for a proton exchange membrane fuel cell (PEMFC) electrode.

  11. Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 2

    NASA Astrophysics Data System (ADS)

    Pech-Pech, I. E.; Gervasio, Dominic F.; Pérez-Robles, J. F.

    2015-02-01

    In the first part of this work, the feasibility of developing a catalyst with high activity for the oxygen electroreduction reaction (ORR) in acid media and with low Pt loading was demonstrated by over coating a silver (Ag) nanoparticle with a shell of platinum (Pt) and palladium (Pd) [7]. The results show that best activity is not directly related to a higher PtPd loading on the surface of the Ag. The best catalyst in a series of this type of catalyst is found with Ag@Pt0.3Pd0.3/C which gives a specific activity for oxygen reduction, jk (in units of mA cm-2 of real area), of 0.07 mA cm-2 at 0.85 V vs. NHE, as compared to 0.04 mA cm-2 when with a commercial Pt on carbon catalyst (Pt20/C) is used in an identical electrode except for the catalyst. The mass activity, jm (in units of mA μg-1 of Pt), for Ag@Pt0.3Pd0.3/C is 0.04 mA μg-1 of Pt at 0.85 V vs. NHE, whereas that for the Pt20/C gives 0.02 mA μg-1 of Pt, showing Ag@Pt0.3Pd0.3/C is a lower-cost catalyst, because using a Ag core and Pd with Pt in the shell gives the highest catalytic activity using less Pt.

  12. Continuous syntheses of Pd@Pt and Cu@Ag core-shell nanoparticles using microwave-assisted core particle formation coupled with galvanic metal displacement.

    PubMed

    Miyakawa, Masato; Hiyoshi, Norihito; Nishioka, Masateru; Koda, Hidekazu; Sato, Koichi; Miyazawa, Akira; Suzuki, Toshishige M

    2014-08-01

    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. PMID:24948122

  13. M-Au/TiO2 (M = Ag, Pd, and Pt) nanophotocatalyst for overall solar water splitting: role of interfaces.

    PubMed

    Melvin, Ambrose A; Illath, Kavya; Das, Tanmay; Raja, Thirumalaiswamy; Bhattacharyya, Somnath; Gopinath, Chinnakonda S

    2015-08-28

    M-Au/TiO2 (M = Ag, Pd, Pt) composites were prepared through a facile one-pot photodeposition synthesis and evaluated for solar water splitting (SWS) with and without a sacrificial agent. The M-Au combination exhibits a dominant role in augmenting the H2 generation activity by forming a bi-metallic system. Degussa P25 was used as a TiO2 substrate to photodeposit Au followed by Au + M (M = Ag/Pd/Pt). The SWS activity of the M-Au/TiO2 was determined through photocatalytic H2 production in the presence of methanol as a sacrificial agent under one sun conditions with an AM1.5 filter. The highest H2 yield was observed for Pt0.5-Au1/TiO2 and was around 1.3 ± 0.07 mmol h(-1) g(-1), with an apparent quantum yield (AQY) of 6.4%. Pt0.5-Au1/TiO2 also demonstrated the same activity for 25 cycles of five hours each for 125 h. Critically, the same Pt0.5-Au1/TiO2 catalyst was active in overall SWS (OSWS) without any sacrificial agent, with an AQY = 0.8%. The amount of Au and/or Pt was varied to obtain the optimum composition and it was found that the Pt0.5-Au1/TiO2 composition exhibits the best activity. Detailed characterization by physico-chemical, spectral and microscopy measurements was carried out to obtain an in-depth understanding of the origin of the photocatalytic activity of Pt0.5-Au1/TiO2. These in-depth studies show that gold interacts predominantly with oxygen vacancies present on titania surfaces, and Pt preferentially interacts with gold for an effective electron-hole pair separation at Pt-Au interfaces and electron storage in metal particles. The Pt in Pt0.5-Au1/TiO2 is electronically and catalytically different from the Pt in Pt/TiO2 and it is predicted that the former suppresses the oxygen reduction reaction. PMID:26199221

  14. DFT study of the adsorption properties of single Pt, Pd, Ag, In and Sn on the γ-Al2O3 (1 1 0) surface

    NASA Astrophysics Data System (ADS)

    Gao, Hongwei

    2016-07-01

    GGA/PW91 exchange-correlation functional within periodic density functional theory (DFT) has been used to investigate the adsorption properties of different metal atoms (Pt, Pd, Ag, Sn and In) on the O-terminated and Al-terminated γ-Al2O3 (1 1 0) surface. The predicted adsorption energies follow the order Sn > In > Ag > Pd > Pt. It is found that O-bridge position is the most favorable site for single Pt, Pd, Ag, Sn and In adsorption on the O-terminated γ-Al2O3 (1 1 0) surface. It is found that the most favorable site on the Al-terminated γ-Al2O3 (1 1 0) surface is O-top position.

  15. The growth, structure, and thermal stability of vapor deposited ultra-thin metal films: Rh on Ag(100), Au on Pd(110), and Pt on Pd(110)

    SciTech Connect

    Schmitz, P.

    1990-09-21

    The growth, structure, and thermal stability of ultra-thin metal films (Rh on Ag(100); Au on Pd(110) and Pt on Pd(110)) is investigated using surface sensitive techniques. The three systems studied present a variety of differing characteristics which can contribute to the growth mode, two-dimensional structure, and thermal stability of the films. The main factors contributing to the differing properties of the three systems presented here are: (1) the different substrate morphologies; (2) the differences in surface free energies between the overlayer and the substrate; (3) the degree of lattice mismatch for a particular system; and (4) the extent of miscibility of the two metals. 200 refs., 38 figs.

  16. Monolayer magnetism of 3d transition metals in Ag, Au, Pd, and Pt hosts: Systematics of local moment variation

    NASA Astrophysics Data System (ADS)

    McHenry, M. E.; MacLaren, J. M.; Clougherty, D. P.

    1991-11-01

    Electronic and magnetic properties of T/Aun, T/Agn (T=Cr, Mn, Fe, Co, and Ni), Fe/Pdn and Fe/Ptn multilayers and sandwiches have been computed using the layer Korringa-Kohn-Rostoker (LKKR) band-structure technique. Enhanced (as compared with bulk) 2D T magnetism is observed in all Cr, Mn, and Fe/host configurations, consistent with weak coupling between Cr, Mn, and Fe d bands and those of the noble metal (NM) hosts and consequently d bandwidths which are exceeded by the exchange splitting. Fe and Cr moments vary systematically with the number of mediating Ag or Au planes and the Fermi energy of the system. These systematics are explained by considering the variation of the Fermi energy (EF) with composition as well as constraints of charge neutrality and strong (single-band) ferromagnetism. For Fe in Pt and Pd hosts, d-d hybridization leads to a nearly invariant Fe moment as a function of the number of mediating Pd or Pt planes but with large induced moments on the host.

  17. Distribution of Precious Metals (Ag, Au, Pd, Pt, and Rh) Between Copper Matte and Iron Silicate Slag

    NASA Astrophysics Data System (ADS)

    Avarmaa, Katri; Johto, Hannu; Taskinen, Pekka

    2016-02-01

    The distributions of precious metals (Ag, Au, Pd, Pt, and Rh) between copper matte and silica-saturated iron silicate slag were determined at 1523 K to 1623 K (1250 °C to 1350 °C), in controlled CO-CO2-SO2-Ar gas mixtures. The experiments were done in silica crucibles and a fixed partial pressure of sulfur dioxide for matte grades of 55, 65, and 75 wt pct Cu. High-temperature equilibration/quenching/electron probe X-ray microanalysis technique was used to obtain compositions of the equilibrated matte and slag. The technique was applied for the first time to the distributions of precious metals in simulated flash smelting conditions. The resolution of electron probe microanalysis became critical as the detection limits were insufficient to measure reliably the precious metals concentrations (except silver) in the slag. The distribution coefficient of silver, L m/s[Ag] = [wt pctAg in matte]/(wt pctAg in slag), was found to be between 200 and 300, which agrees well with the latest studies in the literature. For other precious metals, the minimum values of distribution coefficients were determined according to the detection limits in the slag. The values obtained were for gold and platinum >250, for palladium >1000, and for rhodium >900. The distribution coefficients of palladium, although locating above distribution coefficient of the detection limit, formed a clear dependency with a good repeatability as a function of the matte grade. It increased along with matte grade and was approximately 1000 at 50 pct Cu and 2000 to 3000 at 70 pct Cu. The precious metals replace metal in the matte structure and they are present as sulfides in the copper matte.

  18. The germanides ScTGe (T = Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, Au) - Structure and 45Sc solid state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Heying, Birgit; Haverkamp, Sandra; Rodewald, Ute Ch; Eckert, Hellmut; Peter, Sebastian C.; Pöttgen, Rainer

    2015-01-01

    The germanides ScTGe (T = Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, Au) were obtained in X-ray pure form by arc-melting of the elements. The structures of the members with T = Co, Ni, Cu, Rh, Pd, Ag, Ir, and Pt were refined on the basis of single crystal X-ray diffractometer data. The germanides with T = Cu, Ru, Pd, Ag crystallize with the hexagonal ZrNiAl type structure, space group P 6 bar 2m and those with T = Co, Ni, Rh, Ir, Pt adopt the orthorhombic TiNiSi type. ScAuGe is isotypic with NdPtSb. All germanides exhibit single scandium sites. A simple systematization of the structure type according to the valence electron concentration is not possible. The 45Sc solid state NMR parameters (Knight shifts and nuclear electric quadrupole coupling constants) of those members crystallizing in the TiNiSi structure show systematic trends as a function of valence electron concentration number. Furthermore, within each T-group the Knight shift decreases with increasing atomic number; this correlation also includes previously published results on the isotypic silicide family. The 45Sc quadrupolar interaction tensor components are generally well-reproduced by quantum mechanical electric field gradient calculations using the WIEN2k code.

  19. Copper-based alloys, crystallographic and crystallochemical parameters of alloys in binary systems Cu-Me (Me=Co, Rh, Ir, Cu, Ag, Au, Ni, Pd, Pt)

    NASA Astrophysics Data System (ADS)

    Porobova, Svetlana; Markova, Tat'jana; Klopotov, Vladimir; Klopotov, Anatoliy; Loskutov, Oleg; Vlasov, Viktor

    2016-01-01

    The article presents the results of the analysis of phase equilibrium of ordered phases in binary systems based on copper Cu- Me (where Me - Co, Rh, Ir, Ag, Au, Ni, Pd, Pt) to find correlations of crystallochemical and crystallographic factors. It is established that the packing index in disordered solid solutions in binary systems based on copper is close to the value of 0.74 against the background of an insignificant deviation of atomic volumes from the Zen's law.

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

    PubMed

    Gu, Hui; Yang, Yan; Tian, Jixiang; Shi, Guoyue

    2013-07-24

    For the first time, a series of noble metal (Ag, Au, Pd, and Pt) nanoparticles (NPs) based on new functional graphene were successfully achieved via UV-assisted photocatalytic reduction by ZnO nanorods. The whole preparation strategy for constructing noble metal deposited graphene sheets/ZnO (GS/ZnO) was elucidated in detail in this work. First, graphene oxide based two-dimensional carbon nanostructures served as a support to disperse ZnO nanorods through a hydrothermal route. The ZnO nanorods were self-assembled onto the surface of graphene sheets, forming GS/ZnO nanocomposite, and the graphene oxide was reduced, yielding reduced graphene sheets in this synthetic procedure. Second, the GS/ZnO films were further employed as supporting materials for the dispersion of metal nanoparticles. Photogenerated electrons from UV-irradiated ZnO were transported across GS to stepwise and respectively reduce v μL metal ions (Ag(+), Pd(2+), AuCl4(-), PtCl6(2-), 20 mg/mL) into metal (Ag, Pd, Au, Pt) NPs at a location distinct from the ZnO anchored site, forming five graphene-based hybrid nanocomposites designated as GS/ZnO, GS/ZnO@Agv, GS/ZnO@Pdv, GS/ZnO@Auv, GS/ZnO@Ptv, respectively. The obtained mutihybrid nanoarchitectured materials were clearly characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). According to the diameters and distribution, the four metal NPs on GS/ZnO were divided into two categories: Ag&Au and Pd&Pt. Their difference was rooted in the rival abilities of gathering electron between graphene and different metal islands in the photochemical reduction process. The electrochemical behaviors of the five resultant hybrid nanocomposites were investigated in H2O2 as well as in potassium ferricyanide (Fe(CN)6(3-/4-)) and displayed distinct electrocatalytic activity. PMID:23790187

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

    NASA Astrophysics Data System (ADS)

    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

  2. Pd-Ag Membrane Coupled to a Two-Zone Fluidized Bed Reactor (TZFBR) for Propane Dehydrogenation on a Pt-Sn/MgAl2O4 Catalyst.

    PubMed

    Medrano, José-Antonio; Julián, Ignacio; Herguido, Javier; Menéndez, Miguel

    2013-01-01

    Several reactor configurations have been tested for catalytic propane dehydrogenation employing Pt-Sn/MgAl2O4 as a catalyst. Pd-Ag alloy membranes coupled to the multifunctional Two-Zone Fluidized Bed Reactor (TZFBR) provide an improvement in propane conversion by hydrogen removal from the reaction bed through the inorganic membrane in addition to in situ catalyst regeneration. Twofold process intensification is thereby achieved when compared to the use of traditional fluidized bed reactors (FBR), where coke formation and thermodynamic equilibrium represent important process limitations. Experiments were carried out at 500-575 °C and with catalyst mass to molar flow of fed propane ratios between 15.1 and 35.2 g min mmol-1, employing three different reactor configurations: FBR, TZFBR and TZFBR + Membrane (TZFBR + MB). The results in the FBR showed catalyst deactivation, which was faster at high temperatures. In contrast, by employing the TZFBR with the optimum regenerative agent flow (diluted oxygen), the process activity was sustained throughout the time on stream. The TZFBR + MB showed promising results in catalytic propane dehydrogenation, displacing the reaction towards higher propylene production and giving the best results among the different reactor configurations studied. Furthermore, the results obtained in this study were better than those reported on conventional reactors. PMID:24958620

  3. Pd-Ag Membrane Coupled to a Two-Zone Fluidized Bed Reactor (TZFBR) for Propane Dehydrogenation on a Pt-Sn/MgAl2O4 Catalyst

    PubMed Central

    Medrano, José-Antonio; Julián, Ignacio; Herguido, Javier; Menéndez, Miguel

    2013-01-01

    Several reactor configurations have been tested for catalytic propane dehydrogenation employing Pt-Sn/MgAl2O4 as a catalyst. Pd-Ag alloy membranes coupled to the multifunctional Two-Zone Fluidized Bed Reactor (TZFBR) provide an improvement in propane conversion by hydrogen removal from the reaction bed through the inorganic membrane in addition to in situ catalyst regeneration. Twofold process intensification is thereby achieved when compared to the use of traditional fluidized bed reactors (FBR), where coke formation and thermodynamic equilibrium represent important process limitations. Experiments were carried out at 500–575 °C and with catalyst mass to molar flow of fed propane ratios between 15.1 and 35.2 g min mmol−1, employing three different reactor configurations: FBR, TZFBR and TZFBR + Membrane (TZFBR + MB). The results in the FBR showed catalyst deactivation, which was faster at high temperatures. In contrast, by employing the TZFBR with the optimum regenerative agent flow (diluted oxygen), the process activity was sustained throughout the time on stream. The TZFBR + MB showed promising results in catalytic propane dehydrogenation, displacing the reaction towards higher propylene production and giving the best results among the different reactor configurations studied. Furthermore, the results obtained in this study were better than those reported on conventional reactors. PMID:24958620

  4. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Ye, Feng; Liu, Hui; Yang, Jun

    2016-04-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction.

  5. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction

    PubMed Central

    Chen, Dong; Ye, Feng; Liu, Hui; Yang, Jun

    2016-01-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction. PMID:27079897

  6. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction.

    PubMed

    Chen, Dong; Ye, Feng; Liu, Hui; Yang, Jun

    2016-01-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd(2+) ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction. PMID:27079897

  7. Reactivity of Transition Metals (Pd, Pt, Cu, Ag, Au) toward Molecular Hydrogen Dissociation: Extended Surfaces versus Particles Supported on TiC(001) or Small Is Not Always Better and Large Is Not Always Bad

    SciTech Connect

    Rodriguez, J.A.; Gomez, T.; Florez, E.; Illas, F.

    2011-05-11

    The reactivity of Pd{sub 4}, Pt{sub 4}, Cu{sub 4}, Ag{sub 4}, and Au{sub 4} clusters supported on TiC(001) toward molecular hydrogen dissociation has been studied by means of density functional based theory and periodic models and compared to that of the (111) and (001) surfaces. Pd{sub 4} and Pt{sub 4} interact rather strongly with the TiC(001) substrate, but the interaction of molecular hydrogen with the Pd{sub 4}/TiC and Pt{sub 4}/TiC systems is also very strong. As a consequence of the substantial admetal {leftrightarrow} carbide interactions, the adsorbed H{sub 2} molecule becomes more difficult to dissociate than on the corresponding extended (111) and (001) surfaces. Here, having a small supported particle does not lead to an enhanced chemical activity. On the contrary, for the Cu{sub 4}/TiC, Ag{sub 4}/TiC, and Au{sub 4}/TiC systems the combination of the small size of the particle and the polarization induced by the underlying carbide facilitates the dissociation of the hydrogen molecule with respect to the case of the extended surfaces. Here, the reduced size effectively enhances the activity of the supported particle. Thus, our results for the M(111), M(100), and M{sub 4}/TiC(001) systems show the complex interplay that can take place among the nature of the admetal, particle size effects, and support interactions.

  8. Reactivity of Transition Metals (Pd Pt Cu Ag Au) toward Molecular Hydrogen Dissociation: Extended Surfaces versus Particles Supported on TiC(001) or Small Is Not Always Better and Large Is Not Always Bad

    SciTech Connect

    Rodriguez J. A.; Gomez T.; Florez E.; Illas F.

    2011-06-16

    The reactivity of Pd{sub 4}, Pt{sub 4}, Cu{sub 4}, Ag{sub 4}, and Au{sub 4} clusters supported on TiC(001) toward molecular hydrogen dissociation has been studied by means of density functional based theory and periodic models and compared to that of the (111) and (001) surfaces. Pd{sub 4} and Pt{sub 4} interact rather strongly with the TiC(001) substrate, but the interaction of molecular hydrogen with the Pd{sub 4}/TiC and Pt{sub 4}/TiC systems is also very strong. As a consequence of the substantial admetal {leftrightarrow} carbide interactions, the adsorbed H{sub 2} molecule becomes more difficult to dissociate than on the corresponding extended (111) and (001) surfaces. Here, having a small supported particle does not lead to an enhanced chemical activity. On the contrary, for the Cu{sub 4}/TiC, Ag{sub 4}/TiC, and Au{sub 4}/TiC systems the combination of the small size of the particle and the polarization induced by the underlying carbide facilitates the dissociation of the hydrogen molecule with respect to the case of the extended surfaces. Here, the reduced size effectively enhances the activity of the supported particle. Thus, our results for the M(111), M(100), and M{sub 4}/TiC(001) systems show the complex interplay that can take place among the nature of the admetal, particle size effects, and support interactions.

  9. LaMgX and CeMgX (X = Ga, In, Tl, Pd, Ag, Pt, Au) with ZrNiAl type structure - A systematic view on electronic structure and chemical bonding

    NASA Astrophysics Data System (ADS)

    Matar, Samir F.; Etourneau, Jean; Pöttgen, Rainer

    2015-05-01

    The intermetallic magnesium compounds LaMgX and CeMgX (X = Ga, In, Tl, Pd, Ag, Pt, Au) crystallize with the hexagonal ZrNiAl type structure, space group P 6 bar 2 m , with full Mg-X ordering. From density functional theory calculations carried out exemplarily on four representative compounds: LaMgX and CeMgX with X = Ga, Pd, significant differences were traced out as to the magnetism arising only for the Ce series leading to identify CeMgGa as an antiferromagnet in its ground state, in agreement with experiment. The bulk module magnitudes show the trend of harder transition metal based ternaries and the cohesive energies favor the X = Pd compounds versus X = Ga ones. Such features were clarified by examining the properties of chemical bonding which exhibit more directional bonds thanks to the Pd d states. Rationalizing the trends of charge transfers, negatively charged triel and transition element atoms are observed. The resulting chemical pictures assign these compounds as gallides and palladides.

  10. Why are the 3d-5d compounds CuAu and NiPt stable, whereas the 3d-4d compounds CuAg and NiPd are not

    NASA Astrophysics Data System (ADS)

    Wang, L. G.; Zunger, Alex

    2003-03-01

    We show that the existence of stable, ordered 3d-5d intermetallics CuAu and NiPt, as opposed to the unstable 3d-4d isovalent analogs CuAg and NiPd, results from relativity. First, in shrinking the equilibrium volume of the 5d element, relativity reduces the atomic size mismatch with respect to the 3d element, thus lowering the elastic packing strain. Second, in lowering the energy of the bonding 6s,p bands and raising the energy of the 5d band, relativity enhances (diminishes) the occupation of the bonding (antibonding) bands. The raising of the energy of the 5d band also brings it closer to the energy of the 3d band, improving the 3d-5d bonding.

  11. Electrical properties of thin-film structures formed by pulsed laser deposition of Au, Ag, Cu, Pd, Pt, W, Zr metals on n-6H-SiC crystal

    SciTech Connect

    Romanov, R. I.; Zuev, V. V.; Fominskii, V. Yu. Demin, M. V.; Grigoriev, V. V.

    2010-09-15

    Diode structures with ideality factors of 1.28-2.14 and potential barriers from 0.58 to 0.62 eV on the semiconductor side were formed by pulsed laser deposition of Au, Ag, Cu, Pd, Pt, W, and Zr metal films on n-6H-SiC crystal without epitaxial layer preparation. A high density of surface acceptor and donor states was formed at the metal-semiconductor interface during deposition of the laser-induced atomic flux, which violated the correlation between the potential barrier height and metal work function. The barrier heights determined from characteristic currents and capacitance measurements were in quite good agreement. For the used low-resistance semiconductor and contact elements, the sizes of majority carrier (electron) depletion regions were determined as 26-60 nm.

  12. Heterostructured Au/Pd-M (M = Au, Pd, Pt) nanoparticles with compartmentalized composition, morphology, and electrocatalytic activity.

    PubMed

    Lutz, Patrick S; Bae, In-Tae; Maye, Mathew M

    2015-10-14

    The synthesis, processing, and galvanic exchange of three heterostructured nanoparticle systems is described. The surface accessibility and redox potential of a Au/Pd-Ag dumbbell nanoparticle, where a Au/Pd core/shell region, and a silver region make up the domains, was used to prepare the new nanostructures with controlled composition, morphology, and microstructure. Results indicate that the silver domain was particularly susceptible to galvanic displacement, and was exchanged to Au/Pd-M (M = Au, Pd, Pt). Interestingly, the dumbbell morphology remained after exchange, and the silver region was transformed to hollow, parachute, or concentric domains respectively. The morphology and microstructure change was visualized via TEM and HRTEM, and the composition changes were probed via STEM-EDS imaging and XPS. The electrocatalytic activity of the Au/Pd-M towards methanol oxidation was studied, with results indicating that the Au/Pd-Pt nanoparticles had high activity attributed to the porous nature of the platinum domains. PMID:26351824

  13. Pd surface and Pt subsurface segregation in Pt1-c Pd c nanoalloys.

    PubMed

    De Clercq, A; Giorgio, S; Mottet, C

    2016-02-17

    The structure and chemical arrangement of Pt1-c Pd c nanoalloys with the icosahedral and face centered cubic symmetry are studied using Monte Carlo simulations with a tight binding interatomic potential fitted to density-functional theory calculations. Pd surface segregation from the lowest to the highest coordinated sites is predicted by the theory together with a Pt enrichment at the subsurface, whatever the structure and the size of the nanoparticles, and which subsists when increasing the temperature. The onion-shell chemical configuration is found for both symmetries and is initiated from the Pd surface segregation. It is amplified in the icosahedral symmetry and small sizes but when considering larger sizes, the oscillating segregation profile occurs near the surface on about three to four shells whatever the structure. Pd segregation results from the significant lower cohesive energy of Pd as compared to Pt and the weak ordering tendency leads to the Pt subsurface segregation. The very weak size mismatch does not prevent the bigger atoms (Pt) from occupying subsurface sites which are in compression whereas the smaller ones (Pd) occupy the central site of the icosahedra where the compression is an order of magnitude higher. PMID:26795206

  14. Pd surface and Pt subsurface segregation in Pt1-c Pd c nanoalloys

    NASA Astrophysics Data System (ADS)

    De Clercq, A.; Giorgio, S.; Mottet, C.

    2016-02-01

    The structure and chemical arrangement of Pt1-c Pd c nanoalloys with the icosahedral and face centered cubic symmetry are studied using Monte Carlo simulations with a tight binding interatomic potential fitted to density-functional theory calculations. Pd surface segregation from the lowest to the highest coordinated sites is predicted by the theory together with a Pt enrichment at the subsurface, whatever the structure and the size of the nanoparticles, and which subsists when increasing the temperature. The onion-shell chemical configuration is found for both symmetries and is initiated from the Pd surface segregation. It is amplified in the icosahedral symmetry and small sizes but when considering larger sizes, the oscillating segregation profile occurs near the surface on about three to four shells whatever the structure. Pd segregation results from the significant lower cohesive energy of Pd as compared to Pt and the weak ordering tendency leads to the Pt subsurface segregation. The very weak size mismatch does not prevent the bigger atoms (Pt) from occupying subsurface sites which are in compression whereas the smaller ones (Pd) occupy the central site of the icosahedra where the compression is an order of magnitude higher.

  15. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation

    NASA Astrophysics Data System (ADS)

    Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

    2014-03-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd80Ag20 nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system.

  16. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation

    PubMed Central

    Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

    2014-01-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd80Ag20 nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system. PMID:24608736

  17. Superconductivity in Pd, Ir, and Pt chalcogenide

    NASA Astrophysics Data System (ADS)

    Oh, Yoon Seok; Yang, Junjie; Choi, Y. J.; Hogan, A.; Horibe, Y.; Cheong, S.-W.

    2012-02-01

    Large spin-orbit coupling in materials with heavy chalcogens can result in unique quantum states or functional properties such as topological insulator, giant thermoelectric power, and superconductivity. When materials contain heavy cations in addition to heavy chalcogens, spin-orbit coupling can be further enhanced. For these reasons, we have studied the superconductivity of Pd, Ir, and Pt tellurides and selenides. In the exploration of these chalcogenides, we have focused on the competition between superconductivity and charge density wave that is associated with superlattice reflections.

  18. Why are the 3d-5d compounds CuAu and NiPt stable, whereas the 3d-4d compounds CuAg and NiPd are not*

    NASA Astrophysics Data System (ADS)

    Wang, Ligen; Zunger, Alex

    2003-03-01

    Experiments indicate that the 3d-5d compounds CuAu and NiPt have negative formation enthalpies (ΔH < 0), and thus form stable ordered compounds, whereas the analogous isovalent 3d-4d compounds CuAg and NiPd, made of elements from the same columns in the periodic table, have positive formation enthalpies (ΔH > 0) and thus phase-separate. We explain this long standing puzzle according to the relativistic effect and show, via first-principles calculations, that in binary compounds of late 3d-5d intermetallics, the inter-sublattice 3d-5d coupling is dominant. First, in shrinking the equilibrium volume of the 5d element, relativity reduces the atomic size-mismatch with respect to the 3d element, thus lowering the elastic packing strain. Second, in lowering the energy of the bonding 6s,p bands and raising the energy of the 5d band, relativity enhances (diminishes) the occupation of the bonding (antibonding) bands. The raising of the energy of the 5d band also brings it closer to the energy of the 3d band, improving the 3d-5d bonding. * Supported by DOE-SC-BES-DMS

  19. Adsorption of molecular hydrogen on Pd(Pt) decorated graphene

    NASA Astrophysics Data System (ADS)

    Adhikari, Narayan; Khaniya, Asim; Lamichhane, Saran; Pantha, Nurapati

    2015-03-01

    We have performed the first-principles based Density Functional Theory (DFT) calculations to study the stability, geometrical structures, and electronic properties of a Pd(Pt) atom adsorbed graphene to investigate the possibility of using Pd(Pt) decorated graphene as energy storage materials with reference to pristine graphene. The London dispersion forces have been incorporated by the DFT-D2 levels of calculations implemented in Quantum Espresso packages. Our findings show that Pd and Pt both adsorb on graphene at Bridge site. The electronic structures of Pd(Pt) adsorbed graphene possesses band gap opening due to breaking of the symmetry of graphene. Further we have studied the adsorption of moelcular hydrogen ((H 2) n , n = 1-7) on the Pd(Pt)-graphene system. The adatom Pd(Pt) enhances the binding energy per hydrogen molecule in Pd(Pt)-graphene system in comparison to that in the pristine graphene. The binding energy per hydrogen molecule of the adatom-graphene system decreases as the number of H 2 molecules increases and finally it saturates to 0.15 eV (0.16 eV) per hydrogen molecule for Pd-graphene (Pt-graphene) systems respectively. ICTP-NET 56/TWAS.

  20. Distributions of noble metal Pd and Pt in mesoporous silica

    NASA Astrophysics Data System (ADS)

    Arbiol, J.; Cabot, A.; Morante, J. R.; Chen, Fanglin; Liu, Meilin

    2002-10-01

    Mesoporous silica nanostructures have been synthesized and loaded with Pd and Pt catalytic noble metals. It is found that Pd forms small nanoclusters (3-5 nm) on the surface of the mesoporous structure whereas Pt impregnation results in the inclusion of Pt nanostructures within the silica hexagonal pores (from nanoclusters to nanowires). It is observed that these materials have high catalytic properties for CO-CH4 combustion, even in a thick film form. In particular, results indicate that the Pt and Pd dispersed in mesoporous silica are catalytically active as a selective filter for gas sensors.

  1. Interaction of CO with PtxAg1-x/Pt(111) surface alloys: More than dilution by Ag atoms

    NASA Astrophysics Data System (ADS)

    Schüttler, K. M.; Mancera, L. A.; Diemant, T.; Groß, A.; Behm, R. J.

    2016-08-01

    We have investigated CO adsorption on structurally well-defined PtxAg1-x/Pt(111) surface alloys, combining temperature-programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRRAS) as well as density functional theory (DFT) based calculations. This is part of a systematic approach including previous studies of CO adsorption on closely related Pt(111)- and Pd(111)-based surface alloys. Following changes in the adsorption properties with increasing Ag content and correlating them with structural changes allow us to assign desorption features to specific adsorption sites/ensembles identified in previous scanning tunneling microscopy (STM) measurements, and thus to identify and separate contributions from different effects such as geometric ensemble effects and electronic ligand/strain effects. DFT calculations give further insight into the nature of the metal-CO bond on these bimetallic sites. Most prominently, the growth of a new CO desorption feature at higher temperature (~ 550 K) in the TPD spectra of Ag-rich surface alloys, which is unique for the group of Pt(111)- and Pd(111)-based surface alloys, is attributed to CO adsorption on Pt atoms surrounded by a Ag-rich neighborhood. Adsorption on these sites manifests in an IR band down-shifted to significantly lower wave number. Systematic comparison of the present results with previous findings for CO adsorption on the related Pt(111)- and Pd(111)-based surface alloys gains a detailed insight into general trends in the adsorption behavior of bimetallic surfaces.

  2. Spectroscopy and electronic structure of jet-cooled NiPd and PdPt

    NASA Astrophysics Data System (ADS)

    Taylor, Scott; Spain, Eileen M.; Morse, Michael D.

    1990-03-01

    Resonant two-photon ionization spectroscopy of jet-cooled NiPd and PdPt has revealed a dense vibronic spectrum for NiPd and a much more sparse spectrum for PdPt. Four vibrational progressions have been identified for NiPd, and three have been located for PdPt. High resolution investigations of NiPd have established a ground state bond length of r″0 =2.242±0.005 Å with Ω″=2. The observed spectra have been used to bracket the ionization potentials, giving IP(NiPd)=7.18±0.76 eV and IP(PdPt)=8.27±0.38 eV. In contrast to previous work on Ni2, NiPt, and Pt2, no abrupt onset of rapid predissociation is observed for either NiPd or PdPt. A discussion of this result in terms of the expected potential energy curves for the palladium-containing diatomics is presented, which when combined with the frequencies of the highest energy vibronic bands observed yields estimates of D0(NiPd)≊1.46 eV and D0(PdPt)≊1.98 eV. The lack of observable vibronic transitions in Pd2 above 11 375 cm-1 places D0(Pd2) below 1.41 eV, in agreement with Knudsen effusion mass spectrometry. Finally a comparison of the platinum group dimers and the coinage metal dimers is given, demonstrating the increasing importance of d-orbital contributions to the bonding in the platinum group dimers as one moves down the periodic table. The anomalous behavior of the palladium-containing diatomics is also discussed in terms of the highly stable 4d105s0, 1S0 ground state of atomic palladium.

  3. Heterostructured Au/Pd-M (M = Au, Pd, Pt) nanoparticles with compartmentalized composition, morphology, and electrocatalytic activity

    NASA Astrophysics Data System (ADS)

    Lutz, Patrick S.; Bae, In-Tae; Maye, Mathew M.

    2015-09-01

    The synthesis, processing, and galvanic exchange of three heterostructured nanoparticle systems is described. The surface accessibility and redox potential of a Au/Pd-Ag dumbbell nanoparticle, where a Au/Pd core/shell region, and a silver region make up the domains, was used to prepare the new nanostructures with controlled composition, morphology, and microstructure. Results indicate that the silver domain was particularly susceptible to galvanic displacement, and was exchanged to Au/Pd-M (M = Au, Pd, Pt). Interestingly, the dumbbell morphology remained after exchange, and the silver region was transformed to hollow, parachute, or concentric domains respectively. The morphology and microstructure change was visualized via TEM and HRTEM, and the composition changes were probed via STEM-EDS imaging and XPS. The electrocatalytic activity of the Au/Pd-M towards methanol oxidation was studied, with results indicating that the Au/Pd-Pt nanoparticles had high activity attributed to the porous nature of the platinum domains.The synthesis, processing, and galvanic exchange of three heterostructured nanoparticle systems is described. The surface accessibility and redox potential of a Au/Pd-Ag dumbbell nanoparticle, where a Au/Pd core/shell region, and a silver region make up the domains, was used to prepare the new nanostructures with controlled composition, morphology, and microstructure. Results indicate that the silver domain was particularly susceptible to galvanic displacement, and was exchanged to Au/Pd-M (M = Au, Pd, Pt). Interestingly, the dumbbell morphology remained after exchange, and the silver region was transformed to hollow, parachute, or concentric domains respectively. The morphology and microstructure change was visualized via TEM and HRTEM, and the composition changes were probed via STEM-EDS imaging and XPS. The electrocatalytic activity of the Au/Pd-M towards methanol oxidation was studied, with results indicating that the Au/Pd-Pt nanoparticles had

  4. Morphology and structural stability of Pt-Pd bimetallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Tun-Dong; Zheng, Ji-Wen; Shao, Gui-Fang; Fan, Tian-E.; Wen, Yu-Hua

    2015-03-01

    The morphologies and structures of Pt-Pd bimetallic nanoparticles determine their chemical and physical properties. Therefore, a fundamental understanding of their morphologies and structural stabilities is of crucial importance to their applications. In this article, we have performed Monte Carlo simulations to systematically explore the structural stability and structural features of Pt-Pd alloy nanoparticles. Different Pt/Pd ratios, and particle sizes and shapes were considered. The simulated results reveal that the truncated octahedron, which has the remarkably lowest energy among all the considered shapes, exhibits the best structural stability while the tetrahedron has the worst invariably. Furthermore, all the structures of Pt-Pd alloy nanoparticles present Pd-rich in the outmost layer but Pt-rich in the sub-outmost layer. Especially, atomic distribution and chemical short-range order parameter were applied to further characterize the structural features of Pt-Pd alloy nanoparticles. This study provides a significant insight not only into the structural stability of Pt-Pd alloy nanoparticles with different compositions, and particle sizes and shapes but also to the design of bimetallic nanoparticles. Project supported by the National Natural Science Foundation of China (Grant No. 51271156) and the Natural Science Foundation of Fujian Province, China (Grant Nos. 2013J01255 and 2013J06002).

  5. Electronic Structure and Phase Stability of PdPt Nanoparticles.

    PubMed

    Ishimoto, Takayoshi; Koyama, Michihisa

    2016-03-01

    To understand the origin of the physicochemical nature of bimetallic PdPt nanoparticles, we theoretically investigated the phase stability and electronic structure employing the PdPt nanoparticles models consisting of 711 atoms (ca. 3 nm). For the Pd-Pt core-shell nanoparticle, the PdPt solid-solution phase was found to be a thermodynamically stable phase in the nanoparticle as the result of difference in surface energy of Pd and Pt nanoparticles and configurational entropy effect, while it is well known that the Pd and Pt are the immiscible combination in the bulk phase. The electronic structure of nanoparticles is conducted to find that the electron transfer occurs locally within surface and subsurface layers. In addition, the electron transfer from Pd to Pt at the interfacial layers in core-shell nanoparticles is observed, which leads to unique geometrical and electronic structure changes. Our results show a clue for the tunability of the electronic structure of nanoparticles by controlling the arrangement in the nanoparticles. PMID:26862885

  6. Adsorbate-Induced Segregation in a PdAg Membrane Model System: Pd3Ag(1 1 1)

    SciTech Connect

    Svenum, I. H.; Herron, Jeffrey A.; Mavrikakis, Manos; Venvik, H. J.

    2012-10-15

    Thin PdAg alloy membranes with 20–25% Ag are being developed for hydrogen separation technology. Despite many investigations on such membranes as well as representative experimental and theoretical model systems, unresolved issues remain concerning the effect of the alloy surface structure and composition on adsorption and vice versa. Therefore, the interaction between hydrogen, carbon monoxide or oxygen with the surface of a PdAg model alloy was studied using periodic self-consistent density functional theory (DFT-GGA) calculations. In particular, the adsorption structure, coverage dependence and possible adsorption-induced segregation phenomena were addressed using Pd3Ag(1 1 1) model surfaces with varying degrees of surface segregation. In agreement with previous experimental and theoretical investigations, we predict Ag surface termination to be energetically favorable in vacuum. The segregation of Ag is then reversed upon adsorption of H, CO or O. For these adsorbates, the binding is strongest on Pd three-fold hollow sites, and hence complete Pd termination is favored at high coverage of H or CO, while 25% Ag may remain under oxygen because of the lower O-saturation coverage. CO adsorption provides a somewhat stronger driving force for Pd segregation when compared to H, and this may have implications with respect to permeation properties of PdAg alloy surfaces. Our predictions for high coverage are particularly relevant in underlining the importance of segregation phenomena to the hydrogen transport properties of thin PdAg alloy membranes.

  7. Microstructure and electronic behavior of PtPd@Pt core-shell nanowires

    SciTech Connect

    Han, Wei-Qiang; Su, Dong; Murphy, Michael; Ward, Matthew; Sham, Tsun-Kong; Wu, Lijun; Zhu, Yimei; Hu, Yongfeng; Aoki, Toshihiro

    2010-07-19

    PtPd{at}Pt core-shell ultrathin nanowires were prepared using a one-step phase-transfer approach. The diameters of the nanowires range from 2 to 3 nm, and their lengths are up to hundreds of nanometers. Line scanning electron energy loss spectra showed that PtPd bimetallic nanowires have a core-shell structure, with a PtPd alloy core and a Pt monolayer shell. X-ray absorption near edge structure (XANES) spectra reveal that a strong Pt-Pd interaction exists in this nanowire system in that there is PtPd alloying and/or interfacial interaction. Extended x-ray absorption fine structures (EXAFS) further confirms the PtPd@Pt core-shell structure. The bimetallic nanowires were determined to be face-centered cubic structures. The long-chain organic molecules of n-dodecyl trimethylammonium bromide and octadecylamine, used as surfactants during synthesis, were clearly observed using aberration-corrected TEM operated at 80 KV. The interaction of Pt and surfactants was also revealed by EXAFS.

  8. Hollow raspberry-like PdAg alloy nanospheres: High electrocatalytic activity for ethanol oxidation in alkaline media

    NASA Astrophysics Data System (ADS)

    Peng, Cheng; Hu, Yongli; Liu, Mingrui; Zheng, Yixiong

    2015-03-01

    Palladium-silver (PdAg) alloy nanospheres with unique structure were prepared using a one-pot procedure based on the galvanic replacement reaction. Their electrocatalytic activity for ethanol oxidation in alkaline media was evaluated. The morphology and crystal structure of the samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Electrochemical characterization techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical performance of the PdAg alloy nanospheres. The SEM and TEM images showed that the PdAg alloy nanospheres exhibit a hierarchical nanostructure with hollow interiors and porous walls. Compared to the commercial Pd/C catalyst, the as-prepared PdAg alloy nanospheres exhibit superior electrocatalytic activity and stability towards ethanol electro-oxidation in alkaline media, showing its potential as a new non-Pt electro-catalyst for direct alcohol fuel cells (DAFCs).

  9. A pathway for the growth of core-shell Pt-Pd nanoparticles

    SciTech Connect

    Narula, Chaitanya Kumar; Yang, Xiaofan; Li, Chen; Pennycook, Stephen J; Lupini, Andrew R

    2015-10-12

    In this study, the aging of both Pt-Pd nanoparticles and core-shell Pt-Pd nanoparticles has been reported to result in alloying of Pt with Pd. In comparison to monometallic Pt catalysts, the growth of Pd-Pt bimetallics is slower; however, the mechanism of growth of particles and the mechanism by which Pd improves the hydrothermal durability of bimetallic Pd-Pt particles remains uncertain. In our work on hydrothermal aging of core-shell Pt-Pd nanoparticles, synthesized by solution methods, with varying Pd:Pt ratio of 1:4, 1:1, and 4:1, we compare the growth of core-shell Pt-Pd nanoparticles and find that particles grow by migrating and joining together. The unique feature of the observed growth is that Pd shells from both particles open up and join, allowing the cores to merge. At high temperatures, alloying occurs in good agreement with reports by other workers.

  10. Mesoporous Trimetallic PtPdRu Spheres as Superior Electrocatalysts.

    PubMed

    Jiang, Bo; Ataee-Esfahani, Hamed; Li, Cuiling; Alshehri, Saad M; Ahamad, Tansir; Henzie, Joel; Yamauchi, Yusuke

    2016-05-17

    Mesoporous Trimetallic PtPdRu Spheres with well-defined spherical morphology and uniformly sized pores were synthesized in an aqueous solution using ascorbic acid as the reducing agent and triblock copolymer F127 as the pore directing agent. These mesoporous PtPdRu spheres exhibited enhanced electrocatalytic activity compared to commercial Pt black, resulting in a ∼4.9 times improvement in mass activity for the methanol oxidation reaction. The excellent electrocatalytic activity and stability are due to the unique mesoporous architecture and electronic landscape between different elements. PMID:27072776

  11. Methanol oxidation on Pd/Pt(poly) in alkaline solution

    NASA Astrophysics Data System (ADS)

    Maksic, A.; Rakocevic, Z.; Smiljanic, M.; Nenadovic, M.; Strbac, S.

    2015-01-01

    Bimetallic electrodes prepared by Pd nanoislands spontaneously deposited on polycrystalline platinum, Pt(poly), at submonolayer coverage were explored for methanol oxidation in alkaline media. Characterization of obtained Pd/Pt(poly) nanostructures was performed ex situ by AFM imaging, spectroscopic ellipsometry and by X-ray photoelectron spectroscopy. In situ characterization of the obtained electrodes and subsequent methanol oxidation measurements were performed by cyclic voltammetry in 0.1 M KOH. Platinum surface with 35% Pd coverage exhibited the highest catalytic activity for methanol oxidation in alkaline media, exceeding those of bare Pt and Pd. Both synergistic and electronic effects are responsible for such enhanced catalysis. The origin of the synergistic effect and possible reaction pathways for methanol oxidation were discussed taking into account the activity of obtained bimetallic electrodes for the oxidation of CO and formaldehyde, as the most probable reaction intermediates.

  12. Shape-directional growth of Pt and Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Leong, G. Jeremy; Ebnonnasir, Abbas; Schulze, Maxwell C.; Strand, Matthew B.; Ngo, Chilan; Maloney, David; Frisco, Sarah L.; Dinh, Huyen N.; Pivovar, Bryan; Gilmer, George H.; Kodambaka, Suneel; Ciobanu, Cristian V.; Richards, Ryan M.

    2014-09-01

    The design and synthesis of shape-directed nanoscale noble metal particles have attracted much attention due to their enhanced catalytic properties and the opportunities to study fundamental aspects of nanoscale systems. As such, numerous methods have been developed to synthesize crystals with tunable shapes, sizes, and facets by adding foreign species that promote or restrict growth on specific sites. Many hypotheses regarding how and why certain species direct growth have been put forward, however there has been no consensus on a unifying mechanism of nanocrystal growth. Herein, we develop and demonstrate the capabilities of a mathematical growth model for predicting metal nanoparticle shapes by studying a well known procedure that employs AgNO3 to produce {111} faceted Pt nanocrystals. The insight gained about the role of auxiliary species is then utilized to predict the shape of Pd nanocrystals and to corroborate other shape-directing syntheses reported in literature. The fundamental understanding obtained herein by combining modeling with experimentation is a step toward computationally guided syntheses and, in principle, applicable to predictive design of the growth of crystalline solids at all length scales (nano to bulk).The design and synthesis of shape-directed nanoscale noble metal particles have attracted much attention due to their enhanced catalytic properties and the opportunities to study fundamental aspects of nanoscale systems. As such, numerous methods have been developed to synthesize crystals with tunable shapes, sizes, and facets by adding foreign species that promote or restrict growth on specific sites. Many hypotheses regarding how and why certain species direct growth have been put forward, however there has been no consensus on a unifying mechanism of nanocrystal growth. Herein, we develop and demonstrate the capabilities of a mathematical growth model for predicting metal nanoparticle shapes by studying a well known procedure that

  13. Anion-exchange separation of Pt and Pd using perchloric and hydrochloric acid solutions

    USGS Publications Warehouse

    Petrie, R.K.; Morgan, J.W.

    1982-01-01

    On Biorad Ag-1X8 anion-exchange resin (200-400 mesh), Pd and Pt may be separated from one another by elution with 0.2M HClO4, and 5M HClO4, respectively. If present, Au may be retained by making the elutriants 0.003M in HCl. Alternatively, reduction by H2SO3 enables elution of Pt2+ with 6M HCl before recovery of Pd2+ with 0.2M HClO4??Ir4+ is reduced to Ir3+ by H2SO3 and may be eluted ahead of Pt2+ by 2M HCl. ?? 1982 Akade??miai Kiado??.

  14. The Mechanism of Direct Formic Acid Fuel Cell Using Pd, Pt and Pt-Ru

    NASA Astrophysics Data System (ADS)

    Kamiya, Nobuyuki; Liu, Yan; Mitsushima, Shigenori; Ota, Ken-Ichiro; Tsutsumi, Yasuyuki; Ogawa, Naoya; Kon, Norihiro; Eguchi, Mika

    The electro-oxidation of formic acid, 2-propanol and methanol on Pd black, Pd/C, Pt-Ru/C and Pt/C has been investigated to clear the reaction mechanism. It was suggested that the formic acid is dehydrogenated on Pd surface and the hydrogen is occluded in the Pd lattice. Thus obtained hydrogen acts like pure hydrogen supplied from the outside and the cell performance of the direct formic acid fuel cell showed as high as that of a hydrogen-oxygen fuel cell. 2-propanol did not show such dehydrogenation reaction on Pd catalyst. Platinum and Pt-Ru accelerated the oxidation of C-OH of 2-propanol and methanol. Slow scan voltammogram (SSV) and chronoamperometry measurements showed that the activity of formic acid oxidation increased in the following order: Pd black > Pd 30wt.%/C > Pt50wt.%/C > 27wt.%Pt-13wt.%Ru/C. A large oxidation current for formic acid was found at a low overpotential on the palladium electrocatalysts. These results indicate that formic acid is mainly oxidized through a dehydrogenation reaction. For the oxidation of 2-propanol and methanol, palladium was not effective, and 27wt.%Pt-13wt.%Ru/C showed the best oxidation activity.

  15. Alumina supported model Pd Ag catalysts: A combined STM, XPS, TPD and IRAS study

    NASA Astrophysics Data System (ADS)

    Khan, N. A.; Uhl, A.; Shaikhutdinov, S.; Freund, H.-J.

    2006-05-01

    The bimetallic Pd-Ag model catalysts were prepared by physical vapor deposition on thin alumina films. The morphology and structure of the Pd-Ag particles were studied by STM, XPS, and by TPD and IRAS of CO. The results showed the formation of true alloy particles with Ag segregated at the surface. The addition of Ag first suppresses the most strongly bonded CO on threefold hollow sites of Pd. With further increasing Ag coverage, only isolated Pd atoms surrounded by Ag atoms are likely present on the surface. The results on CO adsorption suggest that the model Pd-Ag system mimics the structure of the real Pd-Ag catalysts.

  16. Study of coordination environments around Pd and Pt in a Pd-core Pt-shell nanoparticle during heating

    NASA Astrophysics Data System (ADS)

    Nishimura, Y. F.; Hamaguchi, T.; Yamaguchi, S.; Takagi, H.; Dohmae, K.; Nonaka, T.; Nagai, Y.

    2016-05-01

    Local coordination environments around Pd and Pt in a Pd-core Pt-shell nanoparticle (NP) at temperatures ranging from 473 to 873 K was evaluated by utilizing in situ XAFS measurement technique to investigate the temperature range in which a core-shell structure is preserved. The core-shell structure was considered to be kept up to 673 K and start to change at about 773 K. Heating to 873 K accelerated atomic mixing in the core-shell NPs. Catalytic properties of the present Pd-core Pt-shell NP are available in the stoichiometric C3H6-O2 atmosphere at temperatures less than 773 K at most.

  17. Shape and Composition Effects on Photocatalytic Hydrogen Production for Pt-Pd Alloy Cocatalysts.

    PubMed

    Luo, Muhua; Lu, Pan; Yao, Weifeng; Huang, Cunping; Xu, Qunjie; Wu, Qiang; Kuwahara, Yasutaka; Yamashita, Hiromi

    2016-08-17

    The shape and composition effects of platinum-palladium (Pt-Pd) alloy nanoparticle cocatalysts on visible-light photocatalytic hydrogen evolution from an aqueous ammonium sulphite solution have been reported and discussed. The activity of Pt-Pd nanoparticles loaded Pt-Pd/CdS photocatalysts are affected based on both the Pt-Pd alloy nanoparticles' shape and their compositions. In this research, two shapes of Pt-Pd nanoparticles have been studied. One is Pt-Pd nanocubes enclosed by {100} crystal planes and the other is nano-octahedra covered with {111} crystal facets. Results show that the photocatalytic turnover frequency (TOF), defined as moles of hydrogen produced per surface mole of Pt-Pd metal atom per second, for Pt-Pd nanocubes/CdS (Pt-Pd NCs/CdS) photocatalyst can be 3.4 times more effective than Pt-Pd nano-octahedra/CdS (Pt-Pd NOTa/CdS) nanocomposite photocatalyst. Along with the shape effect, the atomic ratio of Pt to Pd can also impact the efficiency of Pt-Pd/CdS photocatalysts. When the Pt to Pd atomic ratio changes from 1:0 to about 2:1, the rate of hydrogen production increases from 900 μmol/h for Pt NCs/CdS catalyst to 1837 μmol/h for Pt-Pd (2:1) NCs/CdS photocatalyst-a 104% rate increase. This result suggests that the 33 mol % of more expensive Pt can be replaced with less costly Pd, resulting in a more than 100% hydrogen production rate increase. The finding of this research will lead to the research and development of highly effective catalysts for photocatalytic hydrogen production using solar photonic energy. PMID:27439590

  18. Pt skin on Pd-Co-Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR

    NASA Astrophysics Data System (ADS)

    Xiao, Weiping; Zhu, Jing; Han, Lili; Liu, Sufen; Wang, Jie; Wu, Zexing; Lei, Wen; Xuan, Cuijuan; Xin, Huolin L.; Wang, Deli

    2016-08-01

    Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a highly active, durable, carbon supported, and monolayer Pt coated Pd-Co-Zn nanoparticle is synthesized via a simple impregnation-reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition-activity volcano curve for the Pd-Co-Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd8CoZn/C nanoparticles show a substantial enhancement in both the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd8CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N2-saturated 0.1 M HClO4 solution, Pd8CoZn@Pt/C shows improved mass activity (2.62 A mg-1Pt) and specific activity (4.76 A m-2total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O2-saturated 0.1 M HClO4 solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. The results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation.Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a highly active, durable, carbon supported, and monolayer Pt coated Pd-Co-Zn nanoparticle is synthesized via a simple impregnation-reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition-activity volcano curve for the Pd-Co-Zn nanoparticles and determined that Pd : Co : Zn = 8

  19. A photoemission study of Pd ultrathin films on Pt(111)

    SciTech Connect

    Mun, Bongjin Simon; Lee, Choongman; Stamenkovic, Vojislav; Markovic, Nenad M.; Ross Jr., Philip N.

    2005-05-11

    The origin of surface core-level shift (SCLS) of Pd thin films on Pt(111) substrate is investigated. At sub-monolayer coverage of Pd thin films, the splitting of Pd 3d core level peaks indicate the contribution of both initial and final-state of photo-ionization processes while there is almost no change on valence band (VB) spectra. When the coverage of Pd reaches to single monolayer, the final-state relaxation effect on the Pd 3d vanishes and only the initial-state effect, a negative SCLS, is present. Also, the VB spectrum at Pd monolayer films shows a clear band narrowing, that is the origin of the negative SCLS at monolayer coverage. As the Pd coverage is increased to more than monolayer thickness, the Pd 3d peaks start to show the surface layer contribution from second and third layers, positive SCLS, and the VB spectrum shows even narrower band width, possibly due to the formation of surface states and strained effect of Pd adlayers on top of the first pseudomorphic layer.

  20. Annealing effect of ultrathin Ag films on Ni /Pt(111)

    NASA Astrophysics Data System (ADS)

    Su, C. W.; Yo, H. Y.; Chen, Y. J.; Shern, C. S.

    2005-06-01

    The epitaxial growth and alloy formation of Ag-capped layer on Ni /Pt(111) surface were investigated using Auger electron spectroscopy, ultraviolet photoelectron spectroscopy, and low-energy electron diffraction. The growth of Ag on one ML Ni /Pt(111) transforms from layer-by-layer mode into three-dimensional island mode after the growth of one atomic monolayer of Ag. The starting temperature for the alloy formation of Ni-Pt is dependent of the thickness of Ni films. The interface compositions after the high-temperature annealing were studied with the depth-profile analysis of Ar ion sputtering.

  1. Effects of Ag addition on FePt L10 ordering transition: A direct observation of ordering transition and Ag segregation in FePtAg alloy films

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Gao, Tenghua; Yu, Youxing

    2015-12-01

    FePt and (FePt)91.2Ag8.8 alloy films were deposited by magnetron sputtering. The average coercivity of (FePt)91.2Ag8.8 films reaches 8.51 × 105 A/m, which is 0.63 × 105 A/m higher than that of the corresponding FePt films. Ag addition effectively promotes the FePt L10 ordering transition at a relatively low annealing temperature of 400 °C. The promotion mechanism was investigated by using in situ high-resolution transmission electron microscopy (HRTEM) and ex situ X-ray absorption fine structure (XAFS). The concurrence of ordering transition and Ag segregation in FePtAg alloy films was first observed by using in situ heating HRTEM. The time-resolved evolution reveals more details on the role of Ag addition in FePt low-temperature ordering. Ex situ XAFS results further confirm that Ag replaces Fe sites in the as-deposited films and segregates from FePt-Ag solid solution phase through annealing at elevated temperatures. The segregation of Ag atoms leaves vacancies in the grain. The vacancy formation is believed to accelerate the diffusion of Fe and Pt atoms, which is critical for the L10 ordering transition.

  2. Monodispersed bimetallic PdAg nanoparticles with twinned structures: formation and enhancement for the methanol oxidation.

    PubMed

    Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

    2014-01-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd₈₀Ag₂₀, Pd₆₅Ag₃₅ and Pd₄₆Ag₅₄ can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd₈₀Ag₂₀ nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system. PMID:24608736

  3. Magnetic properties and microstructure of FePtB, FePt(B-Ag) granular films

    NASA Astrophysics Data System (ADS)

    Tsai, Jai-Lin; Huang, Jian-Chiang; Tai, Hsueh-Wei; Tsai, Wen-Chieh; Lin, Yi-Cheng

    2013-03-01

    Multilayers [FePt(1 nm)/B(t nm)]10 (t=0.05-0.6) were alternately deposited on a glass substrate and subsequently annealed by the rapid thermal process (RTP) at 800 °C for 3 min. After RTP, FePt and B layers intermix to form the FePtB film with (0 0 1) texture. The ordering degree of FePt was slightly increased with doped B. The (Fe-Pt)100-xBx (x=0, 5, 10) films show perpendicular magnetization and the minor FeB phase was indexed in isotropic (Fe-Pt)100-xBx (x=30, 40, 60) films. By adding Ag into (Fe-Pt)95B5 film, the ordering degree was slightly increased in (Fe-Pt)95(B0.9Ag0.1)5 film. In (Fe-Pt)100-xBx (x=5, 10) and (Fe-Pt)95(B0.9Ag0.1)5 granular films, the intermixed B or Ag atoms were diffused among FePt grain boundaries to isolate and refine FePt grains uniformly with average grain sizes of 20, 15, and 6.7 nm, respectively.

  4. Pt skin on Pd-Co-Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR.

    PubMed

    Xiao, Weiping; Zhu, Jing; Han, Lili; Liu, Sufen; Wang, Jie; Wu, Zexing; Lei, Wen; Xuan, Cuijuan; Xin, Huolin L; Wang, Deli

    2016-08-21

    Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a highly active, durable, carbon supported, and monolayer Pt coated Pd-Co-Zn nanoparticle is synthesized via a simple impregnation-reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition-activity volcano curve for the Pd-Co-Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd8CoZn/C nanoparticles show a substantial enhancement in both the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd8CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N2-saturated 0.1 M HClO4 solution, Pd8CoZn@Pt/C shows improved mass activity (2.62 A mg(-1)Pt) and specific activity (4.76 A m(-2)total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O2-saturated 0.1 M HClO4 solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. The results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation. PMID:27445114

  5. Synthesis of bimetallic Pt-Pd core-shell nanocrystals and their high electrocatalytic activity modulated by Pd shell thickness.

    PubMed

    Li, Yujing; Wang, Zhi Wei; Chiu, Chin-Yi; Ruan, Lingyan; Yang, Wenbing; Yang, Yang; Palmer, Richard E; Huang, Yu

    2012-02-01

    Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50 mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more resistant to the CO poisoning than Pt NCs and Pt black. It is also demonstrated that the bimetallic Pt-Pd core-shell NCs can enhance the current density of the methanol oxidation reaction, lowering the over-potential by 35 mV with respect to the Pt core NCs. Further investigation reveals that the Pd/Pt ratio of 1/3, which corresponds to nearly monolayer Pd deposition on Pt core NCs, gives the highest oxidation current density and lowest over-potential. This study shows for the first time the systematic investigation of effects of Pd atomic shells on Pt-Pd bimetallic nanocatalysts, providing valuable guidelines for designing high-performance catalysts for fuel cell applications. PMID:22159178

  6. Large faceted Pd nanocrystals supported small Pt nanoparticles as highly durable electrocatalysts for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Zhang, Geng; Lu, Wangting; Cao, Longsheng; Qin, Xiaoping; Ding, Fei; Tang, Shun; Shao, Zhi-Gang; Yi, Baolian

    2016-09-01

    The reduction of Pt content together with the improvement of the durability of the catalyst for oxygen reduction reaction (ORR) is required to the large-scale commercialization of proton exchange membrane fuel cells. In this work, a novel ORR catalyst consisting of large Pd nanocrystal as the core with small Pt nanoparticles supported on the Pd core is prepared by a facile one-step synthesis method. The Pd substrate is presented in the form of well-defined cuboctahedrons and icosahedrons. The type of metal precursors and Pt/Pd molar ratio are important factors to obtain this Pd-supporting-Pt structure. The Pd2-s-Pt1 catalyst with a nominal Pt/Pd atomic ratio at 1/2 shows improved ORR activity: its mass specific activity and area specific activity is 2.5 and 3.5 times that of commercial Pt/C, respectively. More importantly, the Pd2-s-Pt1 catalyst demonstrates outstanding durability against potential cycling which can be ascribed to the slow dissolution of Pd core and the structure transformation from Pd@Pt to hollow PdPt alloyed nanocages. This exciting result provides a new pathway to the design of ORR catalyst with excellent durability.

  7. Controllable galvanic synthesis of triangular Ag-Pd alloy nanoframes for efficient electrocatalytic methanol oxidation.

    PubMed

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Yu, Sijia; Chen, Junze; Liao, Yusen; Xue, Can

    2015-06-01

    Triangular Ag-Pd alloy nanoframes were successfully synthesized through galvanic replacement by using Ag nanoprisms as sacrificial templates. The ridge thickness of the Ag-Pd alloy nanoframes could be readily tuned by adjusting the amount of the Pd source during the reaction. These obtained triangular Ag-Pd alloy nanoframes exhibit superior electrocatalytic activity for the methanol oxidation reaction as compared with the commercial Pd/C catalyst due to the alloyed Ag-Pd composition as well as the hollow-framed structures. This work would be highly impactful in the rational design of future bimetallic alloy nanostructures with high catalytic activity for fuel cell systems. PMID:25925988

  8. Deactivation Mechanisms of Pt/Pd-based Diesel Oxidation Catalysts

    SciTech Connect

    Wiebenga, Michelle H.; Kim, Chang H.; Schmieg, Steven J.; Oh, Se H.; Brown, David B.; Kim, Do Heui; Lee, Jong H.; Peden, Charles HF

    2012-04-30

    Currently precious metal-based diesel oxidation catalysts (DOC) containing platinum (Pt) and palladium (Pd) are most commonly used for the oxidation of hydrocarbon and NO in diesel exhaust hydrocarbon oxidation. The present work has been carried out to investigate the deactivation mechanisms of the DOC from its real-world vehicle operation by coupling its catalytic activity measurements with surface characterization including x-ray diffraction, transmission electron microscopy, and x-ray photoelectron spectroscopy. A production Pt-Pd DOC was obtained after being aged on a vehicle driven for 135,000 miles in order to study its deactivation behavior. The performance of the vehicle-aged part was correlated with that of the simulated hydrothermal lab aged sample assuming that Pt-Pd sintering plays a major role in irreversible catalyst deactivation. In addition to the hydrothermal sintering, the deterioration of hydrocarbon and NO oxidation performance was caused by surface poisoning. The role of the various aging factors in determining long-term performance in mobile applications will be discussed.

  9. Enhanced hydrogenation and reduced lattice distortion in size selected Pd-Ag and Pd-Cu alloy nanoparticles

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Kulriya, P. K.; Khan, S. A.

    2013-10-21

    Important correlation between valence band spectra and hydrogenation properties in Pd alloy nanoparticles is established by studying the properties of size selected and monocrystalline Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles. The X-ray photoelectron spectroscopy and elastic recoil detection analysis show that size induced Pd4d centroid shift is related to enhanced hydrogenation with H/Pd ratio of 0.57 and 0.49 in Pd-Ag and Pd-Cu nanoparticles in comparison to reported bulk values of 0.2 and 0.1, respectively. Pd-alloy nanoparticles show lower hydrogen induced lattice distortion. The reduced distortion and higher hydrogen reactivity of Pd-alloy nanoparticles is important for numerous hydrogen related applications.

  10. High-temperature oxidation of Pt-45Pd-10Rh

    SciTech Connect

    Graham, G.W.; Potter, T.J.; Weber, W.H.; Gandhi, H.S.

    1988-06-01

    The surfaces of Pt-45Pd-10Rh foils oxidized over the range 875-1075 K in a 20% O/sub 2/-Ar mixture at atmospheric pressure were examined by Auger electron, X-ray photoelectron, and Raman spectroscopy. The composition of the oxide formed on the surface was found to vary with temperature from predominantly PdO at 875 K to PdRhO/sub 2/ at 1075 K. Only a few atomic percent Pt was observed, present in both the metallic and (apparently) + 1 oxidation states at 875 K and in the metallic state at 1075 K. The formation of PdRhO/sub 2/ (and no Rh/sub 2/O/sub 3/) at 1075 K was found to persist upon reoxidation following a low-temperature reduction cycle in which the increased Rh concentration on the surface was retained. An oxidation-induced Rh enrichment of the surface of the alloy foil beyond 50 at.% does not appear likely within the temperature/pressure regime investigated.

  11. Highly Active Carbon Supported Pd-Ag Nanofacets Catalysts for Hydrogen Production from HCOOH.

    PubMed

    Wang, Wenhui; He, Ting; Liu, Xuehua; He, Weina; Cong, Hengjiang; Shen, Yangbin; Yan, Liuming; Zhang, Xuetong; Zhang, Jinping; Zhou, Xiaochun

    2016-08-17

    Hydrogen is regarded as a future sustainable and clean energy carrier. Formic acid is a safe and sustainable hydrogen storage medium with many advantages, including high hydrogen content, nontoxicity, and low cost. In this work, a series of highly active catalysts for hydrogen production from formic acid are successfully synthesized by controllably depositing Pd onto Ag nanoplates with different Ag nanofacets, such as Ag{111}, Ag{100}, and the nanofacet on hexagonal close packing Ag crystal (Ag{hcp}). Then, the Pd-Ag nanoplate catalysts are supported on Vulcan XC-72 carbon black to prevent the aggregation of the catalysts. The research reveals that the high activity is attributed to the formation of Pd-Ag alloy nanofacets, such as Pd-Ag{111}, Pd-Ag{100}, and Pd-Ag{hcp}. The activity order of these Pd-decorated Ag nanofacets is Pd-Ag{hcp} > Pd-Ag{111} > Pd-Ag{100}. Particularly, the activity of Pd-Ag{hcp} is up to an extremely high value, i.e., TOF{hcp} = 19 000 ± 1630 h(-1) at 90 °C (lower limit value), which is more than 800 times higher than our previous quasi-spherical Pd-Ag alloy nanocatalyst. The initial activity of Pd-Ag{hcp} even reaches (3.13 ± 0.19) × 10(6) h(-1) at 90 °C. This research not only presents highly active catalysts for hydrogen generation but also shows that the facet on the hcp Ag crystal can act as a potentially highly active catalyst. PMID:27454194

  12. Enhanced electrocatalytic performance of Pt monolayer on nanoporous PdCu alloy for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Hou, Linxi; Qiu, Huajun

    2012-10-01

    By selectively dealloying Al from PdxCu20-xAl80 ternary alloys in 1.0 M NaOH solution, nanoporous PdCu (np-PdCu) alloys with different Pd:Cu ratios are obtained. By a mild electrochemical dealloying treatment, the np-PdCu alloys are facilely converted into np-PdCu near-surface alloys with a nearly pure-Pd surface and PdCu alloy core. The np-PdCu near-surface alloys are then used as substrates to fabricate core-shell catalysts with a Pt monolayer as shell and np-PdCu as core by a Cu-underpotential deposition-Pt displacement strategy. Electrochemical measurements demonstrate that the Pt monolayer on np-Pd1Cu1 (Pt/np-Pd1Cu1) exhibits the highest Pt surface-specific activity towards oxygen reduction, which is ˜5.8-fold that of state-of-the-art Pt/C catalyst. The Pt/np-Pd1Cu1 also shows much enhanced stability with ˜78% active surface retained after 10,000 cycles (0.6-1.2 V vs. RHE). Under the same condition, the active surface of Pt/C drops to ˜28%.

  13. Triangular Ag-Pd alloy nanoprisms: rational synthesis with high-efficiency for electrocatalytic oxygen reduction.

    PubMed

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Zhang, Xiao; Tan, Chaoliang; Li, Hai; Zhang, Hua; Xue, Can

    2014-10-21

    We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag(+)/Pd(2+) is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems. PMID:25155648

  14. Localized Pd Overgrowth on Cubic Pt Nanocrystals for Enhanced Electrocatalytic Oxidation of Formic Acid

    SciTech Connect

    Lee, H.; Habas, S.E.; Somorjai, G.A.; Yang, P.

    2008-03-20

    Binary Pt/Pd nanoparticles were synthesized by localized overgrowth of Pd on cubic Pt seeds for the investigation of electrocatalytic formic acid oxidation. The binary particles exhibited much less self-poisoning and a lower activation energy relative to Pt nanocubes, consistent with the single crystal study.

  15. Characterization of Na+- beta-Zeolite Supported Pd and Pd Ag Bimetallic Catalysts using EXAFS, TEM and Flow Reactor

    SciTech Connect

    Huang,W.; Lobo, R.; Chen, J.

    2008-01-01

    Flow reactor studies of the selective hydrogenation of acetylene in the presence of ethylene have been performed on Na+ exchanged {beta}-zeolite supported Pd, Ag and PdAg catalysts, as an extension of our previous batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. Results from flow reactor studies show that the PdAg/Na+-{beta}-zeolite bimetallic catalyst has lower activity than Pd/Na+-{beta}-zeolite monometallic catalyst, while Ag/Na+-{beta}-zeolite does not show any activity for acetylene hydrogenation. However, the selectivity for the PdAg bimetallic catalyst is much higher than that for either the Pd catalyst or Ag catalyst. The selectivity to byproduct (ethane) is greatly inhibited on the PdAg bimetallic catalyst as well. The results from the current flow reactor studies confirmed the pervious results from batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. In addition, we used transmission electron microscope (TEM), extended X-ray absorption fine structure (EXAFS), and FTIR of CO adsorption to confirm the formation of Pd-Ag bimetallic alloy in the PdAg/Na+-{beta}-zeolite catalyst.

  16. Triangular Ag-Pd alloy nanoprisms: rational synthesis with high-efficiency for electrocatalytic oxygen reduction

    NASA Astrophysics Data System (ADS)

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Zhang, Xiao; Tan, Chaoliang; Li, Hai; Zhang, Hua; Xue, Can

    2014-09-01

    We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag+/Pd2+ is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems.We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag+/Pd2+ is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03600j

  17. A pathway for the growth of core-shell Pt-Pd nanoparticles

    DOE PAGESBeta

    Narula, Chaitanya Kumar; Yang, Xiaofan; Li, Chen; Pennycook, Stephen J; Lupini, Andrew R

    2015-10-12

    In this study, the aging of both Pt-Pd nanoparticles and core-shell Pt-Pd nanoparticles has been reported to result in alloying of Pt with Pd. In comparison to monometallic Pt catalysts, the growth of Pd-Pt bimetallics is slower; however, the mechanism of growth of particles and the mechanism by which Pd improves the hydrothermal durability of bimetallic Pd-Pt particles remains uncertain. In our work on hydrothermal aging of core-shell Pt-Pd nanoparticles, synthesized by solution methods, with varying Pd:Pt ratio of 1:4, 1:1, and 4:1, we compare the growth of core-shell Pt-Pd nanoparticles and find that particles grow by migrating and joiningmore » together. The unique feature of the observed growth is that Pd shells from both particles open up and join, allowing the cores to merge. At high temperatures, alloying occurs in good agreement with reports by other workers.« less

  18. Certification of Pd and Pt single spikes and application to the quantification of Pt and Pd in automotive exhaust emissions

    NASA Astrophysics Data System (ADS)

    Vogl, Jochen; Meyer, Christian; Noordmann, Janine; Rienitz, Olaf; Geilert, Sonja

    2014-05-01

    Numerous epidemiological studies show the effect of increased ambient pollution. Therefore measurement networks for air quality have been installed worldwide and legislation requires the monitoring of air pollution. Besides monitoring it is also important to be able to identify, to quantify and finally to regulate the emission of distinct sources in order to improve the quality of life. Automotive vehicles are a major source of environmental pollution especially through contaminants such as CO, NOX, SOX and hydrocarbons which derive from petrol combustion, while for example Platinum Group Elements (PGE) can be present from catalytic converters. The release of PGE into the environment, however, may be damaging in terms of public health, ecological and economic interests. In order to reliably assess the risks from PGEs, traceable and thus comparable data on the release rates of PGE from automotive catalysers are needed. As no Certified Reference Materials (CRM) are available for such samples the development of analytical procedures enabling SI-traceable results will be challenging. Therefore reference procedures for Pd and Pt in automotive exhaust emissions based on isotope dilution mass spectrometry (IDMS) have been developed and applied to specifically sampled automotive exhaust emissions. Due to the commonly known advantages, IDMS often is applied for quantification PGEs, as is the case within this work. The main reasons here are the required accuracy and the low PGE mass fractions in the sample. In order to perform IDMS analysis the analyte element must be available in an isotopically enriched form as so-called spike material or solution thereof, which is mixed with the sample. Unfortunately, no certified PGE spike solutions are available yet. To fill this gap two single PGE spikes, one 106Pd and one 194Pt spike, have been produced and characterized. The selection of the isotopes, the production of the solutions and the ampoulation will be described in this

  19. Novel mitoviruses in Rhizoctonia solani AG-3PT infecting potato.

    PubMed

    Das, Subha; Falloon, Richard E; Stewart, Alison; Pitman, Andrew R

    2016-03-01

    Double-stranded RNA (dsRNA) elements are ubiquitous in Rhizoctonia solani. Total dsRNA was randomly amplified from a R. solani isolate (RS002) belonging to anastomosis group-3PT (AG-3PT), associated with black scurf in potato. Assembly of resulting cDNA sequences identified a nearly complete genome of a novel virus related to the genus Mitovirus (family Narnaviridae), herein named Rhizoctonia mitovirus 1 RS002 (RMV-1-RS002). The 2797 nucleotide partial genome of RMV-1-RS002 is A-U rich (59.06 %), and can be folded into stable stem-loop structures at 5' and 3' ends. Universal and mold mitochondrial codon usages revealed a large open reading frame in the genome, putatively encoding an 826 amino acid polypeptide, which has conserved motifs for mitoviral RNA-dependent RNA polymerase. The full length putative polypeptide shared 25.6 % sequence identity with the corresponding region of Tuber excavatum mitovirus (TeMV). The partial genome of a second mitovirus (proposed name Rhizoctonia mitovirus 2 RS002 (RMV-2-RS002)) was also amplified from RS002. A nearly identical copy of RMV-1-RS002 was detected in two additional AG-3PT isolates. These data indicate that multiple mitoviruses can exist in a single isolate of R. solani AG-3PT, and that mitoviruses such as RMV-1-RS002 are probably widespread in this pathogen. The roles of mitoviruses in the biology of R. solani AG-3PT remain unknown. PMID:26895862

  20. Desorption of oxygen from alloyed Ag/Pt(111)

    SciTech Connect

    Jankowski, Maciej; Wormeester, Herbert Zandvliet, Harold J. W.; Poelsema, Bene

    2014-06-21

    We have investigated the interaction of oxygen with the Ag/Pt(111) surface alloy by thermal desorption spectroscopy (TDS). The surface alloy was formed during the deposition of sub-monolayer amounts of silver on Pt(111) at 800 K and subsequent cooling to 300 K. The low-temperature phase of the surface alloy is composed of nanometer-sized silver rich stripes, embedded within platinum-rich domains, which were characterized with spot profile analysis low energy electron diffraction. The TDS measurements show that oxygen adsorption is blocked on Ag sites: the saturation coverage of oxygen decreases with increasing Ag coverage. Also, the activation energy for desorption (E{sub des}) decreases with Ag coverage. The analysis of the desorption spectra from clean Pt(111) shows a linear decay of E{sub des} with oxygen coverage, which indicates repulsive interactions between the adsorbed oxygen atoms. In contrast, adsorption on alloyed Ag/Pt(111) leads to an attractive interaction between adsorbed oxygen atoms.

  1. Magnetic properties of ultrathin Co/Ag/Pt(111) films

    NASA Astrophysics Data System (ADS)

    Su, C. W.; Tzeng, C. L.; Ho, H. Y.; Shern, C. S.

    2003-11-01

    The magnetic properties of Co on Pt(111) with 1 ML Ag buffer layer were studied by magneto-optical Kerr effect. The easy axis of the magnetization of Co deposited on 1 ML Ag/Pt(111) switches from the out-of-plane to the in-plane direction when the coverage of Co is larger than 1 ML. The easy axis can transform from the in-plane to the out-of-plane direction after high temperature annealing for 2-7 ML Co/1 ML Ag/Pt(111). The study of Auger electron spectroscopy shows that the spin reorientation transition occurs when 1 ML Ag atoms diffuse to the top layer. The perpendicular magnetic anisotropy is significantly enhanced after further annealing at higher temperatures. The enhancement of the perpendicular magnetic anisotropy is attributed to the formation of Co-Pt alloy after the atomic exchange between Co and Ag. The possible mechanisms for the spin reorientation transition and the enhancement in the perpendicular magnetic anisotropy are discussed.

  2. Precipitations in a dental Ag-Pd-Cu-Au alloy.

    PubMed

    Herø, H; Jørgensen, R; Sørbrøden, E; Suoninen, E

    1982-05-01

    The structure of a dental Ag-PD-Cu-Au alloy has been studied after centrifugal casting and various heat treatments. By transmission electron microscopy, a high density of small fct particles, assumed to be PdCu, was observed, but, in addition, finely-spaced rods of approximately equal to 0.05 micrometer (500 A) diameter with an fcc structure precipitated on the [100] planes of the matrix were found. On the basis of their structure and the pertaining lattice parameter, these rods are assumed to be Cu-rich. They could also be observed by scanning electron microscopy, but not at annealing temperatures lower than 425 degrees C. PMID:6953095

  3. Synthesis of bimetallic Pt-Pd core-shell nanocrystals and their high electrocatalytic activity modulated by Pd shell thickness

    NASA Astrophysics Data System (ADS)

    Li, Yujing; Wang, Zhi Wei; Chiu, Chin-Yi; Ruan, Lingyan; Yang, Wenbing; Yang, Yang; Palmer, Richard E.; Huang, Yu

    2012-01-01

    Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more resistant to the CO poisoning than Pt NCs and Pt black. It is also demonstrated that the bimetallic Pt-Pd core-shell NCs can enhance the current density of the methanol oxidation reaction, lowering the over-potential by 35 mV with respect to the Pt core NCs. Further investigation reveals that the Pd/Pt ratio of 1/3, which corresponds to nearly monolayer Pd deposition on Pt core NCs, gives the highest oxidation current density and lowest over-potential. This study shows for the first time the systematic investigation of effects of Pd atomic shells on Pt-Pd bimetallic nanocatalysts, providing valuable guidelines for designing high-performance catalysts for fuel cell applications.Bimetallic Pt-Pd core-shell nanocrystals (NCs) are synthesized through a two-step process with controlled Pd thickness from sub-monolayer to multiple atomic layers. The oxygen reduction reaction (ORR) catalytic activity and methanol oxidation reactivity of the core-shell NCs for fuel cell applications in alkaline solution are systematically studied and compared based on different Pd thickness. It is found that the Pd shell helps to reduce the over-potential of ORR by up to 50mV when compared to commercial Pd black, while generating up to 3-fold higher kinetic current density. The carbon monoxide poisoning test shows that the bimetallic NCs are more

  4. Ti-Ag-Pd alloy with good mechanical properties and high potential for biological applications.

    PubMed

    Zadorozhnyy, V Yu; Shi, X; Gorshenkov, M V; Kozak, D S; Wada, T; Louzguine-Luzgin, D V; Inoue, A; Kato, H

    2016-01-01

    Ti-based alloys containing Ag were produced by tilt-casting method and their properties were studied. Even in its as-cast state, Ti94Ag3Pd3 showed relatively high tensile properties, good electrochemical behavior, and good biocompatibility. The relatively good mechanical properties of the as-cast α-Ti-type Ti94Ag3Pd3 alloy (tensile strength up to 850 MPa and elongation of ~10%) can be explained by its severely deformed, fine crystalline structure. The high biocompatibility of Ti94Ag3Pd3 can be explained by the Ag-Pd interaction, which inhibits the release of Ag ions from the surface. Ag, in combination with Pd has no toxic effects and demonstrates useful antimicrobial properties. The Ti94Ag3Pd3 alloy shows a good potential to be applied as a biomedical implant alloy. PMID:27122177

  5. Improved catalytic performance of Pd nanowires for ethanol oxidation by monolayer of Pt

    NASA Astrophysics Data System (ADS)

    Huang, Zhongyuan; Zhou, Haihui; Chang, Yiwen; Fu, Chaopeng; Zeng, Fanyan; Kuang, Yafei

    2013-10-01

    Pd nanowires with diameter of 10-20 nm and length of several micrometers were prepared and monolayer of Pt was deposited on the Pd nanowires by using copper underpotential deposition and subsequent replacement of Cu by Pt. The products were characterized by using scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and energy spectrum analysis. The electrocatalytic performance of PdPt nanowires was studied by cyclic voltammetry and chronoamperometry. Electrochemical results show that the monolayer of Pt can improve not only the activity of Pd nanowires but also the stability for ethanol oxidation in alkaline medium.

  6. Low-energy electron diffraction investigation of epitaxial growth: Pt and Pd on Pd(100)

    SciTech Connect

    Flynn-Sanders, D.

    1990-09-21

    We investigate the epitaxial growth of Pt and Pd and Pd(100) via spot profile analysis using conventional low-energy electron diffraction (LEED). We resolve a central-spike and diffuse component in the spot profiles, reflecting the layer-occupations and pair-correlations, respectively. Kinetic limitations inhibit layer-by-layer growth at low temperatures. Our data suggest diffusion switches on at ca. 150 K for Pt and ca. 170 K for Pd indicating activation barriers to surface diffusion of ca. 10 and ca. 13 kcal/mol, respectively. To clarify the role of diffusion in determining the resulting film morphology, we develop a growth model that incorporates the adsorption-site requirement and predicts intensity oscillations. We present a new procedure to experimentally determine out-of-phase scattering conditions. At these energies, ring-structure is evident in the profiles during Pd growth between ca. 200 and 400 K. We report ring intensity oscillations as a function of coverage, which demonstrate the filling of individual layers.

  7. Size and alloying induced shift in core and valence bands of Pd-Ag and Pd-Cu nanoparticles

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Govind

    2014-03-28

    In this report, X-ray photoelectron spectroscopy studies have been carried out on Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles having identical sizes corresponding to mobility equivalent diameters of 60, 40, and 20 nm. The nanoparticles were prepared by the gas phase synthesis method. The effect of size on valence and core levels in metal and alloy nanoparticles has been studied by comparing the values to those with the 60 nm nanoparticles. The effect of alloying has been investigated by comparing the valence and core level binding energies of Pd-Cu and Pd-Ag alloy nanoparticles with the corresponding values for Pd, Ag, and Cu nanoparticles of identical sizes. These effects have been explained in terms of size induced lattice contractions, alloying induced charge transfer, and hybridization effects. The observation of alloying and size induced binding energy shifts in bimetallic nanoparticles is important from the point of view of hydrogen reactivity.

  8. Segregated Pt on Pd nanotubes for enhanced oxygen reduction activity in alkaline electrolyte.

    PubMed

    St John, Samuel; Atkinson, Robert W; Dyck, Ondrej; Sun, Cheng-Jun; Zawodzinski, Thomas A; Papandrew, Alexander B

    2015-12-01

    Nanoscaled Pt domains were integrated with Pd nanotubes via vapor deposition to yield a highly active electrocatalyst for the oxygen reduction reaction (ORR) in alkaline media. The surface-area-normalized ORR activity of these bi-metallic Pt-on-Pd nanotubes (PtPdNTs) was nearly 6× the corresponding carbon-supported Pt nanoparticle (Pt/C) activity at 0.9 V vs. RHE (1.5 vs. 0.24 mA cmmetal(-2), respectively). Furthermore, the high specific activity of the PtPdNTs was achieved without sacrificing mass-normalized activity, which is more than twice that of Pt/C (0.333 A mgPtPdNT(-1)vs. 0.141 A mgPt/C(-1)) and also greater than that of Pd/C (0.221 A mgPd/C(-1)). We attribute the enhancements in specific and mass activity to modifications of the segregated Pt electronic structure and to nanoscale porosity, respectively. PMID:26553367

  9. The isotopic composition of AG in meteorites and the presence of Pd-107 in protoplanets

    NASA Astrophysics Data System (ADS)

    Chen, J. H.; Wasserburg, G. J.

    1990-06-01

    Results are presented on the isotopic composition of Ag and the concentrations of Pd and Ag in metal and sulfide phases in iron meteorites Gibeon, Derrick Peak, and Mundrabilla and in schereibersite in Derrick Peak. It was found that almost all iron meteorite samples with a ratio of Pd-108/Ag-109 greater than about 400 had an excess of Ag-107. The results, in conjunction with the data of Chen and Wasserburg (1983) on IIIA-IIIB meteorites, demonstrate the widespread occurrence of excess Ag-107 in diverse types of small early planetary bodies. The excess Ag-107 is believed to be produced by the decay of Pd-107.

  10. First-principles study of oxygen and hydrogen adsorption on Pt(111) and PtML/Pd(111) surfaces

    NASA Astrophysics Data System (ADS)

    Nie, J. L.; Ao, L.; Zu, X. T.

    2015-11-01

    In this paper, first-principles calculations based on density functional theory (DFT) have been performed to investigate the adsorption of oxygen and hydrogen on Pt(111) and Pd(111) surfaces covered by monolayer (ML) of Pt(PtML/Pd(111)). The results have shown that the oxygen molecule tends to adsorb on fcc site on both surfaces at the coverage of 0.25 ML, which becomes degeneration with hcp site when the coverage increases to 1 ML. For both oxygen and hydrogen, the adsorption on PtML/Pd(111) surface are stronger than those on Pt(111) surface. The adsorption energy difference for oxygen on the two surfaces is ˜0.2 eV at the coverage of 1 ML, which increases to ˜0.6 eV with the coverage decreasing to 0.25 ML. The similar energy difference was also found for hydrogen adsorption. The density of states analysis have demonstrated the chemical interaction of adsorbed oxygen with both pure Pt(111) and PtML/Pd(111) surfaces with certain shift of O2p states to lower level compared to isolated oxygen. For hydrogen adsorption, the hybridization of H1s with Pt5d states were observed for both surfaces, indicating the covalent bonding component of H-Pt bond.

  11. Ag/Pd core-shell nanoparticles by a successive method: Pulsed laser ablation of Ag in water and reduction reaction of PdCl2

    NASA Astrophysics Data System (ADS)

    Mottaghi, N.; Ranjbar, M.; Farrokhpour, H.; Khoshouei, M.; Khoshouei, A.; Kameli, P.; Salamati, H.; Tabrizchi, M.; Jalilian-Nosrati, M.

    2014-02-01

    In this study Ag/Pd nanoparticles (NPs) have been fabricated by a successive method; first, colloids of Ag nanoparticles (NPs) have been prepared in water by pulsed laser ablation in liquid (PLAL) method. Then PdCl2 solution (up to 0.2 g/l) were added to the as-prepared or aged colloidal Ag NPs. Characterizations were done using UV-vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmissions electron microscopy (TEM) techniques. Spectroscopy data showed that surface plasmon resonance (SPR) peaks of as-prepared Ag NPs at about λ = 400 nm were completely extinguished after addition of PdCl2 solution while this effect was not observed when aged Ag NPs are used. XRD and XPS results revealed that by addition of the PdCl2 solution into the as-prepared Ag NPs, metallic palladium, and silver chloride composition products are generated. TEM images revealed that as a result of this reaction, single and core-shell nanoparticles are obtained and their average sizes are 2.4 nm (Ag) and 3.2 nm (Ag/Pd). The calculated d-spacing values form XRD data with observations on high magnification TEM images were able to explain the chemical nature of different parts of Ag/Pd NPs.

  12. Alumina-supported Pd-Ag catalysts for low-temperature CO and methanol oxidation

    NASA Technical Reports Server (NTRS)

    Mccabe, R. W.

    1987-01-01

    Pd-Ag bimetallic catalysts, supported on gamma-Al2O3, have been evaluated as exhaust catalysts for methanol-fueled vehicles. Laboratory studies have shown that a 0.01% Pd-5% Ag catalyst has greater CO and CH3OH oxidation activity than either 0.01% Pd or 5% Ag catalysts alone. Moreover, Pd and Ag interact synergistically in the bimetallic catalyst to produce greater CO and CH3OH oxidation rates and lower yields of methanol partial oxidation products than expected from a mixture of the single-component catalysts. The Pd-Ag synergism results from Pd promoting the rate of O2 adsorption and reaction with CO and CH3OH on Ag. Rate enhancement by the bimetallic catalyst is greatest at short reactor residence times where the oxygen adsorption rate limits the overall reaction rate.

  13. Observation of Single Pt Nanoparticle Collisions: Enhanced Electrocatalytic Activity on a Pd Ultramicroelectrode.

    PubMed

    Shin, Changhwan; Park, Tae Eun; Park, Changki; Kwon, Seong Jung

    2016-06-01

    Single Pt nanoparticle (NP) collisions on an electrode surface were detected by using an electrocatalytic amplification method with a Pd ultramicroelectrode (UME). Pd is not a preferred material for UMEs for the detection of single Pt NP collisions, because Pd shows similar electrocatalytic activity compared with Pt for hydrazine oxidation, thus resulting in a high background current level. However, a Pt NP colliding on the Pd UME shows greatly enhanced activity compared with a Pt NP on an inert UME, such as a Au UME, which is usually used for the detection of single Pt NP collisions. The use of an electroactive UME material instead of an inert one facilitated the study of single-NP activity on the various solid supports, which is important in many NP applications. PMID:26955784

  14. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    NASA Astrophysics Data System (ADS)

    Sun, Yu; Hsieh, Yu-Chi; Chang, Li-Chung; Wu, Pu-Wei; Lee, Jyh-Fu

    2015-03-01

    Nanoparticles of PdRu, Pd3Ru, and Pd9Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x = 1/3/9), suggest successful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd9Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1 M aqueous HClO4 solution. Subsequently, the Pd9Ru/C undergoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd9Ru surface (Pd9Ru@Pt). The Pd9Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg-1Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg-1Pt). The mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd9Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.

  15. Design of Pt-Pd Binary Superlattices Exploiting Shape Effects and Synergistic Effects for Oxygen Reduction Reactions

    SciTech Connect

    Kang, YJ; Ye, XC; Chen, J; Cai, Y; Diaz, RE; Adzic, RR; Stach, EA; Murray, CB

    2013-01-09

    Large-area icosahedral-AB(13)-type Pt-Pd binary superlattices (BNSLs) are fabricated through self-assembly of 6 nm Pd nanocrystals (NCs) and 13 nm Pt octahedra at a liquid air interface. The Pt-Pd BNSLs enable a high activity toward electrocatalysis of oxygen reduction reaction (ORR) by successfully exploiting the shape effects of Pt-NCs and synergistic effects of Pt-Pd into a single crystalline nanostructure. The Pt-Pd BNSLs are promising catalysts for the oxygen electrode of fuel cells.

  16. Tailoring Silica-alumina Supported Pt-Pd As Poison Tolerant Catalyst For Aromatics Hydrogenation

    SciTech Connect

    Yu, Yanzhe; Gutierrez, Oliver Y.; Haller, Gary L.; Colby, Robert J.; Kabius, Bernd C.; Rob van Veen, J. A.; Jentys, Andreas; Lercher, Johannes A.

    2013-08-01

    The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt-Pd catalysts supported on amorphous silica-alumina is studied. Electron energy loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt-Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, which was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt-Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt-Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt-Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts towards sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal-sulfur bond on the electron deficient Pt atoms. Thus, increasing the fraction of electron deficient Pt on the surface of the bimetallic particles increases the efficiency of the catalyst in the presence of sulfur.

  17. Comparative study in annealing effects of Ag/Co/Pt(1 1 1) and Co/Ag/Pt(1 1 1) ultrathin films

    NASA Astrophysics Data System (ADS)

    Su, C. W.; Wu, Y. E.; Shern, C. S.

    2001-06-01

    Low-energy electron diffraction (LEED), Auger electron spectroscopy and depth profile were used to study the growth and annealing effects of mirror systems: Ag/Co/Pt(1 1 1) and Co/Ag/Pt(1 1 1). An anomalous behavior of specular beam intensity of LEED versus temperature was found in the annealing process for Ag/Co/Pt(1 1 1). A dramatic increase of the beam intensity occurs after Co-Pt alloy formation is complete. The exchange between Co and Ag atoms of Co/Ag/Pt(1 1 1) occurs when the annealing temperature is high enough. The Co-Pt alloy develops after the atomic exchange is complete. The chemical compositions at the interfaces of these two ultrathin films were investigated. The mechanisms of the different behaviors of the two systems in the annealing processes are discussed.

  18. Sulfuration resistance of five experimental Ag-Pd-Au-Cu alloys with low Pd content of 10 or 12%.

    PubMed

    Saitoh, Setsuo; Araki, Yoshima; Taira, Masayuki

    2006-06-01

    Commercial Ag-based alloy (46Ag-20Pd-12Au-20Cu alloy) is widely used in Japan as a casting alloy. As opposed to the commercial composition, we prepared five experimental Ag-based alloys with reduced Pd content of 10 or 12%, increased Au content of 20 to 30%, and reduced Cu content of 12 to 20%. We then evaluated their sulfuration resistance by analyzing cast specimen surfaces dipped in 0.1% Na2S solution with SEM/EPMA, TF-XRD, and XPS. It became evident that all alloys were susceptible to sulfuration in the segregated Ag-rich Pd-poor phases. The degree and speed of sulfuration, however, differed among the six alloys examined. In particular, one experimental alloy (46Ag-10Pd-30Au-12Cu) possessed a sulfuration resistance equal or superior to that of commercial Ag-based alloy, while the other four experimental alloys were inferior in sulfuration resistance. Based on the results of this study, we concluded that our newly developed 46Ag-10Pd-30Au-12Cu alloy could be employed as a new sulfuration-resistant Ag-based casting alloy--which is especially useful if the price of Pd is skyrocketing again. PMID:16916236

  19. Pt-Pd alloy nanoparticle-decorated carbon nanotubes: a durable and methanol tolerant oxygen reduction electrocatalyst

    NASA Astrophysics Data System (ADS)

    Ghosh, Sourov; Sahu, Ranjan K.; Retna Raj, C.

    2012-09-01

    We describe the decoration of multiwalled carbon nanotubes (MCNTs) with Pt-Pd alloy nanoelectrocatalysts of three different compositions and their electrocatalytic performance toward the oxygen reduction reaction (ORR). The decoration of the MCNTs involves polymer-assisted impregnation of metal precursors {{PtCl}}_{6}^{2-} and {{PdCl}}_{4}^{2-} and the subsequent reduction of the impregnated precursors by a modified polyol route. The composition of the catalyst was controlled by tuning the molar ratio of the precursors during their impregnation. Electron probe microscopic analysis shows that the catalysts have compositions of Pt46Pd54, Pt64Pd36 and Pt28Pd72. The Pt46Pd54 and Pt64Pd36 catalysts have truncated octahedral and icosahedral shapes with a size ranging from 8 to 10 nm. On the other hand, the catalyst of Pt28Pd72 composition has a spherical/quasispherical shape with a size distribution of 1-2 nm. The XPS measurement confirms the signature of metallic Pt and Pd. The Pt46Pd54 catalyst has a pronounced electrocatalytic activity toward the ORR with a specific and mass activity of 378 ~\\mu {A}~{{cm}}_{{Pt}-{Pd}}^{-2} and 6 4~\\mu {A}~\\mu {{g}}_{{Pt}-{Pd}}^{-1}, respectively at 0.8 V. Moreover, the Pt46Pd54 nanoelectrocatalyst is highly durable and it retains its initial catalytic activity even after 1000 extensive cycles. Interestingly, this catalyst has a very high tolerance toward methanol and it does not favor the oxidation of methanol in the potential window of 0.1-1.4 V. The electrocatalytic activity of the alloy electrocatalyst is compared with commercially available Pt black and MCNT-supported spherical Pt nanoparticles. The catalytic activity of the Pt46Pd54 nanoelectrocatalyst is higher than the other catalysts. The Pt46Pd54 catalyst outperforms the electrocatalytic activity of all other catalysts.

  20. Pd2Ag triangle supported by two micro3-amidopyridine ligands.

    PubMed

    Shen, Wei-Zheng; Costisella, Burkhard; Lippert, Bernhard

    2007-02-28

    [Pd(tmeda)(Hampy-N1)(H2O)]2+ (tmeda=N,N,N',N'-tetramethylethylenediamine; Hampy=2-aminopyridine) forms in the presence of Ag+ at pH 8-9 a triangular Pd2Ag complex containing two deprotonated ampy- ligands. It has been crystallized and structurally characterized with nitrate anions and a second co-crystallized AgNO3, [{Pd(ampy)(tmeda)}2Ag(micro-NO3)2Ag(NO3)2]. The two amidopyridine ligands are triply bridging, binding to Ag+ in a monodentate fashion viaN1, and to two PdII centres in a micro2-bridging fashion via the monodeprotonated N2 position. The resulting four-membered Pd(ampy)2Pd metallacycle is syn-planar with Pd[dot dot dot]Pd separations of 3.0878(13) A. The Pd...Ag distances are 3.0879(14) A in (isosceles triangle). In solution (D2O), the two ampy- ligand in are non-equivalent as concluded from a detailed 1H NMR spectroscopic study and confirmed by a 13C NMR spectrum. Removal of Ag+ from, as achieved by addition of Cl-, causes cluster degradation and linkage isomerization of PdII(tmeda) from the exocyclic N2 to the endocyclic N1 position. PMID:17297512

  1. Synthesis of Pt-Pd bimetallic nanoparticles anchored on graphene for highly active methanol electro-oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Yuting; Chang, Gang; Shu, Honghui; Oyama, Munetaka; Liu, Xiong; He, Yunbin

    2014-09-01

    A simple, one-step reduction route was employed to synthesize bimetallic Pt-Pd nanoparticles (Pt-PdNPs) supported on graphene (G) sheets, in which the reduction of graphite oxide and metal precursor was carried out simultaneously using ascorbic acid as a soft reductant. The morphology and structure of Pt-PdNPs/G composites were characterized using X-ray diffraction, Transmission Electron Microscopy, Field Emission Scanning Electron Microscopy and X-ray Photoelectron Spectroscopy analysis. The results show that Pt-Pd bimetallic nanoparticles were successfully synthesized and evenly anchored on the graphene sheets. Electrochemical experiments, including cyclic voltammetry and chronoamperometric measurements, were performed to investigate the electrochemical and electrocatalytic properties of the Pt-PdNPs/G composites. It was found that Pt-PdNPs/G composites show better electrocatalytic activity and stability towards the electro-oxidation of methanol than its counterparts such as composites composed of graphene-supported monometallic nanoparticles (PtNPs/G, PdNPs/G) and free-standing (Pt-PdNPs) and Vulcan-supported bimetallic Pt-Pd nanoparticles (Pt-PdNPs/V). The results could be attributed to the synergetic effects of the Pt-Pd nanoparticles and the enhanced electron transfer of graphene. The electrocatalytic activity of Pt-PdNPs/G changed with the Pd content in the Pt-Pd alloy, and the best performance was achieved with a Pt-Pd ratio of 1/3 in an alkaline environment. Our study indicates the potential use of Pt-PdNPs/G as new anode catalyst materials for direct methanol fuel cells.

  2. Intermartensitic Transformation and Enhanced Exchange Bias in Pd (Pt) -doped Ni-Mn-Sn alloys.

    PubMed

    Dong, S Y; Chen, J Y; Han, Z D; Fang, Y; Zhang, L; Zhang, C L; Qian, B; Jiang, X F

    2016-01-01

    In this work, we studied the phase transitions and exchange bias of Ni50-xMn36Sn14Tx (T = Pd, Pt; x = 0, 1, 2, 3) alloys. An intermartensitic transition (IMT), not observed in Ni50Mn36Sn14 alloy, was induced by the proper application of negative chemical pressure by Pd(Pt) doping in Ni50-xMn36Sn14Tx (T = Pd, Pt) alloys. IMT weakened and was suppressed with the increase of applied field; it also disappeared with further increase of Pd(Pt) content (x = 3 for Pd and x = 2 for Pt). Another striking result is that exchange bias effect, ascribed to the percolating ferromagnetic domains coexisting with spin glass phase, is notably enhanced by nonmagnetic Pd(Pt) addition. The increase of unidirectional anisotropy by the addition of Pd(Pt) impurities with strong spin-orbit coupling was explained by Dzyaloshinsky-Moriya interactions in spin glass phase. PMID:27170057

  3. Exploring PtSO4 and PdSO4 phases: an evolutionary algorithm based investigation.

    PubMed

    Sharma, Hom; Sharma, Vinit; Huan, Tran Doan

    2015-07-21

    Metal sulfate formation is one of the major challenges to the emission aftertreatment catalysts. Unlike the incredibly sulfation prone nature of Pd to form PdSO4, no experimental evidence exists for PtSO4 formation. Given the mystery of nonexistence of PtSO4, we explore PtSO4 using a combined approach of an evolutionary algorithm based search technique and quantum mechanical computations. Experimentally known PdSO4 is considered for the comparison and validation of our results. We predict many possible low-energy phases of PtSO4 and PdSO4 at 0 K, which are further investigated in a wide range of temperature-pressure conditions. An entirely new low-energy (tetragonal P42/m) structure of PtSO4 and PdSO4 is predicted, which appears to be the most stable phase of PtSO4 and a competing phase of the experimentally known monoclinic C2/c phase of PdSO4. Phase stability at a finite temperature is further examined and verified by Gibbs free energy calculations of sulfates towards their possible decomposition products. Finally, temperature-pressure phase diagrams are computationally established for both PtSO4 and PdSO4. PMID:26103206

  4. Intermartensitic Transformation and Enhanced Exchange Bias in Pd (Pt) -doped Ni-Mn-Sn alloys

    PubMed Central

    Dong, S. Y.; Chen, J. Y.; Han, Z. D.; Fang, Y.; Zhang, L.; Zhang, C. L.; Qian, B.; Jiang, X. F.

    2016-01-01

    In this work, we studied the phase transitions and exchange bias of Ni50−xMn36Sn14Tx (T = Pd, Pt; x = 0, 1, 2, 3) alloys. An intermartensitic transition (IMT), not observed in Ni50Mn36Sn14 alloy, was induced by the proper application of negative chemical pressure by Pd(Pt) doping in Ni50−xMn36Sn14Tx (T = Pd, Pt) alloys. IMT weakened and was suppressed with the increase of applied field; it also disappeared with further increase of Pd(Pt) content (x = 3 for Pd and x = 2 for Pt). Another striking result is that exchange bias effect, ascribed to the percolating ferromagnetic domains coexisting with spin glass phase, is notably enhanced by nonmagnetic Pd(Pt) addition. The increase of unidirectional anisotropy by the addition of Pd(Pt) impurities with strong spin-orbit coupling was explained by Dzyaloshinsky-Moriya interactions in spin glass phase. PMID:27170057

  5. Structures of small Pd Pt bimetallic clusters by Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Cheng, Daojian; Huang, Shiping; Wang, Wenchuan

    2006-11-01

    Segregation phenomena of Pd-Pt bimetallic clusters with icosahedral and decahedral structures are investigated by using Monte Carlo method based on the second-moment approximation of the tight-binding (TB-SMA) potentials. The simulation results indicate that the Pd atoms generally lie on the surface of the smaller clusters. The three-shell onion-like structures are observed in 55-atom Pd-Pt bimetallic clusters, in which a single Pd atom is located in the center, and the Pt atoms are in the middle shell, while the Pd atoms are enriched on the surface. With the increase of Pd mole fraction in 55-atom Pd-Pt bimetallic clusters, the Pd atoms occupy the vertices of clusters first, then edge and center sites, and finally the interior shell. It is noticed that some decahedral structures can be transformed into the icosahedron-like structure at 300 and 500 K. Comparisons are made with previous experiments and theoretical studies of Pd-Pt bimetallic clusters.

  6. Corrosion of Ti-STS dissimilar joints brazed by a Ag interlayer and Ag-Cu-(Pd) alloy fillers

    NASA Astrophysics Data System (ADS)

    Lee, M. K.; Park, J. J.; Lee, G. J.; Lee, J. G.; Kim, D. W.; Lim, C. H.; Rhee, C. K.; Lee, Y. B.; Lee, J. K.; Hong, S. J.

    2011-02-01

    Corrosion behavior of dissimilar brazed joints between titanium Gr. 2 (Ti) and S31254 stainless steel (STS) was investigated. For the study, a Ag interlayer and two Ag-base eutectic alloys, 72Ag-28Cu and 66.2Ag-25.8Cu-8Pd (wt.%), were introduced as a diffusion control layer and fillers, respectively, between the base materials. The joints commonly had a layered structure of Ti(base)/TiAg/Ag solid solution/STS(base), but the one brazed by the Ag-Cu-Pd filler was slightly alloyed with the noble Pd elements over the Ag-rich solid solution region. A series of corrosion test experiments in a sea water revealed that a corrosion of TiAg layer and a stress-induced cracking at the TiAg/Ag solid solution interface were dominant due to a galvanic attack, but notably the Ti-STS dissimilar joint's resistance to corrosion was significantly improved by alloying the Pd in the joint. The corrosion behavior of such dissimilar metal joints was discussed based on galvanic corrosion effect.

  7. CO adsorption and kinetics on well-characterized Pd films on Pt(111) in alkaline solutions

    SciTech Connect

    Arenz, M.; Stamenkovic, V.; Wandelt, K.; Ross, P.N.; Markovic, N.M.

    2002-01-01

    The electrochemistry of CO on a bare Pt(111) electrode as well as a Pt(111) electrode modified with pseudomorphic thin palladium films has been studied in alkaline solution by means of Fourier transform infrared (FTIR) spectroscopy. First Pd films were prepared and well characterized in UHV and subsequently transferred into the electrochemical cell for the registration of the voltammetric profiles. The charge corresponding to the formation of underpotentially deposited hydrogen (H{sub upd}) on these Pt(111)-xPd surfaces was established in sulfuric acid solution as a function of x (0 {le} x {le} 1 Pd monolayer (ML)). All subsequent measurements were then performed on electrochemically deposited palladium films using the above H{sub upd}-charge vs. Pd coverage relationship to evaluate the amount of electrochemically deposited palladium. FTIR spectra for CO adsorbed on one monolayer and a submonolayer coverage are compared to those of the unmodified Pt(111) surface, all surfaces having identical 2D lattice structures. Infrared absorption bands of CO bound on either Pt(111) or Pt(111)-1ML Pd are clearly distinguished. Spectra of CO adsorbed on Pd submonolayers show characteristic features of both CO bound to Pt and to Pd, indicating that on Pt(111)-xPd surfaces there is no coupling between Pt-CO{sub ad} and Pd-CO{sub ad} molecules. The kinetics of CO oxidation on these surfaces is determined either by rotating disk electrode (RDE) measurements or by FTIR spectroscopy, monitoring the CO{sub 3}{sup 2-} production. The oxidation of CO{sub ad} on Pt(111) and on Pd modified platinum surfaces starts at the same potential, ca. at 0.2 V. The oxidation rate is, however, considerably lower on the Pt(111)-xPd surfaces than on the Pt(111) surface. The kinetics of CO oxidation appears to be determined by the nature of adsorbed hydroxyl anions (OH{sub ad}), which are more strongly (less active) adsorbed on the highly oxophilic Pd atoms.

  8. Pt/Pd thermocouple resilience over 327 operating hours in an industrial calibration laboratory

    NASA Astrophysics Data System (ADS)

    Elliott, C. J.; Pearce, J. V.; Machin, G.; Ford, T.; Hicks, K.

    2013-09-01

    Two Pt/Pd thermocouples have been manufactured industrially at CCPI-Europe to a robust design optimised by NPL. The first has been exposed to temperatures up to 1000 °C for 93 operating hours and the second exposed to higher temperatures (up to 1300 °C) for 327 operating hours, over the course of a year. No significant drift is observed in the temperature measurement for either Pt/Pd thermocouple, when compared against reference Type R thermocouples. This work demonstrates the long-term stability and reliability of Pt/Pd thermocouples in use within an industrial calibration environment with this optimised, robust design.

  9. Size selected cluster deposition on well characterized surfaces: Ag{sub n}/Pd(100)

    SciTech Connect

    Vandoni, G.; Felix, C.; Harbich, W.; Monot, R.; Buttet, J.; Massobrio, C.

    1997-06-20

    We study the deposition of Ag ions, and size selected Ag{sub 7} and Ag{sub 19} cluster ions on Pd(100) at total kinetic energies of 20 eV and 95 eV using Thermal Energy Atom Scattering and Molecular Dynamics simulations. We find that at all energies Ag atoms are implanted into the substrate and Pd atoms are ejected in the adlayer. The experimental results in the case of Ag{sub 7} can be understood in taking into account both implantation of Ag atoms and heavy fragmentation. In the case of Ag{sub 19} the deposition leads at low temperature to non compact structures localized around the impact point. We propose a model in which morphology changes take place between 200 K and 300 K resulting in well separated compact structures formed of Ag and Pd adatoms.

  10. Kinetic study of Pt nanocrystal deposition on Ag nanowires with clean surfaces via galvanic replacement

    PubMed Central

    2012-01-01

    Without using any templates or surfactants, this study develops a high-yield process to prepare vertical Ag-Pt core-shell nanowires (NWs) by thermally assisted photoreduction of Ag NWs and successive galvanic replacement between Ag and Pt ions. The clean surface of Ag nanowires allows Pt ions to reduce and deposit on it and forms a compact sheath comprising Pt nanocrystals. The core-shell structural feature of the NWs thus produced has been demonstrated via transmission electron microscopy observation and Auger electron spectroscopy elemental analysis. Kinetic analysis suggests that the deposition of Pt is an interface-controlled reaction and is dominated by the oxidative dissolution of Ag atoms. The boundaries in between Pt nanocrystals may act as microchannels for the transport of Ag ions during galvanic replacement reactions. PMID:22559242

  11. Structural and Electronic Transformations of Pt/C, Pd@Pt(1 ML)/C and Pd@Pt(2 ML)/C Cathode Catalysts in Polymer Electrolyte Fuel Cells during Potential-step Operating Processes Characterized by In-situ Time-resolved XAFS

    NASA Astrophysics Data System (ADS)

    Nagamatsu, Shin-ichi; Takao, Shinobu; Samjeské, Gabor; Nagasawa, Kensaku; Sekizawa, Oki; Kaneko, Takuma; Higashi, Kotaro; Uruga, Tomoya; Gayen, Sirshendu; Velaga, Srihari; Saniyal, Milan K.; Iwasawa, Yasuhiro

    2016-06-01

    The dynamic structural and electronic transformations of Pt/C, Pd@Pt(1 ML)/C, Pd@Pt(2 ML)/C cathode catalysts in polymer electrolyte fuel cells (PEFCs) during the potential-step operating processes between 0.4 and 1.4 VRHE (potential vs RHE) were characterized by in-situ (operando) time-resolved Pt LIII-edge quick-XAFS at 100 ms time-resolution. Potential-dependent surface structures and oxidation states of Pt, Pd@Pt(1 ML) and Pd@Pt(2 ML) nanoparticles on carbon at 0.4 and 1.4 VRHE were also analyzed by in-situ Pt LIII-edge and Pd K-edge quick-XAFS. The Pt, Pd@Pt(1 ML) and Pd@Pt(2 ML) nanoparticle surfaces were restructured and disordered at 1.4 VRHE, which were induced by strong Pt-O bonds as well as alloying effects. The rate constants for the changes of Pt valence, CN(Pt-Pt), CN(Pt-Pd) and CN(Pt-O) (CN: coordination number) in the potential-step operating processes were also determined and discussed in relation to the origin of oxygen reduction reaction (ORR) activities of the Pt/C, Pd@Pt(1 ML)/C and Pd@Pt(2 ML)/C cathode catalysts.

  12. One‐Electron Oxidation of [M(PtBu3)2] (M=Pd, Pt): Isolation of Monomeric [Pd(PtBu3)2]+ and Redox‐Promoted C−H Bond Cyclometalation

    PubMed Central

    Troadec, Thibault; Tan, Sze‐yin; Wedge, Christopher J.; Rourke, Jonathan P.; Unwin, Patrick R.

    2016-01-01

    Abstract Oxidation of zero‐valent phosphine complexes [M(PtBu3)2] (M=Pd, Pt) has been investigated in 1,2‐difluorobenzene solution using cyclic voltammetry and subsequently using the ferrocenium cation as a chemical redox agent. In the case of palladium, a mononuclear paramagnetic PdI derivative was readily isolated from solution and fully characterized (EPR, X‐ray crystallography). While in situ electrochemical measurements are consistent with initial one‐electron oxidation, the heavier congener undergoes C−H bond cyclometalation and ultimately affords the 14 valence‐electron PtII complex [Pt(κ 2 PC‐PtBu2CMe2CH2)(PtBu3)]+ with concomitant formation of [Pt(PtBu3)2H]+. PMID:26879233

  13. Chemical bonding in EuTGe (T=Ni, Pd, Pt) and physical properties of EuPdGe

    SciTech Connect

    Rocquefelte, Xavier; Gautier, Regis; Halet, Jean-Francois Muellmann, Ralf; Rosenhahn, Carsten; Mosel, Bernd D.; Kotzyba, Gunter; Poettgen, Rainer

    2007-02-15

    EuPdGe was prepared from the elements by reaction in a sealed tantalum tube in a high-frequency furnace. Magnetic susceptibility measurements show Curie-Weiss behavior above 60 K with an experimental magnetic moment of 8.0(1){mu} {sub B}/Eu indicating divalent europium. At low external fields antiferromagnetic ordering is observed at T {sub N}=8.5(5) K. Magnetization measurements indicate a metamagnetic transition at a critical field of 1.5(2) T and a saturation magnetization of 6.4(1){mu} {sub B}/Eu at 5 K and 5.5 T. EuPdGe is a metallic conductor with a room-temperature value of 5000{+-}500 {mu}{omega} cm for the specific resistivity. {sup 151}Eu Moessbauer spectroscopic experiments show a single europium site with an isomer shift of {delta}=-9.7(1) mm/s at 78 K. At 4.2 K full magnetic hyperfine field splitting with a hyperfine field of B=20.7(5) T is observed. Density functional calculations show the similarity of the electronic structures of EuPdGe and EuPtGe. T-Ge interactions (T=Pd, Pt) exist in both compounds. An ionic formula splitting Eu{sup 2+} T {sup 0}Ge{sup 2-} seems more appropriate than Eu{sup 2+} T {sup 2+}Ge{sup 4-} accounting for the bonding in both compounds. Geometry optimizations of EuTGe (T=Ni, Pt, Pd) show weak energy differences between the two structural types. - Graphical abstract: Cutouts of the [PdGe] and [PtGe] polyanions in the structures of EuPdGe and EuPtGe. Atom designations and some relevant interatomic distances are given.

  14. Effect of metal support interaction on surface segregation in Pd Pt nanoparticles

    NASA Astrophysics Data System (ADS)

    De Sarkar, A.; Menon, Mahesh; Khanra, Badal C.

    2001-10-01

    In this work, we present the results of our Monte Carlo (MC) simulation studies for the segregation behavior of supported, clean and gas-covered Pd-Pt nanoparticles as a function of the metal-support interaction. For preferential Pd-support interaction, the base of the nanoparticle is found to get enriched with Pd atoms; while for preferential interaction of Pt atoms with the support the base gets enriched in Pt. The composition of the rest of the particle changes slightly with the metal-support interaction. The presence of oxygen and hydrogen atoms does not influence the role of the metal-support interaction on the surface composition of Pd-Pt nanoparticles. The simulation results are found to be in total agreement with the known experimental results.

  15. Spin pumping damping and magnetic proximity effect in Pd and Pt spin-sink layers

    NASA Astrophysics Data System (ADS)

    Caminale, M.; Ghosh, A.; Auffret, S.; Ebels, U.; Ollefs, K.; Wilhelm, F.; Rogalev, A.; Bailey, W. E.

    2016-07-01

    We investigated the spin pumping damping contributed by paramagnetic layers (Pd, Pt) in both direct and indirect contact with ferromagnetic Ni81Fe19 films. We find a nearly linear dependence of the interface-related Gilbert damping enhancement Δ α on the heavy-metal spin-sink layer thicknesses tN in direct-contact Ni81Fe19 /(Pd, Pt) junctions, whereas an exponential dependence is observed when Ni81Fe19 and (Pd, Pt) are separated by 3 nm Cu. We attribute the quasilinear thickness dependence to the presence of induced moments in Pt, Pd near the interface with Ni81Fe19 , quantified using x-ray magnetic circular dichroism measurements. Our results show that the scattering of pure spin current is configuration-dependent in these systems and cannot be described by a single characteristic length.

  16. Preparation of PdAg and PdAu nanoparticle-loaded carbon black catalysts and their electrocatalytic activity for the glycerol oxidation reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Lam, Binh Thi Xuan; Chiku, Masanobu; Higuchi, Eiji; Inoue, Hiroshi

    2015-11-01

    PdAg and PdAu alloy nanoparticle catalysts for the glycerol oxidation reaction (GOR) were prepared at room temperature by a wet method. The molar ratio of the precursors controlled the bulk composition of the PdAg and PdAu alloys, and their surface composition was Ag-enriched and Pd-enriched, respectively. On PdAg-loaded carbon black (PdAg/CB) electrodes, the onset potential of GOR was 0.10-0.15 V more negative than on the Pd/CB electrode due to the electronic effect. The ratio of GOR peak current densities in the backward and forward sweeps of CVs (ib/if) was smaller because of the improved tolerance to the poisoning species. The ratio of the GOR current density at 60 and 5 min (i60/i5) for the PdAg/CB electrodes was higher for more negative potentials than the Pd/CB electrode. In contrast, the PdAu-loaded CB (PdAu/CB) electrodes had an onset potential of GOR similar to the Pd/CB electrode and a higher GOR peak current density owing to the bi-functional effect. However, the ib/if ratio was higher for PdAu/CB because of the increase in ib as the Pd surface was recovered, and the i60/i5 ratio was higher for more positive potentials, similar to the Pd/CB electrode.

  17. Pt/Pd electrocatalyst electrons for fuel cells

    DOEpatents

    Stonehart, P.

    1981-11-03

    This invention relates to improved electrochemical cells and to novel electrodes for use therein. In particular, the present invention comprises a fuel cell used primarily for the consumption of impure hydrogen fuels containing carbon monoxide or carbonaceous fuels where the electrode in contact with the fuel is not substantially poisoned by carbon monoxide. The anode of the fuel cell comprises a Pd/Pt alloy supported on a graphitized or partially graphitized carbon material. Fuel cells which comprise as essential elements a fuel electrode, an oxidizing electrode, and an electrolyte between said electrodes are devices for the direct production of electricity through the electrochemical combustion of a fuel and oxidant. These devices are recognized for their high efficiency as energy conversion units, since unlike conventional combustion engines, they are not subject to the limitations of the Carnot heat cycle. It is the primary object of the present invention to provide an electrode having high electrochemical activity for an electrochemical cell. It is another object of the present invention to provide an electrode having an electro-catalyst which is highly resistant to the corrosive environment of an electrochemical cell.

  18. Impurity scattering effect in Pd-doped superconductor SrPt3P

    NASA Astrophysics Data System (ADS)

    Hu, Kang-Kang; Gao, Bo; Ji, Qiu-Cheng; Ma, Yong-Hui; Zhang, Hui; Mu, Gang; Huang, Fu-Qiang; Cai, Chuan-Bing; Xie, Xiao-Ming

    2016-08-01

    We present a systematic study of the impurity scattering effect induced by Pd dopants in the superconductor SrPt3P. Using a solid-state reaction method, we fabricated the Pd-doped superconductor Sr(Pt1- x Pd x )3P.We found that the residual resistivity ρ 0 increases quickly with Pd doping, whereas the residual resistance ratio (RRR) displays a dramatic reduction. In addition, both the nonlinear field-dependent behavior of the Hall resistivity ρ xy and the strong temperature dependence of the Hall coefficient R H at low temperature are suppressed by Pd doping. All the experimental results can be explained by an increase in scattering by impurities induced by doping. Our results suggest that the Pt position is very crucial to the carrier conduction in the present system.

  19. Pt-Decorated PdCo@Pd/C Core-Shell Nanoparticles with Enhanced Stability and Electrocatalytic Activity for the Oxygen Reduction Reaction

    SciTech Connect

    Wang, Deli; Xin, Huolin L.; Yu, Yingchao; Wang, Hongsen; Rus, Eric; Muller, David A.; Abruña, Héctor D.

    2010-11-24

    A simple method for the preparation of PdCo@Pd core-shell nanoparticles supported on carbon based on an adsorbate-induced surface segregation effect has been developed. The stability of these PdCo@Pd nanoparticles and their electrocatalytic activity for the oxygen reduction reaction (ORR) were enhanced by decoration with a small amount of Pt deposited via a spontaneous displacement reaction. The facile method described herein is suitable for large-scale, lower-cost production and significantly lowers the Pt loading and thus the cost. The as-prepared PdCo@Pd and Pd-decorated PdCo@Pd nanocatalysts have a higher methanol tolerance than Pt/C in the ORR and are promising cathode catalysts for fuel cell applications.

  20. Core-shell Au@Pd nanoparticles with enhanced catalytic activity for oxygen reduction reaction via core-shell Au@Ag/Pd constructions

    PubMed Central

    Chen, Dong; Li, Chengyin; Liu, Hui; Ye, Feng; Yang, Jun

    2015-01-01

    Core-shell nanoparticles often exhibit improved catalytic properties due to the lattice strain created in these core-shell particles. Herein, we demonstrate the synthesis of core-shell Au@Pd nanoparticles from their core-shell Au@Ag/Pd parents. This strategy begins with the preparation of core-shell Au@Ag nanoparticles in an organic solvent. Then, the pure Ag shells are converted into the shells made of Ag/Pd alloy by galvanic replacement reaction between the Ag shells and Pd2+ precursors. Subsequently, the Ag component is removed from the alloy shell using saturated NaCl solution to form core-shell Au@Pd nanoparticles with an Au core and a Pd shell. In comparison with the core-shell Au@Pd nanoparticles upon directly depositing Pd shell on the Au seeds and commercial Pd/C catalysts, the core-shell Au@Pd nanoparticles via their core-shell Au@Ag/Pd templates display superior activity and durability in catalyzing oxygen reduction reaction, mainly due to the larger lattice tensile effect in Pd shell induced by the Au core and Ag removal. PMID:26144550

  1. Effects of Ag addition on FePt L1{sub 0} ordering transition: A direct observation of ordering transition and Ag segregation in FePtAg alloy films

    SciTech Connect

    Wang, Lei; Yu, Youxing; Gao, Tenghua

    2015-12-21

    FePt and (FePt){sub 91.2}Ag{sub 8.8} alloy films were deposited by magnetron sputtering. The average coercivity of (FePt){sub 91.2}Ag{sub 8.8} films reaches 8.51 × 10{sup 5} A/m, which is 0.63 × 10{sup 5} A/m higher than that of the corresponding FePt films. Ag addition effectively promotes the FePt L1{sub 0} ordering transition at a relatively low annealing temperature of 400 °C. The promotion mechanism was investigated by using in situ high-resolution transmission electron microscopy (HRTEM) and ex situ X-ray absorption fine structure (XAFS). The concurrence of ordering transition and Ag segregation in FePtAg alloy films was first observed by using in situ heating HRTEM. The time-resolved evolution reveals more details on the role of Ag addition in FePt low-temperature ordering. Ex situ XAFS results further confirm that Ag replaces Fe sites in the as-deposited films and segregates from FePt-Ag solid solution phase through annealing at elevated temperatures. The segregation of Ag atoms leaves vacancies in the grain. The vacancy formation is believed to accelerate the diffusion of Fe and Pt atoms, which is critical for the L1{sub 0} ordering transition.

  2. Gram-Scale-Synthesized Pd2Co-Supported Pt Monolayer Electrocatalysts for Oxygen Reduction Reaction

    SciTech Connect

    Zhou, W.; Sasaki, K; Su, D; Zhu, Y; Wang, J; Adzic, R

    2010-01-01

    Gram-scale synthesis of Pt{sub ML} electrocatalysts with a well-defined core-shell structure has been carried out using method involving galvanic displacement of an underpotential deposition Cu layer. The Pt shell thickness can be controlled by stepwise deposition. The Pt{at}Pd{sub 2}Co/C nanoparticles were characterized by X-ray powder diffraction, aberration-corrected scanning transmission electron microscopy, high-resolution energy-loss spectrometry, and in situ X-ray absorption spectroscopy. A complete Pt shell of 0.6 nm on a Pd{sub 2}Co core has been confirmed. The Pt{at}Pd{sub 2}Co/C core-shell electrocatalysts showed a very high activity for the oxygen reduction reaction; the Pt mass and specific activity were 0.72 A mg{sub Pt}{sup -1} and 0.5 mA cm{sup -2}, respectively (3.5 and 2.5 times higher than the corresponding values for commercial Pt catalysts), at 0.9 V in 0.1 M HClO{sub 4} at room temperature. In an accelerated potential cycling test, a loss in active surface area and a decrease in catalytic activity for gram-scale-synthesized Pt{sub ML} catalysts were also determined.

  3. Band structures of nonmagnetic transition-metal oxides: PdO and PtO

    SciTech Connect

    Hass, K.C. ); Carlsson, A.E. )

    1992-08-15

    The electronic band structures of PdO and PtO are calculated using the augmented-spherical-wave method and the local-density approximation. Our results are consistent with the widely held view of these materials as conventional band insulators with the crystal-field splitting of metal {ital d} states primarily responsible for gap formation. A significant role for correlation effects as well cannot be ruled out. The predicted valence-band structure for PdO agrees well with published photoemission data. The electronic structure of PtO is qualitatively similar. In both cases the calculated gap is direct and occurs at the {ital M} point of the Brillouin zone. The magnitude of the gap is found to be larger in PtO, which we attribute to the more relativistic nature of Pt compared to Pd.

  4. Millimeter thick ionic polymer membrane-based IPMCs with bimetallic Pd-Pt electrodes

    NASA Astrophysics Data System (ADS)

    Palmre, Viljar; Kim, Sung Jun; Kim, Kwang

    2011-04-01

    Ionic polymer metal composites (IPMC) are a low-voltage driven Electroactive Polymers (EAP) that can be used as actuators or sensors. This paper presents a comparative study of millimeter thick ionic polymer membrane-based IPMCs with high-performance Pd-Pt electrodes and conventional Pt electrodes. IPMCs assembled with different electrodes are characterized in terms of electromechanical, -chemical and mechanolelectrical properties. The SEM and energy dispersive X-ray (EDS) analysis are used to investigate the distribution of deposited electrode metals in the cross-section of Pd-Pt IPMCs. The study shows that IPMCs assembled with millimeter thick ionic polymer membranes and bimetallic Pd-Pt electrodes are superior in mechanoelectrical sensing and, also, show considerably higher blocking forces compared to the conventional type of IPMCs. Blocking forces more than 30 grams are measured under 4V DC. However, the actuation response is slower than conventional IPMCs having approximately 0.2-0.3 mm thickness.

  5. PdPt bimetallic nanoparticles enabled by shape control with halide ions and their enhanced catalytic activities

    NASA Astrophysics Data System (ADS)

    Zhang, Jinfeng; Wan, Lei; Liu, Lei; Deng, Yida; Zhong, Cheng; Hu, Wenbin

    2016-02-01

    In this study, a new and convenient one step approach is described for synthesizing shape controlled PdPt bimetallic nanoparticles. It is found that the resultant morphologies of these PdPt nanoparticles can be well controlled by simply altering the participation of different halide ions that serve as shape controlling agents in the reaction solution. The dendritic core-shell PdPt bimetallic nanoparticles generated with Pt atoms adopt usual island growth pattern in the presence of Cl- ions, whereas the introduction of Br- ions with a relatively strong adsorption effect facilitate the formation of a layered core-shell structure due to the layered growth mode of Pt atoms on the exterior surface of the central Pd core. Moreover, the stronger adsorption function of I- ions and the resulting fast atomic diffusion promoted the generation of mesoporous core-shell PdPt bimetallic nanoparticles with many pore channels. In addition, the size of these synthesized PdPt nanoparticles exhibited a significant dependence on the concentration of the halide ions involved. Due to their specific structural features and synergistic effects, these PdPt catalysts exhibited shape-dependent catalytic performance and drastically enhanced electrocatalytic activities relative to that of commercial Pt black and Pt/C toward methanol oxidation.In this study, a new and convenient one step approach is described for synthesizing shape controlled PdPt bimetallic nanoparticles. It is found that the resultant morphologies of these PdPt nanoparticles can be well controlled by simply altering the participation of different halide ions that serve as shape controlling agents in the reaction solution. The dendritic core-shell PdPt bimetallic nanoparticles generated with Pt atoms adopt usual island growth pattern in the presence of Cl- ions, whereas the introduction of Br- ions with a relatively strong adsorption effect facilitate the formation of a layered core-shell structure due to the layered growth

  6. Morphology, dimension, and composition dependence of thermodynamically preferred atomic arrangements in Ag-Pt nanoalloys.

    PubMed

    Deng, Lei; Deng, Huiqiu; Xiao, Shifang; Tang, Jianfeng; Hu, Wangyu

    2013-01-01

    The present article is on Metropolis Monte Carlo simulations coupled with semiempirical potentials to obtain the thermodynamically preferred configurations of Ag-Pt nanoalloys. The effects of particle size, morphology or alloy composition on the surface segregation and the chemical ordering patterns were investigated. Surface segregation of Ag is observed in all Ag-Pt nanoalloys. Such segregation develops quickly as the increase of particle sizes or global Ag composition. Generally, Ag surface enrichment is more apparent for more open particles except for large sized icosahedron (ICO) nanoalloys. The most energetically favorable chemical ordering patterns gradually evolve from Pt-core/Ag-shell to onion-like structures when the global Ag composition increases. Due to the site preference of Ag segregation, the presence of partly alloyed facets and Ag blocked vertices or edges at low global Ag compositions can modify the electronic and geometric structures on the nanoalloys' surface. The coupling between Pt and Ag sites is a topic of particular interest for catalysis. The detailed atomistic understanding of atomic arrangements in Ag-Pt nanoalloys is essential to intelligently design robust and active nanocatalysts with a low cost. PMID:24015590

  7. Bimetallic PdAg nanoparticle arrays from monolayer films of diblock copolymer micelles

    NASA Astrophysics Data System (ADS)

    Ehret, E.; Beyou, E.; Mamontov, G. V.; Bugrova, T. A.; Prakash, S.; Aouine, M.; Domenichini, B.; Cadete Santos Aires, F. J.

    2015-07-01

    The self-assembly technique provides a highly efficient route to generate well-ordered structures on a nanometer scale. In this paper, well-ordered arrays of PdAg alloy nanoparticles on flat substrates with narrow distributions of particle size (6-7 nm) and interparticle spacing (about 60 nm) were synthesized by the block copolymer micelle approach. A home-made PS-b-P4VP diblock copolymer was prepared to obtain a micellar structure in toluene. Pd and Ag salts were then successfully loaded in the micellar core of the PS-b-P4VP copolymer. A self-assembled monolayer of the loaded micelles was obtained by dipping the flat substrate in the solution. At this stage, the core of the micelles was still loaded with the metal precursor rather than with a metal. Physical and chemical reducing methods were used to reduce the metal salts embedded in the P4VP core into PdAg nanoparticles. HRTEM and EDX indicated that Pd-rich PdAg alloy nanoparticles were synthesized by chemical or physical reduction; UV-visible spectroscopy observations confirmed that metallic PdAg nanoparticles were quickly formed after chemical reduction; XPS measurements revealed that the PdAg alloy nanoparticles were in a metallic state after a short time of exposure to O2 plasma and after hydrazine reduction.

  8. Stellated Ag-Pt bimetallic nanoparticles: An effective platform for catalytic activity tuning

    NASA Astrophysics Data System (ADS)

    Liu, Hui; Ye, Feng; Yao, Qiaofeng; Cao, Hongbin; Xie, Jianping; Lee, Jim Yang; Yang, Jun

    2014-02-01

    The usefulness of Pt-based nanomaterials for catalysis can be greatly enhanced by coupling morphology engineering to the strategic presence of a second or even third metal. Here we demonstrate the design and preparation of stellated Ag-Pt bimetallic nanoparticles where significant activity difference between the methanol oxidation reaction (MOR) and the oxygen reduction reaction (ORR) may be realized by relegating Ag to the core or by hollowing out the core. In particular the stellated Pt surface, with an abundance of steps, edges, corner atoms, and {111} facets, is highly effective for the ORR but is ineffective for MOR. MOR activity is only observed in the presence of a Ag core through electronic coupling to the stellated Pt shell. The bimetallic Ag-Pt stellates therefore demonstrate the feasibility of tuning a Pt surface for two very different structure sensitive catalytic reactions. Stellated bimetallics may therefore be an effective platform for highly tunable catalyst designs.

  9. Stellated Ag-Pt bimetallic nanoparticles: An effective platform for catalytic activity tuning

    PubMed Central

    Liu, Hui; Ye, Feng; Yao, Qiaofeng; Cao, Hongbin; Xie, Jianping; Lee, Jim Yang; Yang, Jun

    2014-01-01

    The usefulness of Pt-based nanomaterials for catalysis can be greatly enhanced by coupling morphology engineering to the strategic presence of a second or even third metal. Here we demonstrate the design and preparation of stellated Ag-Pt bimetallic nanoparticles where significant activity difference between the methanol oxidation reaction (MOR) and the oxygen reduction reaction (ORR) may be realized by relegating Ag to the core or by hollowing out the core. In particular the stellated Pt surface, with an abundance of steps, edges, corner atoms, and {111} facets, is highly effective for the ORR but is ineffective for MOR. MOR activity is only observed in the presence of a Ag core through electronic coupling to the stellated Pt shell. The bimetallic Ag-Pt stellates therefore demonstrate the feasibility of tuning a Pt surface for two very different structure sensitive catalytic reactions. Stellated bimetallics may therefore be an effective platform for highly tunable catalyst designs. PMID:24495979

  10. PdCuPt Nanocrystals with Multibranches for Enzyme-Free Glucose Detection.

    PubMed

    Fu, Shaofang; Zhu, Chengzhou; Song, Junhua; Engelhard, Mark; Xia, Haibing; Du, Dan; Lin, Yuehe

    2016-08-31

    By carefully controlling the synthesis condition, branched PtCu bimetallic templates were synthesized in aqueous solution. After the galvanic replacement reaction between PtCu templates and the Pt precursors, PdCuPt trimetallic nanocrystals with branched structures were obtained. Owing to the open structure and the optimized composition, the electrochemical experimental results reveal that the PdCuPt trimetallic nanocrystals possess high electrocatalytic activity, selectivity and stability for the oxidation of glucose in alkaline solution. In detail, a detection limit of 1.29 μM and a sensitivity of 378 μA/mM/cm(2) are achieved. The good electrocatalytic performance should be attributed to the unique branched nanostructure as well as the synergistic effect among metals. The superior catalytic properties suggest that these nanocrystals are promising for enzyme-free detection of glucose. PMID:27494365

  11. Mechanism of coercivity enhancement by Ag addition in FePt-C granular films for heat assisted magnetic recording media

    SciTech Connect

    Varaprasad, B. S. D. Ch. S.; Takahashi, Y. K. Wang, J.; Hono, K.; Ina, T.; Nakamura, T.; Ueno, W.; Nitta, K.; Uruga, T.

    2014-06-02

    We investigated the Ag distribution in a FePtAg-C granular film that is under consideration for a heat assisted magnetic recording medium by aberration-corrected scanning transmission electron microscope-energy dispersive X-ray spectroscopy and X-ray absorption fine structure. Ag is rejected from the core of FePt grains during the deposition, forming Ag-enriched shell surrounding L1{sub 0}-ordered FePt grains. Since Ag has no solubility in both Fe and Pt, the rejection of Ag induces atomic diffusions thereby enhancing the kinetics of the L1{sub 0}-order in the FePt grains.

  12. Mixed-phase Pd-Pt bimetallic alloy on graphene oxide with high activity for electrocatalytic applications

    NASA Astrophysics Data System (ADS)

    Khan, Majid; Yousaf, Ammar Bin; Chen, Mingming; Wei, Chengsha; Wu, Xibo; Huang, Ningdong; Qi, Zeming; Li, Liangbin

    2015-05-01

    Bimetallic PdPt alloy nanoparticles on graphene oxide (GO) have been prepared by a simple and facile chemical route, in which the reduction of metal precursors is carried out using CO as a reductant. Structural and morphological characterizations of GO/PdPt composites are performed using X-ray diffraction, X-ray photoelectron spectroscopy analysis and transmission electron microscopy. It is found that PdPt bimetallic nanoparticles are successfully synthesized and uniformly attached on the graphene sheets. The electrocatalytic and electrochemical properties of GO/PdPt composites including methanol oxidation reaction (MOR), oxygen reduction reaction (ORR) and methanol tolerant oxygen reduction reaction (MTORR) are studied in HClO4 aqueous solution. A significant improvement in the electrocatalytic activities is observed by increasing the atomic ratio of Pt in PdPt bimetallic alloys compared to the freestanding Pd nanoparticles on GO. The prepared GO/PdPt composites with an (Pd:Pt) atomic ratio of 40:60 exhibits higher methanol oxidation activity, higher specific ORR activity and better tolerance to CO poisoning. The results can be attributed to the collective effects of the PdPt nanoparticles and the enhanced electron transfer of graphene.

  13. SERS monitoring of Pd-catalysed reduction processes of nitroarenes adsorbed on Ag/Pd colloidal nanoparticles

    NASA Astrophysics Data System (ADS)

    Muniz-Miranda, Maurizio; Pergolese, Barbara; Bigotto, Adriano

    2006-05-01

    The catalytic activity of palladium has been verified in Ag/Pd colloids for two different nitroarenes, 2-amino,5-nitropyridine (ANP) and 4-nitrobenzoic acid (PNBA). Palladium, deposited as nanoclusters onto the silver core, can act as catalyst for the ligands, while silver ensures the SERS enhancement, which is necessary to detect the Raman spectra of the adsorbates. The SERS measurements show that the nitrogroup of ANP is reduced to aminogroup in Ag/Pd colloids, whereas, in the case of PNBA, the azo-derivative is obtained as stable product.

  14. Size-dependent adhesion energy of shape-selected Pd and Pt nanoparticles

    NASA Astrophysics Data System (ADS)

    Ahmadi, M.; Behafarid, F.; Cuenya, B. Roldan

    2016-06-01

    Thermodynamically stable shape-selected Pt and Pd nanoparticles (NPs) were synthesized via inverse micelle encapsulation and a subsequent thermal treatment in vacuum above 1000 °C. The majority of the Pd NPs imaged via scanning tunneling microscopy (STM) had a truncated octahedron shape with (111) top and interfacial facets, while the Pt NPs were found to adopt a variety of shapes. For NPs of identical shape for both material systems, the NP-support adhesion energy calculated based on STM data was found to be size-dependent, with large NPs (e.g. ~6 nm) having lower adhesion energies than smaller NPs (e.g. ~1 nm). This phenomenon was rationalized based on support-induced strain that for larger NPs favors the formation of lattice dislocations at the interface rather than a lattice distortion that may propagate through the smaller NPs. In addition, identically prepared Pt NPs of the same shape were found to display a lower adhesion energy compared to Pd NPs. While in both cases, a transition from a lattice distortion to interface dislocations is expected to occur with increasing NP size, the higher elastic energy in Pt leads to a lower transition size, which in turn lowers the adhesion energy of Pt NPs compared to Pd.Thermodynamically stable shape-selected Pt and Pd nanoparticles (NPs) were synthesized via inverse micelle encapsulation and a subsequent thermal treatment in vacuum above 1000 °C. The majority of the Pd NPs imaged via scanning tunneling microscopy (STM) had a truncated octahedron shape with (111) top and interfacial facets, while the Pt NPs were found to adopt a variety of shapes. For NPs of identical shape for both material systems, the NP-support adhesion energy calculated based on STM data was found to be size-dependent, with large NPs (e.g. ~6 nm) having lower adhesion energies than smaller NPs (e.g. ~1 nm). This phenomenon was rationalized based on support-induced strain that for larger NPs favors the formation of lattice dislocations at the

  15. Component conversion from pure Au nanorods to multiblock Ag-Au-Ag nanorods assisted by Pt nanoframe templates.

    PubMed

    Lee, Sangji; Jang, Hee-Jeong; Jang, Ho Young; Kim, Seong Kyu; Park, Sungho

    2016-07-14

    We developed a new method for synthesizing multiblock Ag-Au-Ag nanorods using Pt nanoframes that had been deposited on the edges of Au nanorod seeds. As a function of Au etching time, the length of the Au nanorod decreased symmetrically starting from the two ends, leading to the formation of empty inner space at the ends. Subsequent reduction of Ag ions could be selectively performed in the inner space confined by Pt nanoframes and the resulting Ag-Au-Ag nanorods exhibited characteristic LSPR modes originating from each block component (in a transverse direction) and SPR coupling (in a longitudinal direction). The high quality of the resulting multiblock nanorods enabled observation of the longitudinal quadrupole mode that was induced by Ag-Au SPR coupling in a long axis. The mode exhibited high sensitivity in accordance with the change in the surrounding media, demonstrating great potential for sensor applications. PMID:27315144

  16. Nanoporous PtAg and PtCu alloys with hollow ligaments for enhanced electrocatalysis and glucose biosensing.

    PubMed

    Xu, Caixia; Liu, Yunqing; Su, Fa; Liu, Aihua; Qiu, Huajun

    2011-09-15

    Nanoporous silver (NPS) and copper (NPC) obtained by dealloying AgAl and CuAl alloys, respectively, were used as both three-dimensional templates and reducing agents for the fabrication of nanoporous PtAg (NPS-Pt) and PtCu (NPC-Pt) alloys with hollow ligaments by a simple galvanic replacement reaction with H(2)PtCl(6). Electron microscopy and X-ray diffraction characterizations demonstrate that NPS and NPC with similar ligament sizes (30-50 nm) have different effects on the formed hollow nanostructures. For NPS-Pt, the shell of the hollow ligament is seamless. However, the shell of NPC-Pt is comprised of small pores and alloy nanoparticles with a size of ∼3 nm. The as-prepared NPS-Pt and NPC-Pt exhibit remarkably improved electrocatalytic activities towards the oxidation of ethanol and H(2)O(2) compared with state-of-the-art Pt/C catalyst, and can be used for sensitive electrochemical sensing applications. The hierarchical nanoporous structure also provides a good microenvironment for enzymes. After immobilization of glucose oxidase (GOx), the enzyme modified nanoporous electrode can sensitively detect glucose in a wide linear range (0.6-20 mM). PMID:21778046

  17. Physical properties of FePt nanocomposite doped with Ag atoms: First-principles study

    NASA Astrophysics Data System (ADS)

    Jia, Yong-Fei; Shu, Xiao-Lin; Xie, Yong; Chen, Zi-Yu

    2014-07-01

    L10 FePt nanocomposite with high magnetocrystalline anisotropy energy has been extensively investigated in the fields of ultra-high density magnetic recording media. However, the order—disorder transition temperature of the nanocomposite is higher than 600 °C, which is a disadvantage for the use of the material due to the sustained growth of FePt grain under the temperature. To address the problem, addition of Ag atoms has been proposed, but the magnetic properties of the doped system are still unclear so far. Here in this paper, we use first-principles method to study the lattice parameters, formation energy, electronic structure, atomic magnetic moment and order—disorder transition temperature of L10 FePt with Ag atom doping. The results show that the formation energy of a Ag atom substituting for a Pt site is 1.309 eV, which is lower than that of substituting for an Fe site 1.346 eV. The formation energy of substituting for the two nearest Pt sites is 2.560 eV lower than that of substituting for the further sites 2.621 eV, which indicates that Ag dopants tend to segregate L10 FePt. The special quasirandom structures (SQSs) for the pure FePt and the FePt doped with two Ag atoms at the stable Pt sites show that the order—disorder transition temperatures are 1377 °C and 600 °C, respectively, suggesting that the transition temperature can be reduced with Ag atom, and therefore the FePt grain growth is suppressed. The saturation magnetizations of the pure FePt and the two Ag atoms doped FePt are 1083 emu/cc and 1062 emu/cc, respectively, indicating that the magnetic property of the doped system is almost unchanged.

  18. Phase stability and magnetism in NiPt and NiPd alloys

    NASA Astrophysics Data System (ADS)

    Paudyal, Durga; Mookerjee, Abhijit

    2004-08-01

    We show that the differences in stability of 3d-5d NiPt and 3d-4d NiPd alloys arise mainly due to relativistic corrections. The magnetic properties of disordered NiPd and NiPt alloys also differ due to these corrections, which lead to increase in the separation between the s-d bands of 5d elements in these alloys. For the magnetic case we also analyse the results in terms of splitting of majority and minority spin d band centres of the 3d elements. We further examine the effect of relativistic corrections to the pair energies and order-disorder transition temperatures in these alloys. The magnetic moments and Curie temperatures have also been studied along with the short range ordering/segregation effects in NiPt/NiPd alloys.

  19. To the mechanism coarsening of Ostwald ripening of Pt, Pd catalysts and their compounds

    NASA Astrophysics Data System (ADS)

    Vengrenovich, R. D.; Ivanskii, B. V.; Panko, I. I.; Fesiv, I. V.; Kryvetskyi, V. I.; Stasyk, M. O.

    2015-11-01

    A comparison between the generalized Chakraverty-Wagner and Lifshits-Slyozov-Wagner distributions with experimental histograms for Pt, Pd -nanocrystals and their compounds has been performed according to the modified LSW theory applied to the surface (2D) and bulk (3D) systems. Pt and Pd nanocrystals were synthesized and deposited from vapor phase and a liquid solution. Good correlation between the experimental histograms and the theoretical curves proves that two mechanisms of the nanocrystals' growth (dissolution) can be involved simultaneously during the Ostwald ripening stage. One of them is controlled by diffusion, while the chemical reaction rate controls the other mechanism. Details of comparison between the experimental histograms and theoretical curves prove that growth of Pt and Pd -nanoparticles is controlled mainly by the chemical reaction rate (i.e. Wagner's mechanism) regardless of the synthesis method in the process of Ostwald ripening.

  20. A Comprehensive Search for Stable Pt-Pd Nanoalloy Configurations and Their Use as Tunable Catalysts

    SciTech Connect

    Tan, Teck L.; Wang, Lin-Lin; Johnson, Duane D.; Bai, Kewu

    2012-08-15

    Using density-functional theory, we predict stable alloy configurations (ground states) for a 1 nm Pt–Pd cuboctahedral nanoparticle across the entire composition range and demonstrate their use as tunable alloy catalysts via hydrogen-adsorption studies. Unlike previous works, we use simulated annealing with a cluster expansion Hamiltonian to perform a rapid and comprehensive search that encompasses both high and low-symmetry configurations. The ground states show Pt(core)–Pd(shell) type configurations across all compositions but with specific Pd patterns. For catalysis studies at room temperatures, the ground states are more realistic structural models than the commonly assumed random alloy configurations. Using the ground states, we reveal that the hydrogen adsorption energy increases (decreases) monotonically with at. % Pt for the {111} hollow ({100} bridge) adsorption site. Such trends are useful for designing tunable Pd–Pt nanocatalysts for the hydrogen evolution reaction.

  1. Component conversion from pure Au nanorods to multiblock Ag-Au-Ag nanorods assisted by Pt nanoframe templates

    NASA Astrophysics Data System (ADS)

    Lee, Sangji; Jang, Hee-Jeong; Jang, Ho Young; Kim, Seong Kyu; Park, Sungho

    2016-06-01

    We developed a new method for synthesizing multiblock Ag-Au-Ag nanorods using Pt nanoframes that had been deposited on the edges of Au nanorod seeds. As a function of Au etching time, the length of the Au nanorod decreased symmetrically starting from the two ends, leading to the formation of empty inner space at the ends. Subsequent reduction of Ag ions could be selectively performed in the inner space confined by Pt nanoframes and the resulting Ag-Au-Ag nanorods exhibited characteristic LSPR modes originating from each block component (in a transverse direction) and SPR coupling (in a longitudinal direction). The high quality of the resulting multiblock nanorods enabled observation of the longitudinal quadrupole mode that was induced by Ag-Au SPR coupling in a long axis. The mode exhibited high sensitivity in accordance with the change in the surrounding media, demonstrating great potential for sensor applications.We developed a new method for synthesizing multiblock Ag-Au-Ag nanorods using Pt nanoframes that had been deposited on the edges of Au nanorod seeds. As a function of Au etching time, the length of the Au nanorod decreased symmetrically starting from the two ends, leading to the formation of empty inner space at the ends. Subsequent reduction of Ag ions could be selectively performed in the inner space confined by Pt nanoframes and the resulting Ag-Au-Ag nanorods exhibited characteristic LSPR modes originating from each block component (in a transverse direction) and SPR coupling (in a longitudinal direction). The high quality of the resulting multiblock nanorods enabled observation of the longitudinal quadrupole mode that was induced by Ag-Au SPR coupling in a long axis. The mode exhibited high sensitivity in accordance with the change in the surrounding media, demonstrating great potential for sensor applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03484e

  2. PdPt bimetallic nanoparticles enabled by shape control with halide ions and their enhanced catalytic activities.

    PubMed

    Zhang, Jinfeng; Wan, Lei; Liu, Lei; Deng, Yida; Zhong, Cheng; Hu, Wenbin

    2016-02-21

    In this study, a new and convenient one step approach is described for synthesizing shape controlled PdPt bimetallic nanoparticles. It is found that the resultant morphologies of these PdPt nanoparticles can be well controlled by simply altering the participation of different halide ions that serve as shape controlling agents in the reaction solution. The dendritic core-shell PdPt bimetallic nanoparticles generated with Pt atoms adopt usual island growth pattern in the presence of Cl(-) ions, whereas the introduction of Br(-) ions with a relatively strong adsorption effect facilitate the formation of a layered core-shell structure due to the layered growth mode of Pt atoms on the exterior surface of the central Pd core. Moreover, the stronger adsorption function of I(-) ions and the resulting fast atomic diffusion promoted the generation of mesoporous core-shell PdPt bimetallic nanoparticles with many pore channels. In addition, the size of these synthesized PdPt nanoparticles exhibited a significant dependence on the concentration of the halide ions involved. Due to their specific structural features and synergistic effects, these PdPt catalysts exhibited shape-dependent catalytic performance and drastically enhanced electrocatalytic activities relative to that of commercial Pt black and Pt/C toward methanol oxidation. PMID:26511671

  3. Evaluation of the catalytic activity of Pd-Ag alloys on ethanol oxidation and oxygen reduction reactions in alkaline medium

    NASA Astrophysics Data System (ADS)

    Oliveira, M. C.; Rego, R.; Fernandes, L. S.; Tavares, P. B.

    2011-08-01

    Pd-Ag alloys containing different amounts of Ag (8, 21 and 34 at.%) were prepared in order to evaluate their catalytic activity towards the ethanol oxidation (EOR) and oxygen reduction (ORR) reactions. A sequential electroless deposition of Ag and Pd on a stainless steel disc, followed by annealing at 650 °C under Ar stream, was used as the alloy electrode deposition process. From half-cell measurements in a 1.0 M NaOH electrolyte at ≅20 °C, it was found that alloying Pd with Ag leads to an increases of the ORR and EOR kinetics, relative to Pd. Among the alloys under study, the 21 at.% Ag content alloy presents the highest catalytic activity for the EOR and the lowest Ag content alloy (8 at.% Ag) shows the highest ORR activity. Moreover, it was found that the selectivity of Pd-Ag alloys towards ORR is sustained when ethanol is present in the electrolyte.

  4. Transition voltages of vacuum-spaced and molecular junctions with Ag and Pt electrodes

    SciTech Connect

    Wu, Kunlin; Bai, Meilin; Hou, Shimin; Sanvito, Stefano

    2014-07-07

    The transition voltage of vacuum-spaced and molecular junctions constructed with Ag and Pt electrodes is investigated by non-equilibrium Green's function formalism combined with density functional theory. Our calculations show that, similarly to the case of Au-vacuum-Au previously studied, the transition voltages of Ag and Pt metal-vacuum-metal junctions with atomic protrusions on the electrode surface are determined by the local density of states of the p-type atomic orbitals of the protrusion. Since the energy position of the Pt 6p atomic orbitals is higher than that of the 5p/6p of Ag and Au, the transition voltage of Pt-vacuum-Pt junctions is larger than that of both Ag-vacuum-Ag and Au-vacuum-Au junctions. When one moves to analyzing asymmetric molecular junctions constructed with biphenyl thiol as central molecule, then the transition voltage is found to depend on the specific bonding site for the sulfur atom in the thiol group. In particular agreement with experiments, where the largest transition voltage is found for Ag and the smallest for Pt, is obtained when one assumes S binding at the hollow-bridge site on the Ag/Au(111) surface and at the adatom site on the Pt(111) one. This demonstrates the critical role played by the linker-electrode binding geometry in determining the transition voltage of devices made of conjugated thiol molecules.

  5. Geometric structures of thin film: Pt on Pd(110) and NiO on Ni(100)

    SciTech Connect

    Warren, O.L.

    1993-07-01

    This thesis is divided into 3 papers: dynamical low-energy electron- diffraction investigation of lateral displacements in topmost layer of Pd(110); determination of (1{times}1) and (1{times}2) structures of Pt thin films on Pd(110) by dynamical low-energy electron-diffraction analysis; and structural determination of a NiO(111) film on Ni(100) by dynamical low-energy electron-diffraction analysis.

  6. Reactions of Pd(II) and Pt(II) Complexes With Tetraethylthiouram Disulfide

    PubMed Central

    Cervantes, G.; Molins, E.; Miravitlles, C.

    1997-01-01

    The reactions of tetraethylthiouram disulfide (DTS), an inhibitor of the nephrotoxicity of Pt(II) drugs, an efficient agent in the treatment of chronic alcoholism, in the treatment of HIV infections, AIDS and heavy metal toxicity, and a fungicide and herbicide, with K2[PtCl4], in ratio 1:1 and 1:2, gave the compounds [PtCl2DTS] and [Pt(S2CNEt2)2] respectively. The reaction of the complexes K2[PdCl4], Pd(AcO)2 and [PdCl2(PhCN)2], where PhCN = Benzonitrile, with tetraethylthiouram disulfide in ratio 1:1 or 1:2, yielded orange crystals identified as [Pd(S2CNEt2)2]. The crystals were suitable for study by X-ray diffraction. The -S-S- bridge in the tetraethylthiouram disulfude molecule was broken and the two molecules of the thiocarbamate derivative were bound to the Pd(II) by the equivalents sulfur atoms. All the compounds were characterized by IR, 1H and 13C NMR spectroscopies. PMID:18475812

  7. The Effect of Sulfur Fugacity on Pt, Pd and Au in Magmatic-Hydrothermal Systems

    NASA Astrophysics Data System (ADS)

    Bell, A.; Simon, A.

    2009-05-01

    We have constrained experimentally the effect of sulfur fugacity (fS2) and sulfide saturation on the fractionation and partitioning behavior of Pt, Pd and Au in a felsic silicate melt + sulfide crystal/melt + oxide + supercritical aqueous fluid phase + Pt + Pd + Au system. Experiments were performed at 800°C, 150 MPa, with oxygen fugacity (fO2) fixed at approximately the nickel + nickel oxide buffer (NNO). Sulfur fugacity in the experiments was varied five orders of magnitude from approximately logfS2 = 0 to logfS2 = -5 by using two different sulfide phase assemblages. Sulfide assemblage one consisted initially of chalcopyrite plus pyrrhotite and assemblage two consisted of chalcopyrite plus bornite. At run conditions, in both assemblages, pyrrhotite transformed compositionally to monosulfide solid solution (mss), chalcopyrite to intermediate solid solution (Iss), and in assemblage two chalcopyrite and bornite formed a sulfide melt. Run- product silicate glass (i.e., quenched silicate melt) and crystalline materials were analyzed by using both electron probe microanalysis (EPMA) for major elements and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for major and trace elements. The measured concentrations of Pt, Pd, and Au in quenched silicate melt in runs with logfS2 values ranging from approximately 0 to -5, do not exhibit any apparent dependence on the dissolved sulfur content of the melt. The measured Pt, Pd and Au concentrations in mss vary as a function of fS2. The measured Pt, Pd and Au concentrations in Iss do not appear to be dependent on fS2. The system variables fS2 and fO2, working in concert with each other, control the stable magmatic sulfide phase assemblage. Additionally, the system fS2 strongly influences the solubility of Pt, Pd, and Au as lattice bound components in some common crystalline magmatic sulfide phases. Both the stable magmatic sulfide phase assemblage and the solubility of Pt, Pd, and Au as constituents in

  8. Size-dependent adhesion energy of shape-selected Pd and Pt nanoparticles.

    PubMed

    Ahmadi, M; Behafarid, F; Cuenya, B Roldan

    2016-06-01

    Thermodynamically stable shape-selected Pt and Pd nanoparticles (NPs) were synthesized via inverse micelle encapsulation and a subsequent thermal treatment in vacuum above 1000 °C. The majority of the Pd NPs imaged via scanning tunneling microscopy (STM) had a truncated octahedron shape with (111) top and interfacial facets, while the Pt NPs were found to adopt a variety of shapes. For NPs of identical shape for both material systems, the NP-support adhesion energy calculated based on STM data was found to be size-dependent, with large NPs (e.g. ∼6 nm) having lower adhesion energies than smaller NPs (e.g. ∼1 nm). This phenomenon was rationalized based on support-induced strain that for larger NPs favors the formation of lattice dislocations at the interface rather than a lattice distortion that may propagate through the smaller NPs. In addition, identically prepared Pt NPs of the same shape were found to display a lower adhesion energy compared to Pd NPs. While in both cases, a transition from a lattice distortion to interface dislocations is expected to occur with increasing NP size, the higher elastic energy in Pt leads to a lower transition size, which in turn lowers the adhesion energy of Pt NPs compared to Pd. PMID:27216883

  9. Plasma Syntheses of Carbon Nanotube-Supported Pt-Pd Nanoparticles

    NASA Astrophysics Data System (ADS)

    Song, Ye; Wang, Qi; Meng, Yuedong

    2016-04-01

    It is reported that the highly dispersed Pt nanoparticles on carbon nanotubes can be synthesized under mild conditions by in situ plasma treatment. The carbon nanotube was pretreated by O2 plasma to transform into oxide carbon nanotubes (O-CNTs), and then it was mixed with the precursors (the mixture of H2PtCl6 and PdCl6). After that, the O-CNTs and the precursors were simultaneously treated by H2 plasma. The precursors were transformed into Pt-Pd nanoparticles (NPs) and the O-CNTs transformed into CNT. The synthesized CNT-based Pt-Pd nanoparticles were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. All the analysis showed that the Pt-Pd nanoparticles were deposited on CNT as a form of face-centered cubical structure. supported by National Natural Science Foundation of China (Nos. 11305218,11575253), the Youth Innovation Promotion Association of the Chinese Academy of Sciences (No. 2015262), the CASHIPS Director's Fund (No. YZJJ201505) and Anhui Provincial Natural Science Foundation for Distinguished Young Scholars of China (No. 1608085J03)

  10. Formation of Ag-Pd contacts on Y-Ba-CuO ceramic and contact properties

    NASA Astrophysics Data System (ADS)

    Gartsman, K. G.; Duguzhev, Sh. M.; Parfen'eva, L. S.; Smirnov, I. A.

    1991-01-01

    Ag-Pd (30 pct Pd) contacts were formed on pellets of Y-Ba-CuO ceramic in the process of powder compaction by pressing a thin layer of Ag-Pd alloy, deposited on a 6-micron-thick organic film, to the end surfaces of the ceramic pellet. Cold pressing was followed by annealing, during which the organic substrate burned out and a bond was formed between the ceramic and the metal alloy. The resistance of the contacts produced by this method is 0.0026 ohm/sq cm, which is significantly better than that of contacts produced by using silver pastes.

  11. Alloying of Co ultrathin films on Pt(111) with Ag buffer layers

    NASA Astrophysics Data System (ADS)

    Shern, C. S.; Su, C. W.; Wu, Y. E.; Fu, T. Y.

    2000-07-01

    The structure at the interfaces of Co/Ag/Pt(111) was studied by low-energy electron diffraction, ultraviolet photoelectron spectroscopy, Auger electron spectroscopy, and depth profiling. An atomic exchange occurs between Co and Ag before the formation of a Co-Pt alloy. Ag atoms start moving to the top at 425 K when the coverage of Co is one monolayer. The temperature of the complete exchange between Ag atoms and Co atoms is dependent on the thickness of the Ag buffer layer. The Co-Pt alloy develops after the atomic exchange is complete. The especially small surface free energy of Ag and large strain energy in this system are proposed as the driving force for the exchange.

  12. Magnetic properties of Ag/Co/Pt( 1 1 1 ) ultrathin films

    NASA Astrophysics Data System (ADS)

    Su, C. W.; Chen, F. C.; Wu, Y. E.; Shern, C. S.

    2002-06-01

    The magnetic anisotropy of Ag/Co/Pt(1 1 1) ultrathin films was studied by the surface magneto-optic Kerr effect. Some interesting magnetic properties were observed. The location of Ag atoms on Co sites seems to prevent the spin reversal of Co. The saturated magnetization is not significantly changed after Ag ultrathin films are deposited on the Co/Pt(1 1 1) surfaces. The Curie temperatures increase after the Ag ultrathin film deposition. During thermal annealing, the out-of-plane magnetization in the Ag capped films is enhanced dramatically. The structural changes and the evolution of the chemical composition at the interfaces during the annealing were studied by low-energy electron diffraction and Auger electron spectroscopy, respectively. The giant enhancement of the out-of-plane magnetization is due to the formation of Co-Pt alloy and Ag overlayer improving the interface structure.

  13. Crystallinity-induced shape evolution of Pt-Ag nanosheets from branched nanocrystals.

    PubMed

    Mahmood, Azhar; Saleem, Faisal; Lin, Haifeng; Ni, Bing; Wang, Xun

    2016-08-18

    Crystallinity offers countless opportunities for the controlled synthesis of multimetallic 2D and 3D nanomaterials. Herein we have successfully synthesized 2D Pt-Ag ultrathin nanosheets through the oxidative etching of twin seeds and 3D Pt-Ag-Cu tetrapods via altering the crystallinity through the incorporation of copper into the Pt-Ag alloy. A better electrocatalytic activity is obtained for the oxidation of formic acid which is 3.8 times higher than that of a commercial platinum catalyst as the stepped surface atom densities are higher on the nanosheets. PMID:27494004

  14. Novel PdAgCu ternary alloy: Hydrogen permeation and surface properties

    NASA Astrophysics Data System (ADS)

    Tarditi, Ana M.; Braun, Fernando; Cornaglia, Laura M.

    2011-05-01

    Dense PdAgCu ternary alloy composite membranes were synthesized by the sequential electroless plating of Pd, Ag and Cu on top of both disk and tubular porous stainless steel substrates. X-ray diffraction and scanning electron microscopy were employed to study the structure and morphology of the tested samples. The hydrogen permeation performance of these membranes was investigated over a 350-450 °C temperature range and a trans-membrane pressure up to 100 kPa. After annealing at 500 °C in hydrogen stream followed by permeation experiments, the alloy layer presented a FCC crystalline phase with a bulk concentration of 68% Pd, 7% Ag and 25% Cu as revealed by EDS. The PdAgCu tubular membrane was found to be stable during more than 300 h on hydrogen stream. The permeabilities of the PdAgCu ternary alloy samples were higher than the permeabilities of the PdCu alloy membranes with a FCC phase. The co-segregation of silver and copper to the membrane surface was observed after hydrogen permeation experiments at high temperature as determined by XPS.

  15. High electrocatalytic activity of Pt-Pd binary spherocrystals chemically assembled in vertically aligned TiO2 nanotubes.

    PubMed

    Lei, Yanzhu; Zhao, Guohua; Tong, Xili; Liu, Meichuan; Li, Dongming; Geng, Rong

    2010-01-18

    To obtain noble metal catalysts with high efficiency, long-term stability, and poison resistance, Pt and Pd are assembled in highly ordered and vertically aligned TiO(2) nanotubes (NTs) by means of the pulsed-current deposition (PCD) method with assistance of ultrasonication (UC). Here, Pd serves as a dispersant which prevents agglomeration of Pt. Thus Pt-Pd binary catalysts are embed into TiO(2) NTs array under UC in sunken patterns of composite spherocrystals (Sps). Owing to this synthesis method and restriction by the NTs, the these catalysts show improved dispersion, more catalytically active sites, and higher surface area. This nanotubular metallic support material with good physical and chemical stability prevents catalyst loss and poisoning. Compared with monometallic Pt and Pd, the sunken-structured Pt-Pd spherocrystal catalyst exhibits better catalytic activity and poison resistance in electrocatalytic methanol oxidation because of its excellent dispersion. The catalytic current density is enhanced by about 15 and 310 times relative to monometallic Pt and Pd, respectively. The poison resistance of the Pt-Pd catalyst was 1.5 times higher than that of Pt and Pd, and they show high electrochemical stability with a stable current enduring for more than 2100 s. Thus, the TiO(2) NTs on a Ti substrate serve as an excellent support material for the loading and dispersion of noble metal catalysts. PMID:19924757

  16. Pd@Pt Core–Shell Nanoparticles with Branched Dandelion-like Morphology as Highly Efficient Catalysts for Olefin Reduction

    EPA Science Inventory

    A facile synthesis based on the addition of ascorbic acid to a mixture of Na2PdCl4, K2PtCl6, and Pluronic P123 results in highly branched core–shell nanoparticles (NPs) with a micro–mesoporous dandelion-like morphology comprising Pd core and Pt shell. The slow reduction kinetics ...

  17. Interdiffusion and stress development in single-crystalline Pd/Ag bilayers

    NASA Astrophysics Data System (ADS)

    Noah, Martin A.; Flötotto, David; Wang, Zumin; Mittemeijer, Eric J.

    2016-04-01

    Interdiffusion and stress evolution in single-crystalline Pd/single-crystalline Ag thin films were investigated by Auger electron spectroscopy sputter-depth profiling and in-situ X-ray diffraction, respectively. The concentration-dependent chemical diffusion coefficient, as well as the impurity diffusion coefficient of Ag in Pd could be determined in the low temperature range of 356 °C-455 °C. As a consequence of the similarity of the strong concentration-dependences of the intrinsic diffusion coefficients, the chemical diffusion coefficient varies only over three orders of magnitude over the whole composition range, despite the large difference of six orders of magnitude of the self-diffusion coefficients of Ag in Ag and Pd in Pd. It is shown that the Darken-Manning treatment should be adopted for interpretation of the experimental data; the Nernst-Planck treatment yielded physically unreasonable results. Apart from the development of compressive thermal stress, the development of stress in both sublayers separately could be ascribed to compositional stress (tensile in the Ag sublayer and compressive in the Pd sublayer) and dominant relaxation processes, especially in the Ag sublayer. The effect of these internal stresses on the values determined for the diffusion coefficients is shown to be negligible.

  18. Study of Ag-Pd bimetallic nanoparticles modified glassy carbon electrode for detection of L-cysteine

    NASA Astrophysics Data System (ADS)

    Murugavelu, M.; Karthikeyan, B.

    2014-11-01

    Ag-Pd bimetallic nanoparticles (Ag-Pd BNPs) as an enhanced sensing material with improved electronic transmission rates in the electrochemical sensing of L-cysteine (L-cys) has been reported. The morphology of Ag-Pd BNPs was characterized with X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and cyclic voltammetry (CV). Oxidation of L-cys on Ag-Pd BNPs is investigated in detail by discussing the effect of the structure and from the electrocatalytic oxidation of L-cys. We found that the Ag-Pd BNPs exhibited high electrocatalytic activity towards L-cys oxidation in neutral condition and could be used for the development of nonenzymatic L-cys sensor. Based on the efficient catalytic ability of Ag-Pd BNPs, the fabricated biosensor exhibited a wide linear range of responses to the L-cys with the concentration detection limit of nearly down to 2 mM with fast response time.

  19. Relating adatom emission to improved durability of Pt-Pd diesel oxidation catalysts

    SciTech Connect

    Johns, Tyne Richele; Goeke, Ronald S.; Ashbacher, Valerie; Thune, Peter C.; Niemantsverdriet, J. W.; Kiefer, Boris; Kim, Chang H.; Balogh, Michael P.; Datye, Abhaya K.

    2015-06-05

    Sintering of nanoparticles is an important contributor to loss of activity in heterogeneous catalysts, such as those used for controlling harmful emissions from automobiles. But mechanistic details, such as the rates of atom emission or the nature of the mobile species, remain poorly understood. Herein we report a novel approach that allows direct measurement of atom emission from nanoparticles. We use model catalyst samples and a novel reactor that allows the same region of the sample to be observed after short-term heat treatments (seconds) under conditions relevant to diesel oxidation catalysts (DOCs). Monometallic Pd is very stable and does not sinter when heated in air (T ≤ 800 °C). Pt sinters readily in air, and at high temperatures (≥800 °C) mobile Pt species emitted to the vapor phase cause the formation of large, faceted particles. In Pt–Pd nanoparticles, Pd slows the rate of emission of atoms to the vapor phase due to the formation of an alloy. However, the role of Pd in Pt DOCs in air is quite complex: at low temperatures, Pt enhances the rate of Pd sintering (which otherwise would be stable as an oxide), while at higher temperature Pd helps to slow the rate of Pt sintering. DFT calculations show that the barrier for atom emission to the vapor phase is much greater than the barrier for emitting atoms to the support. Thus, vapor-phase transport becomes significant only at high temperatures while diffusion of adatoms on the support dominates at lower temperatures.

  20. Relating adatom emission to improved durability of Pt-Pd diesel oxidation catalysts

    DOE PAGESBeta

    Johns, Tyne Richele; Goeke, Ronald S.; Ashbacher, Valerie; Thune, Peter C.; Niemantsverdriet, J. W.; Kiefer, Boris; Kim, Chang H.; Balogh, Michael P.; Datye, Abhaya K.

    2015-06-05

    Sintering of nanoparticles is an important contributor to loss of activity in heterogeneous catalysts, such as those used for controlling harmful emissions from automobiles. But mechanistic details, such as the rates of atom emission or the nature of the mobile species, remain poorly understood. Herein we report a novel approach that allows direct measurement of atom emission from nanoparticles. We use model catalyst samples and a novel reactor that allows the same region of the sample to be observed after short-term heat treatments (seconds) under conditions relevant to diesel oxidation catalysts (DOCs). Monometallic Pd is very stable and does notmore » sinter when heated in air (T ≤ 800 °C). Pt sinters readily in air, and at high temperatures (≥800 °C) mobile Pt species emitted to the vapor phase cause the formation of large, faceted particles. In Pt–Pd nanoparticles, Pd slows the rate of emission of atoms to the vapor phase due to the formation of an alloy. However, the role of Pd in Pt DOCs in air is quite complex: at low temperatures, Pt enhances the rate of Pd sintering (which otherwise would be stable as an oxide), while at higher temperature Pd helps to slow the rate of Pt sintering. DFT calculations show that the barrier for atom emission to the vapor phase is much greater than the barrier for emitting atoms to the support. Thus, vapor-phase transport becomes significant only at high temperatures while diffusion of adatoms on the support dominates at lower temperatures.« less

  1. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    DOE PAGESBeta

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; Wu, Pu -Wei; Lee, Jyh -Fu

    2014-11-22

    Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1more » M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.« less

  2. Novel fine-disperse bimetallic Pt-Pd/Al2O3 catalysts for glycerol oxidation with molecular oxygen

    NASA Astrophysics Data System (ADS)

    Dubencovs, K.; Chornaja, S.; Sproge, E.; Kampars, V.; Markova, D.; Kulikova, L.; Serga, V.; Cvetkovs, A.

    2013-12-01

    Using extractive-pyrolytic method several Pt-Pd bimetallic catalysts supported on plasma-processed alumina nanopowder were synthesized. Pt-Pd loading and glycerol oxidation process parameter influence on catalyst activity and selectivity was determined oxidizing glycerol in mild conditions. Novel bimetallic catalysts in neutral water solutions were practically inactive (glycerol conversion was only 3%) whereas in alkaline solutions they were active and selective to glyceric acid. Using 1.2%Pt-1.2%Pd/Al2O3 catalyst glyceric acid was obtained with 65% selectivity (glycerol conversion was 96%). It was shown that novel fine-disperse bimetallic Pt-Pd/Al2O3 catalysts were more active compared to analogous monometallic Pt/Al2O3 and Pd/Al2O3 catalysts.

  3. Electronic and magnetic properties of X-doped (X=Ni, Pd, Pt) WS2 monolayer

    NASA Astrophysics Data System (ADS)

    Zhao, Xu; Xia, Congxin; Dai, Xianqi; Wang, Tianxing; Chen, Peng; Tian, Liang

    2016-09-01

    We investigate the electronic and magnetic properties of X-doped (X=Ni, Pd, Pt) WS2 monolayer using the first-principles methods based on density functional theory. The results show that WS2 monolayer doped by Ni, Pd and Pt is ferromagnetic. The impurity states near the Fermi level depend highly on the atomic size and electronegativity. For different X-doped WS2, the formation energy is lower under S-rich conditions, which indicates that it is energy favorable and relatively easier to incorporate X atom into WS2 under S-rich experimental conditions. Moreover, Ni-doped system owns the lowest formation energy compared with other atoms under S-rich experimental condition. Our studies predict X-doped (X=Ni, Pd, Pt) WS2 monolayers to be candidates for thin dilute magnetic semiconductors. Ni-doped WS2 has relatively wide half-metallic gap. So Ni-doped WS2 is the most ideal for spin injection among Ni, Pd, and Pt, which is important for application in semiconductor spintronics.

  4. High viscosity to highly dispersed PtPd bimetallic nanocrystals for enhanced catalytic activity and stability.

    PubMed

    Ying, Jie; Hu, Zhi-Yi; Yang, Xiao-Yu; Wei, Hao; Xiao, Yu-Xuan; Janiak, Christoph; Mu, Shi-Chun; Tian, Ge; Pan, Mu; Van Tendeloo, Gustaaf; Su, Bao-Lian

    2016-07-01

    A facile high-viscosity-solvent method is presented to synthesize PtPd bimetallic nanocrystals highly dispersed in different mesostructures (2D and 3D structures), porosities (large and small pore sizes), and compositions (silica and carbon). Further, highly catalytic activity, stability and durability of the nanometals have been proven in different catalytic reactions. PMID:27222099

  5. Electrochemistry of cholesterol biosensor based on a novel Pt-Pd bimetallic nanoparticle decorated graphene catalyst.

    PubMed

    Cao, Shurui; Zhang, Lei; Chai, Yaqin; Yuan, Ruo

    2013-05-15

    A new electrochemical biosensor with enhanced sensitivity was developed for detection of cholesterol by using platinum-palladium-chitosan-graphene hybrid nanocomposites (PtPd-CS-GS) functionalized glassy carbon electrode (GCE). An electrodeposition method was applied to form PtPd nanoparticles-doped chitosan-graphene hybrid nanocomposites (PtPd-CS-GS), which were characterized by scanning electron microscopy (SEM) and electrochemical methods. The presence of the PtPd-CS-GS nanocomposites not only accelerated direct electron transfer from the redox enzyme to the electrode surface, but also enhanced the immobilized amount of cholesterol oxidase (ChOx). Under optimal conditions, the fabricated biosensor exhibited wide linear ranges of responses to cholesterol in the concentration ranges of 2.2×10(-6) to 5.2×10(-4)M, the limit of detection was 0.75 μM (S/N=3). The response time was less than 7s and the Michaelis-Menten constant (Km(app)) was found as 0.11 mM. In addition, the biosensor also exhibited excellent reproducibility and stability. Along with these attractive features, the biosensor also displayed very high specificity to cholesterol with complete elimination of interference from UA, AA, and glucose. PMID:23618155

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

    EPA Science Inventory

    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...

  7. Atomistic modeling of ternary additions to NiTi and quaternary additions to Ni-Ti-Pd, Ni-Ti-Pt and Ni-Ti-Hf shape memory alloys

    NASA Astrophysics Data System (ADS)

    Mosca, H. O.; Bozzolo, G.; del Grosso, M. F.

    2012-08-01

    The behavior of ternary and quaternary additions to NiTi shape memory alloys is investigated using a quantum approximate method for the energetics. Ternary additions X to NiTi and quaternary additions to Ni-Ti-Pd, Ni-Ti-Pt, and Ni-Ti-Hf alloys, for X=Au, Pt, Ir, Os, Re, W, Ta,Ag, Pd, Rh, Ru, Tc, Mo, Nb, Zr, Zn, Cu, Co, Fe, Mn, V, Sc, Si, Al and Mg are considered. Bulk properties such as lattice parameter, energy of formation, and bulk modulus of the B2 alloys are studied for variations due to the presence of one or two simultaneous additives.

  8. A comparison study of oxygen reduction on the supported Pt, Pd, Au monolayer on WC(0001)

    NASA Astrophysics Data System (ADS)

    Zhang, Xilin; Lu, Zhansheng; Yang, Zongxian

    2016-07-01

    Using the first principles methods, the geometric and electronic structures of the metal monolayers supported on WC(0001) surfaces (MML/WC(0001) (M = Pt, Pd, and Au)) and their catalytic activity toward the oxygen reduction reaction (ORR) were comparatively studied. Both the kinetics and the density of states results demonstrated that the direct dissociation of O2 on all three MML/WC(0001) surfaces are almost impossible. Yet the barriers of the formation and dissociation of OOH on AuML/WC(0001) are much smaller than those on the PtML/WC(0001) and the PdML/WC(0001) surfaces, implying that the AuML/WC(0001) exhibits the highest catalytic activity for ORR via a combination of 2e- hydrogenation of O2 and 4e- dissociation of OOH. The rate-limiting step barrier of 0.83 eV for the hydrogenation of OH forming H2O is also comparable to that on the traditional Pt-based catalysts. The deactivation mechanism of PtML/WC(0001) and the performance of PdML/WC(0001) for ORR were identified. The present study is conductive to designing new efficient catalyst without using of the precious Pt for efficiently promoting ORR.

  9. Size and alloying induced changes in lattice constant, core, and valance band binding energy in Pd-Ag, Pd, and Ag nanoparticles: Effect of in-flight sintering temperature

    NASA Astrophysics Data System (ADS)

    Sengar, Saurabh K.; Mehta, B. R.; Govind

    2012-07-01

    In the present study, we report the growth of size selected Pd, Ag, and Pd-Ag alloy nanoparticles by an integrated method comprising of the gas phase synthesis, electrical mobility size selection, and in-flight sintering steps. Effect of temperature during in-flight sintering on nanoparticle size, crystal structure, and electronic properties has been studied. XRD studies show lattice expansion in Pd and Ag nanoparticles and lattice contraction in Pd-Ag alloy nanoparticles on increasing the sintering temperatures. In case of Pd and Ag nanoparticles, size induced changes in lattice constants are consistent with the changes in the binding energy positions with respect to bulk values. In case of Pd-Ag alloy nanoparticles, change in nanoparticle size and composition on sintering affect the lattice constant and binding energy positions. Large changes in Pd4d valance band centroid in Pd-Ag nanoparticles are due to size and alloying effects. The results of this study are important for understanding the correlation between electronic properties and Pd-H interaction in Pd alloy nanoparticles.

  10. Ultrathin Co/Pt and Co/Pd multilayered films as magneto-optical recording materials

    NASA Astrophysics Data System (ADS)

    Hashimoto, S.; Ochiai, Y.; Aso, K.

    1990-02-01

    Co/Pt and Co/Pd multilayered films were prepared by two-source dc magnetron sputtering. The multilayers with thin Co layers, one to three atoms thick, exhibited a perfect squareness of Kerr loop and an enhancement of Kerr rotation when the total film thickness became below several hundred angstroms. These ultrathin films have a high Kerr rotation of 0.2°-0.45° and strong perpendicular magnetic anisotropy even in the very thin-film thickness. The figure of merit of the ultrathin Co/Pt films is superior to that of TbFeCo system at 780 nm and becomes larger at shorter wavelength. The ultrathin multilayers possess very high corrosion resistance, and the layered structure is thermally stable up to 400 °C. Consequently, the ultrathin Co/Pt and Co/Pd multilayered films can be new magneto-optical recording materials, especially for higher density recording using a shorter wavelength laser.

  11. Synthesis and characteristics of Ag/Pt bimetallic nanocomposites by arc-discharge solution plasma processing.

    PubMed

    Pootawang, Panuphong; Saito, Nagahiro; Takai, Osamu; Lee, Sang-Yul

    2012-10-01

    Arc discharge in solution, generated by applying a high voltage of unipolar pulsed dc to electrodes of Ag and Pt, was used as a method to form Ag/Pt bimetallic nanocomposites via electrode erosion by the effects of the electric arc at the cathode (Ag rod) and the sputtering at the anode (Pt rod). Ag/Pt bimetallic nanocomposites were formed as colloidal particles dispersed in solution via the reduction of hydrogen radicals generated during discharge without the addition of chemical precursor or reducing agent. At a discharge time of 30 s, the fine bimetallic nanoparticles with a mean particle size of approximately 5 nm were observed by transmission electron microscopy (TEM). With increasing discharge time, the bimetallic nanoparticle size tended to increase by forming an agglomeration. The presence of the relatively small amount of Pt dispersed in the Ag matrix could be observed by the analytical mapping mode of energy-dispersive x-ray spectroscopy and high-resolution TEM. This demonstrated that the synthesized particle was in the form of a nanocomposite. No contamination of other chemical substances was detected by x-ray photoelectron spectroscopy. Hence, solution plasma could be a clean and simple process to effectively synthesize Ag/Pt bimetallic nanocomposites and it is expected to be widely applicable in the preparation of several types of nanoparticle. PMID:22968093

  12. Dispersal and accumulation of Pt, Pd and Rh derived from a roundabout in Sheffield (UK): From stream to tidal estuary.

    PubMed

    Prichard, H M; Jackson, M T; Sampson, J

    2008-08-15

    The Coisley Hill roundabout, a typical urban source for PGE in stream sediments, has anomalously high values of up to 408 ppb Pt, 444 ppb Pd and 113 ppb Rh in road dust, up to 416 ppb Pt and 278 ppb Pd in gulley sediment and up to 606 ppb Pt and 1050 ppb Pd in verge soil. For samples collected at the same time, the road dust values are much higher than in sediments in the Shire Brook stream, that drains the roundabout, with values of 3-64 ppb Pt, 4-57 ppb Pd and up to 7 ppb Rh. Downstream sediments from rivers Rother and Don have lower values of 2-35 ppb Pt, 2-14 ppb Pd and up to 3 ppb Rh. The Humber estuary values are low with 6-8 ppb Pt, 5-8 ppb Pd and 1-2 ppb Rh. Pt/Pd increases down catchment with Coisley Hill 0.8, Shire Brook 1.0, Trent and Don 1.5 and the Humber estuary 2.0. Pt/Rh and Pd/Rh also increase downstream. Precious metals are generally dispersed away from their vehicle catalytic source and Pd is dispersed more than Pt and Rh but Pt and Pd are re-concentrated in acid mine drainage in the Shire Brook, with concentrations varying with stream flow. Pt and Pd values are slightly elevated at the tidal limit and in mud deposited when the river is in spate. On Coisley Hill, values of 133 ppb Pt and 230 ppb Pd occur in dust from a new road surface (two weeks old when sampled). These are similar to those on much older road surfaces suggesting that Pt and Pd collect and disperse rapidly from roads. Au is low in road dust and higher values in conurbations suggest the presence of more Au sources in urban rather than in rural areas. Au values are not diluted downstream as much as PGE suggesting different processes of dispersion and sedimentation. PMID:18486195

  13. The effect of specific chloride adsorption on the electrochemicalbehavior of ultrathin Pd films deposited on Pt(111) in acidsolution

    SciTech Connect

    arenz@thch.uni-bonn.de

    2002-10-01

    The electrochemical behavior of thin Pd films supported on a Pt(111) electrode is investigated by cyclic voltammetry (CV) and in-situ Fourier transform infrared (FTIR) spectroscopy. It is demonstrated that in perchloric acid solution underpotential deposition of hydrogen (H{sub upd}) and hydroxyl adsorption (OH{sub ad}) is in strong competition with the adsorption of Cl- anions, the latter being present as a trace impurity in HClO{sub 4}. The interaction of Cl- with Pd is rather strong, controlling the adsorption of H{sub upd} and OH{sub ad} as well as the kinetic rate of CO oxidation. The microscopic insight (the binding sites) of the adsorbed CO (CO{sub ad}) and the rate of CO oxidation (established from CO2 production) on Pt(111) modified with a (sub)monolayer of Pd is elucidated by means of Fourier infrared (FTIR) spectroscopy. The appearance of both the characteristic Pt(111)-CO{sub ad} and Pt(111)1 ML Pd-CO{sub ad} stretching bands on a Pt(111) surface covered by 0.5 ML Pd confirms previous findings that the Pd atoms agglomerate into islands and that the bare Pt areas and the Pd islands behave according to their own surface chemistry. The systematic increase of the Pd surface coverage results in a gradual change in the catalytic properties of Pt(111)-xPd electrodes towards CO oxidation, from those characteristic of bare Pt(111) to those which are characteristic for Pt(111) covered with 1 ML of Pd.

  14. L10 ordered phase formation in FePt, FePd, CoPt, and CoPd alloy thin films epitaxially grown on MgO(001) single-crystal substrates

    NASA Astrophysics Data System (ADS)

    Ohtake, Mitsuru; Ouchi, Shouhei; Kirino, Fumiyoshi; Futamoto, Masaaki

    2012-04-01

    The FePt, FePd, CoPt, and CoPd epitaxial thin films are prepared on MgO(001) single-crystal substrates by ultrahigh vacuum RF magnetron sputtering. The effects of the magnetic material and the substrate temperature on the film growth, the film structure, and the magnetic properties are investigated. The L10 ordered phase formation is observed for FePt, FePd, and CoPt films prepared at temperatures higher than 200, 400, and 600 °C, respectively, whereas that is not recognized for CoPd films. The L10-FePd(001) single-crystal films with the c-axis normal to the substrate surface are formed, whereas the FePt and CoPt epitaxial films include L10(100) crystals whose c-axis is parallel to the substrate surface, in addition to the L10(001) crystals. Upon increasing the substrate temperature, the ordering degree increases. A higher ordering parameter is observed in the order of FePd > FePt > CoPt. The magnetic properties are influenced by the crystal structure, the crystallographic orientation of the L10 crystal, and the ordering degree.

  15. Facile synthesis of Pt-Pd@Silicon nanostructure as an advanced electrocatalyst for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Ensafi, Ali A.; Jafari-Asl, M.; Rezaei, B.; Abarghoui, M. Mokhtari; Farrokhpour, H.

    2015-05-01

    In this work, platinum-palladium (Pt-Pd) is assembled in-situ on the surface of porous silicon flour (PSiF) through chemical reduction of PtCl62-/PdCl42- and oxidation of the precursor solution SiF64-. The components and the morphological properties of the Pt-Pd on PSiF is investigated by means of transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction techniques. In the next stage, screen printed graphene electrode (SPGE) is prepared by electro-reduction of exfoliated graphene oxide at the surface of a screen printed carbon electrode (SPCE), which is subsequently characterized by FT-IR, Raman spectroscopy, FE-SEM, and electrochemical methods. Finally, a combination of Pt-Pd@PSi nanostructure and SPGE is used for the electro-oxidation of methanol in direct methanol fuel cell. The electrochemical results demonstrate that the Pt-Pd@PSiF-SPGE exhibits an excellent electrocatalytic activity for methanol oxidation. In addition, the electron transfer kinetic of methanol oxidation on Pt-Pd@PSiF-SPGE is investigated by electrochemical impedance spectroscopy. The results showed that the surface of Pt-Pd@PSiF-SPGE is not affected (poisoned) by intermediate products such as CO.

  16. First principles investigation of the activity of thin film Pt, Pd and Au surface alloys for oxygen reduction.

    PubMed

    Tripkovic, Vladimir; Hansen, Heine Anton; Rossmeisl, Jan; Vegge, Tejs

    2015-05-01

    Further advances in fuel cell technologies are hampered by kinetic limitations associated with the sluggish cathodic oxygen reduction reaction. We have investigated a range of different formulations of binary and ternary Pt, Pd and Au thin films as electrocatalysts for oxygen reduction. The most active binary thin films are near-surface alloys of Pt with subsurface Pd and certain PdAu and PtAu thin films with surface and/or subsurface Au. The most active ternary thin films are with pure metal Pt or Pd skins with some degree of Au in the surface and/or subsurface layer and the near-surface alloys of Au with mixed Pt-Pd skins. The activity of the binary and ternary catalysts is explained through weakening of the OH binding energy caused by solute elements. However, given the low alloy formation energies it may be difficult to tune and retain the composition under operating conditions. This is particularly challenging for alloys containing Au due to a high propensity of Au to segregate to the surface. We also show that once Au is on the surface it will diffuse to defect sites, explaining why small amounts of Au retard dissolution of Pt nanoparticles. For the PtPd thin films there is no pronounced driving force for surface segregation, diffusion to defects or surface self-assembling. On the basis of stability and activity analysis we conclude that the near surface alloy of Pd in Pt and some PdAu binary and PtPdAu ternary thin films with a controlled amount of Au are the best catalysts for oxygen reduction. PMID:25865333

  17. Facile synthesis of PdAgTe nanowires with superior electrocatalytic activity

    NASA Astrophysics Data System (ADS)

    Hong, Wei; Wang, Jin; Wang, Erkang

    2014-12-01

    In this work, ultrathin Te nanowires (NWs) with high-aspect-ratio are prepared by a simple hydrothermal method. By using Te NWs as the sacrificial template, we demonstrate a facile and efficient method for the synthesis of PdAgTe NWs with high-quality through the partly galvanic replacement between Te NWs and the corresponding noble metal salts precursors in an aqueous solution. The compositions of PdAgTe NWs can be tuned by simply altering the concentration of the precursors. After cyclic voltammetry treatment, multi-component PdAgTe NW with a highly active and stable surface can be obtained. The structure and composition of the as-prepared nanomaterials are analyzed by transmission electron microscope, X-ray diffraction, energy dispersive X-ray spectroscopy, inductively coupled plasma-mass spectroscopy and X-ray photoelectron spectroscopy. Electrochemical catalytic measurement results prove that the as synthesized PdAgTe NWs present superior catalytic activity toward ethanol electrooxidation in alkaline solution than the commercial Pd/C catalyst, which making them can be used as effective catalysts for the direct ethanol fuel cells.

  18. Effect of Annealing Twins on Electromigration in Ag-8Au-3Pd Bonding Wires

    NASA Astrophysics Data System (ADS)

    Chuang, Tung-Han; Wang, Hsi-Ching; Chuang, Chien-Hsun; Lee, Jun-Der; Tsai, Hsing-Hua

    2013-03-01

    An innovative Ag-8Au-3Pd bonding wire with a high twin density has been produced. The grain size of this annealing-twinned wire changes moderately during electrical stressing, unlike that of the conventional grained wire, which increases drastically and even leads to a bamboo structure. In addition, the durability against electromigration of the annealing-twinned Ag-8Au-3Pd alloy wire is higher than that of the conventional grained wire. This higher durability can be ascribed to the surface reconstruction of a stepwise morphology and slow grain growth resulting from the abundance of annealing twins in this wire.

  19. Graphene nanosheet-tailored PtPd concave nanocubes with enhanced electrocatalytic activity and durability for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Lu, Yizhong; Jiang, Yuanyuan; Chen, Wei

    2014-02-01

    Here, we demonstrate that graphene oxide (GO) can act as a structure-directing agent for the formation of PtPd alloy concave nanocubes enclosed by high index facets. In the presence of GO, PtPd alloy concave nanocubes could be easily tailored by a simple hydrothermal reaction. In sharp contrast, only cubic PtPd alloy nanocrystals were obtained in the absence of GO. Moreover, compared to the unsupported PtPd nanocubes, the composition ratio of Pt to Pd changed significantly from 1 : 1 to 3 : 1. Due to the exposed high-index facets and the strong interaction between catalysts and graphene support, the as-synthesized PtPd concave nanocubes exhibited enhanced electrocatalytic activity and high durability toward methanol oxidation. The present work highlights the unique role of GO in the formation of metal nanocrystals as not only a catalyst support but also a structure- and/or morphology-directing agent, due to the presence of various functional groups on GO sheets. The present GO-assisted approach provides a new avenue to the synthesis of nanocrystals with high-index facets and initiates new opportunities for the exploration of high-performance graphene-based nanocatalysts.Here, we demonstrate that graphene oxide (GO) can act as a structure-directing agent for the formation of PtPd alloy concave nanocubes enclosed by high index facets. In the presence of GO, PtPd alloy concave nanocubes could be easily tailored by a simple hydrothermal reaction. In sharp contrast, only cubic PtPd alloy nanocrystals were obtained in the absence of GO. Moreover, compared to the unsupported PtPd nanocubes, the composition ratio of Pt to Pd changed significantly from 1 : 1 to 3 : 1. Due to the exposed high-index facets and the strong interaction between catalysts and graphene support, the as-synthesized PtPd concave nanocubes exhibited enhanced electrocatalytic activity and high durability toward methanol oxidation. The present work highlights the unique role of GO in the formation of

  20. Alloy formation of Ni ultrathin films on Pt(1 1 1) with Ag buffer layers

    NASA Astrophysics Data System (ADS)

    Ho, H. Y.; Su, C. W.; Chu, Y. W.; Shern, C. S.

    2004-10-01

    Low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), and depth profiling were used to study growth mode and structure in the interfaces of Ni/Ag/Pt(1 1 1). An atomic exchange occurs between Ni and Ag when the annealing temperature is high enough and the starting exchange temperature does not depend on the thickness of Ni. Nevertheless, the complete exchange temperature is higher when the coverage of Ni increases. Experimental evidence shows that the Ni-Pt alloy develops after the atomic exchange between Ag and Ni is complete. The atomic exchange between Ag and Ni, and the formation of Ni-Pt alloy were confirmed by the depth profile. The mechanisms of the atomic exchange are discussed.

  1. Magnetic and Fermi Surface Properties of Ferromagnets EuPd2 and EuPt2

    NASA Astrophysics Data System (ADS)

    Nakamura, Ai; Akamine, Hiromu; Ashitomi, Yousuke; Honda, Fuminori; Aoki, Dai; Takeuchi, Tetsuya; Matsubayashi, Kazuyuki; Uwatoko, Yoshiya; Tatetsu, Yasutomi; Maehira, Takahiro; Hedo, Masato; Nakama, Takao; Ōnuki, Yoshichika

    2016-08-01

    We succeeded in growing single crystals of the ferromagnets EuPd2 and EuPt2 with the Laves-type cubic structure by the Bridgman method, namely, heating constituting materials in a Mo crucible up to a high temperature of about 1500 °C. The ferromagnetic properties of EuPd2 and EuPt2 with Curie temperatures of 74 and 100 K, respectively, were confirmed from the results of electrical resistivity, specific heat, and magnetization measurements. The ordered moment is 7 μB/Eu, revealing the Eu-divalent ferromagnetism. The present Eu-divalent electronic state is found to be robust against high pressures of up to 8 GPa and is not changed into the Eu-trivalent state. We also carried out de Haas-van Alphen (dHvA) experiments for EuPd2. The detected dHvA branches in EuPd2 are well explained by the relativistic linearized augmented plane wave (RLAPW) energy band calculations for SrPd2, revealing a closed hole Fermi surface and compensated four closed electron Fermi surfaces.

  2. Pd@Ag Nanosheets in Combination with Amphotericin B Exert a Potent Anti-Cryptococcal Fungicidal Effect

    PubMed Central

    Wang, Guizhen; Fang, Wei; Ye, Chen; Hu, Hanhua; Fa, Zhenzong; Yi, Jiu; Liao, Wan-qing

    2016-01-01

    Silver nanoparticles have received considerable interest as new “nanoantibiotics” with the potential to kill drug-resistant microorganisms. Recently, a class of new core-shell nanostructures, Pd@Ag nanosheets (Pd@Ag NSs), were created using deposition techniques and demonstrated excellent inhibitory effects on various bacteria in vitro. In this study, we evaluated the antifungal activity of Pd@Ag NSs against common invasive fungal pathogens. Among these organisms, Cryptococcus neoformans complex species was most susceptible to Pd@Ag NSs, which exhibited potent antifungal activity against various molecular types or sources of cryptococcal strains including fluconazole-resistant isolates. The anticryptococcal activity of Pd@Ag NSs was significantly greater than fluconazole and similar to that of amphotericin B (AmB). At relatively high concentrations, Pd@Ag NSs exhibited fungicidal activity against Cryptococcus spp., which can likely be attributed to the disruption of cell integrity, intracellular protein synthesis, and energy metabolism. Intriguingly, Pd@Ag NSs also exhibited strong synergistic anti-cryptococcal fungicidal effects at low concentrations in combination with AmB but exhibited much better safety in erythrocytes than AmB, even at the minimal fungicidal concentration. Therefore, Pd@Ag NSs may be a promising adjunctive agent for treating cryptococcosis, and further investigation for clinical applications is required. PMID:27271376

  3. Improving Electrocatalysts for O2 Reduction by Fine-Tuning the Pt-Support Interaction: Pt Monolayer on the Surfaces of a Pd3Fe(111) Single-Crystal Alloy

    SciTech Connect

    Zhou, W.P.; Yang, X.; Vukmirovic, M.B.; Koel, B.E.; Jiao, J.; Peng, G.; Mavrikakis, M.; Adzic, R.R.

    2009-09-09

    We improved the effectiveness of Pt monolayer electrocatalysts for the oxygen-reduction reaction (ORR) using a novel approach to fine-tuning the Pt monolayer interaction with its support, exemplified by an annealed Pd{sub 3}Fe(111) single-crystal alloy support having a segregated Pd layer. Low-energy ion scattering and low-energy electron diffraction studies revealed that a segregated Pd layer, with the same structure as Pd (111), is formed on the surface of high-temperature-annealed Pd{sub 3}Fe(111). This Pd layer is considerably more active than Pd(111); its ORR kinetics is comparable to that of a Pt(111) surface. The enhanced catalytic activity of the segregated Pd layer compared to that of bulk Pd apparently reflects the modification of Pd surface's electronic properties by underlying Fe. The Pd{sub 3}Fe(111) suffers a large loss in ORR activity when the subsurface Fe is depleted by potential cycling (i.e., repeated excursions to high potentials in acid solutions). The Pd{sub 3}Fe(111) surface is an excellent substrate for a Pt monolayer ORR catalyst, as verified by its enhanced ORR kinetics on PT{sub ML}/Pd/Pd{sub 3}Fe(111). Our density functional theory studies suggest that the observed enhancement of ORR activity originates mainly from the destabilization of OH binding and the decreased Pt-OH coverage on the Pt/Pd/Pd{sub 3}Fe(111) surface. The activity of Pt{sub ML}/Pd(111) and Pt(111) is limited by OH removal, whereas the activity of Pt{sub ML}/Pd/Pd{sub 3}Fe(111) is limited by the O-O bond scission, which places these two surfaces on the two sides of the volcano plot.

  4. Core/shell face-centered tetragonal FePd/Pd nanoparticles as an efficient non-Pt catalyst for the oxygen reduction reaction

    SciTech Connect

    Zhu, Huiyuan; Jiang, Guangming; Zhang, Xu; Shen, Bo; Wu, Liheng; Zhang, Sen; Lu, Gang; Wu, Zhongbiao; Sun, Shouheng

    2015-10-04

    We report the synthesis of core/shell face-centered tetragonal (fct)-FePd/Pd nanoparticles (NPs) via reductive annealing of core/shell Pd/Fe3O4 NPs followed by temperature-controlled Fe etching in acetic acid. Among three different kinds of core/shell FePd/Pd NPs studied (FePd core at similar to 8 nm and Pd shell at 0.27, 0.65, or 0.81 nm), the fct-FePd/Pd-0.65 NPs are the most efficient catalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO4 with Pt-like activity and durability. This enhanced ORR catalysis arises from the desired Pd lattice compression in the 0.65 nm Pd shell induced by the fct-FePd core. Lastly, our study offers a general approach to enhance Pd catalysis in acid for ORB.

  5. Core/shell face-centered tetragonal FePd/Pd nanoparticles as an efficient non-Pt catalyst for the oxygen reduction reaction

    DOE PAGESBeta

    Zhu, Huiyuan; Jiang, Guangming; Zhang, Xu; Shen, Bo; Wu, Liheng; Zhang, Sen; Lu, Gang; Wu, Zhongbiao; Sun, Shouheng

    2015-10-04

    We report the synthesis of core/shell face-centered tetragonal (fct)-FePd/Pd nanoparticles (NPs) via reductive annealing of core/shell Pd/Fe3O4 NPs followed by temperature-controlled Fe etching in acetic acid. Among three different kinds of core/shell FePd/Pd NPs studied (FePd core at similar to 8 nm and Pd shell at 0.27, 0.65, or 0.81 nm), the fct-FePd/Pd-0.65 NPs are the most efficient catalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO4 with Pt-like activity and durability. This enhanced ORR catalysis arises from the desired Pd lattice compression in the 0.65 nm Pd shell induced by the fct-FePd core. Lastly, our study offersmore » a general approach to enhance Pd catalysis in acid for ORB.« less

  6. Density functional theory study of structural, electronic, and thermal properties of Pt, Pd, Rh, Ir, Os and PtPd X (X = Ir, Os, and Rh) alloys

    NASA Astrophysics Data System (ADS)

    Shabbir, Ahmed; Muhammad, Zafar; M, Shakil; M, A. Choudhary

    2016-03-01

    The structural, electronic, mechanical, and thermal properties of Pt, Pd, Rh, Ir, Os metals and their alloys PtPdX (X = Ir, Os and Rh) are studied systematically using ab initio density functional theory. The groundstate properties such as lattice constant and bulk modulus are calculated to find the equilibrium atomic position for stable alloys. The electronic band structure and density of states are calculated to study the electronic behavior of metals on making their alloys. The electronic properties substantiate the metallic behavior for all studied materials. The firstprinciples density functional perturbation theory as implemented in quasi-harmonic approximation is used for the calculations of thermal properties. We have calculated the thermal properties such as the Debye temperature, vibrational energy, entropy and constant-volume specific heat. The calculated properties are compared with the previously reported experimental and theoretical data for metals and are found to be in good agreement. Calculated results for alloys could not be compared because there is no data available in the literature with such alloy composition.

  7. Tunable Catalysis of Water to Peroxide with Anionic, Cationic, and Neutral Atomic Au, Ag, Pd, Rh, and Os

    NASA Astrophysics Data System (ADS)

    Suggs, K.; Kiros, F.; Tesfamichael, A.; Felfli, Z.; Msezane, A. Z.

    2015-05-01

    Fundamental anionic, cationic, and neutral atomic metal predictions utilizing density functional theory calculations validate the recent discovery identifying the interplay between Regge resonances and Ramsauer-Townsend minima obtained through complex angular momentum analysis as the fundamental atomic mechanism underlying nanoscale catalysis. Here we investigate the optimization of the catalytic behavior of Au, Ag, Pd, Rh, and Os atomic systems via polarization effects and conclude that anionic atomic systems are optimal and therefore ideal for catalyzing the oxidation of water to peroxide, with anionic Os being the best candidate. The discovery that cationic systems increase the transition energy barrier in the synthesis of peroxide could be important as inhibitors in controlling and regulating catalysis. These findings usher in a fundamental and comprehensive atomic theoretical framework for the generation of tunable catalytic systems. The ultimate aim is to design giant atomic catalysts and sensors, in the context of the recently synthesized tri-metal Ag@Au@Pt and bimetal Ag@Au nanoparticles for greatly enhanced plasmonic properties and improved chemical stability for chemical and biological sensing. Research was supported by U.S. DOE Office of Basic Energy Sciences.

  8. Anisotropic thermal expansion of Ni, Pd and Pt germanides and silicides

    NASA Astrophysics Data System (ADS)

    Geenen, F. A.; Knaepen, W.; Moens, F.; Brondeel, L.; Leenaers, A.; Van den Berghe, S.; Detavernier, C.

    2016-07-01

    Silicon or germanium-based transistors are nowadays used in direct contact with silicide or germanide crystalline alloys for semiconductor device applications. Since these compounds are formed at elevated temperatures, accurate knowledge of the thermal expansion of both substrate and the contact is important to address temperature depending effects such as thermal stress. Here we report the linear coefficients of thermal expansion of Ni-, Pd- and Pt-based mono-germanides, mono-silicides and di-metal-silicides as determined by powder-based x-ray diffraction between 300 and 1225 K. The investigated mono-metallic compounds, all sharing the MnP crystal structure, as well as Pd2Si and Pt2Si exhibit anisotropic expansion. By consequence, this anisotropic behaviour should be taken into account for evaluating the crystal unit’s cell at elevated temperatures.

  9. Density functional theory study of oxygen reduction reaction on Pt/Pd3Al(111) alloy electrocatalyst.

    PubMed

    Xiao, B B; Jiang, X B; Jiang, Q

    2016-05-25

    Developing efficient catalysts for the oxygen reduction reaction (ORR) to reduce cathode Pt loading without sacrificing the performance has been under intensive research. Herein, by using density functional theory calculations, the activity and stability of a Pt monolayer supported on Pd3Al(111) as the ORR catalyst have been systematically studied. The simulations demonstrate that due to alloying, the ORR intermediates bind weakly on Pt/Pd3Al(111) with optimal adsorption energy of O and OH. By considering the elemental ORR steps, the ORR mechanism is predicted to be an OOH dissociation mechanism. The rate determining step is OOH dissociation with a reaction barrier of 0.37 eV, lower than the corresponding value on Pt/Pt3Al(111) and Pt(111), indicating the superior activity of Pt/Pd3Al(111). Even considering the unfeasible H adsorption under high potential, the ORR mechanism on Pt/Pd3Al(111) would proceed via O2 hydration, OOH hydration, H2O formation, and H2O desorption, indicating a good ORR electrocatalyst. Furthermore, stability was evaluated by calculating the alloy formation energy and the electrochemical potential shift of surface Pt dissolution. The exceptionally negative alloy formation energy of Pd3Al and the positive dissolution potential shift of the surface Pt atoms show the enhanced durability of Pt/Pd3Al(111). The improved activity, in combination with its enhanced stability, makes the novel ternary alloy electrocatalyst very promising for development of new cathode catalysts for fuel cells. PMID:27167779

  10. Population genetic structure of Rhizoctonia solani AG 3-PT from potatoes in South Africa.

    PubMed

    Muzhinji, Norman; Woodhall, James W; Truter, Mariette; van der Waals, Jacquie E

    2016-05-01

    Rhizoctonia solani AG 3-PT is an important potato pathogen causing significant yield and quality losses in potato production. However, little is known about the levels of genetic diversity and structure of this pathogen in South Africa. A total of 114 R. solani AG 3-PT isolates collected from four geographic regions were analysed for genetic diversity and structure using eight microsatellite loci. Microsatellite analysis found high intra-population genetic diversity, population differentiation and evidence of recombination. A total of 78 multilocus genotypes were identified with few shared among populations. Low levels of clonality (13-39 %) and high levels of population differentiation were observed among populations. Most of the loci were in Hardy-Weinberg equilibrium and all four populations showed evidence of a mixed reproductive mode of both clonality and recombination. The PCoA clustering method revealed genetically distinct geographic populations of R. solani AG 3-PT in South Africa. This study showed that populations of R. solani AG 3-PT in South Africa are genetically differentiated and disease management strategies should be applied accordingly. This is the first study of the population genetics of R. solani AG 3-PT in South Africa and results may help to develop knowledge-based disease management strategies. PMID:27109367

  11. Heterointegration of Pt/Si/Ag Nanowire Photodiodes and Their Photocatalytic Properties

    PubMed Central

    Qu, Yongquan; Xue, Teng; Zhong, Xing; Lin, Yung-Chen; Liao, Lei; Choi, Jina; Duan, Xiangfeng

    2010-01-01

    Photocatalyst mediated photoelectrochemical processes can make use of the photogenerated electrons and holes onsite for photocatalytic redox reactions, and enable the harness and conversion of solar energy into chemical energy, in analogy to natural photosynthesis. However, the photocatalysts available to date are limited by either poor efficiency in the visible light range or insufficient photoelectrochemical stability. We show that a Pt/Si/Ag nanowire heterostructure can be rationally synthesized to integrate a nanoscale metal-semiconductor Schottky diode encased in a protective insulating shell with two exposed metal catalysts. The synthesis of Pt/Si/Ag nanowire diodes involves a scalable process including the formation of silicon nanowire array through wet chemical etching, electrodeposition of platinum and photoreduction of silver. We further demonstrated that the Pt/Si/Ag diodes exhibited highly efficient photocatalytic activity for a wide range of applications including environmental remediation and solar fuel production in the visible range. In this article, photodegradation of indigo carmine and 4-nitrophenol were used to evaluate the photoactivity of Pt/Si/Ag diodes. The Pt/Si/Ag diodes also show high activity for photoconversion of formic acid into carbon dioxide and hydrogen. PMID:21629399

  12. Novel strategy for preparation of graphene-Pd, Pt composite, and its enhanced electrocatalytic activity for alcohol oxidation.

    PubMed

    Gao, Lina; Yue, Wenbo; Tao, Shanshan; Fan, Louzhen

    2013-01-22

    As advanced electrodes for direct alcohol fuel cells, graphene-Pd and graphene-Pt composites with a trace of SnO(2) have been successfully synthesized by a modified electroless plating technique. The surface of graphene oxide is first sensitized by Sn(2+) ions, and subsequently, Pd or Pt nanoparticles are deposited on the surface of graphene oxide. Finally, graphene oxide was reduced to graphene by further adding NaBH(4). Compared to other carbon-(e.g., Vulcan XC-72R) supported Pd and Pt, the resultant graphene-Pd and Pt composites exhibit better electrocatalytic activity and long-term stability toward alcohol electrooxidation. Additionally, a trace amount of SnO(2) formed around active catalysts may also be beneficial to the enhancement of electrochemical activity. PMID:23259819

  13. Improving Electrocatalysts for O2 Reduction by Fine-Tuning the Pt-Support Interaction: Pt Monolayer on the Surfaces of a Pd3Fe(111) Single-Crystal Alloy

    SciTech Connect

    Zhou, Wei-Ping; Yang, Xiaofang; Vukmirovic, Miomir B.; Koel, Bruce E.; Jiao, Jiao; Peng, Guowen; Mavrikakis, Manos; Adzic, Radoslav R.

    2009-09-09

    We improved the effectiveness of Pt monolayer electrocatalysts for the oxygen-reduction reaction (ORR) using a novel approach to fine-tuning the Pt monolayer interaction with its support, exemplified by an annealed Pd3Fe(111) single-crystal alloy support having a segregated Pd layer. Low-energy ion scattering and low-energy electron diffraction studies revealed that a segregated Pd layer, with the same structure as Pd (111), is formed on the surface of high-temperature-annealed Pd3Fe(111). This Pd layer is considerably more active than Pd(111); its ORR kinetics is comparable to that of a Pt(111) surface. The enhanced catalytic activity of the segregated Pd layer compared to that of bulk Pd apparently reflects the modification of Pd surface’s electronic properties by underlying Fe. The Pd3Fe(111) suffers a large loss in ORR activity when the subsurface Fe is depleted by potential cycling (i.e., repeated excursions to high potentials in acid solutions). The Pd3Fe(111) surface is an excellent substrate for a Pt monolayer ORR catalyst, as verified by its enhanced ORR kinetics on PTML/Pd/Pd3Fe(111). Our density functional theory studies suggest that the observed enhancement of ORR activity originates mainly from the destabilization of OH binding and the decreased Pt-OH coverage on the Pt/Pd/Pd3Fe(111) surface. The activity of PtML/Pd(111) and Pt(111) is limited by OH removal, whereas the activity of PtML/Pd/Pd3Fe(111) is limited by the O-O bond scission, which places these two surfaces on the two sides of the volcano plot.

  14. Enhanced electrocatalytic activity and stability of Pd3V/C nanoparticles with a trace amount of Pt decoration for the oxygen reduction reaction

    DOE PAGESBeta

    Liu, Sufen; Han, Lili; Zhu, Jing; Xiao, Weiping; Wang, Jie; Liu, Hongfang; Xin, Huolin; Wang, Deli

    2015-09-14

    In this study, carbon supported Pd3V bimetallic alloy nanoparticles (Pd3V/C) have been successfully synthesized via a simple impregnation–reduction method, followed by high temperature treatment under a H2 atmosphere. Electrochemical tests reveal that the half-wave potential of Pd3V/C-500 shifts positively 40 mV compared with Pd/C. However, the catalytic activity of Pd3V/C-500 suffers from serious degradation after 1k cycles. By a spontaneous displacement reaction or co-reduction method, a trace amount of Pt was decorated on the surface or inside of the Pd3V/C nanoparticles. The catalytic activity and stability of the Pd3V@Pt/C and Pt-Pd3V/C catalysts for the oxygen reduction reaction (ORR) are enhancedmore » significantly, and are comparable to commercial Pt/C. In addition, the Pt mass activity of Pd3V@Pt/C and Pt-Pd3V/C improves by factors of 10.9 and 6.5 at 0.80 V relative to Pt/C. Moreover, Pt-decorated Pd3V/C nanoparticles show almost no obvious morphology change after durability tests, because the Pt-rich shell plays an important role in preventing degradation.« less

  15. Morphology and N₂ Permeance of Sputtered Pd-Ag Ultra-Thin Film Membranes.

    PubMed

    Fernandez, Ekain; Sanchez-Garcia, Jose Angel; Viviente, Jose Luis; van Sint Annaland, Martin; Gallucci, Fausto; Tanaka, David A Pacheco

    2016-01-01

    The influence of the temperature during the growth of Pd-Ag films by PVD magnetron sputtering onto polished silicon wafers was studied in order to avoid the effect of the support roughness on the layer growth. The surfaces of the Pd-Ag membrane films were analyzed by atomic force microscopy (AFM), and the results indicate an increase of the grain size from 120 to 250-270 nm and film surface roughness from 4-5 to 10-12 nm when increasing the temperature from around 360-510 K. After selecting the conditions for obtaining the smallest grain size onto silicon wafer, thin Pd-Ag (0.5-2-µm thick) films were deposited onto different types of porous supports to study the influence of the porous support, layer thickness and target power on the selective layer microstructure and membrane properties. The Pd-Ag layers deposited onto ZrO₂ 3-nm top layer supports (smallest pore size among all tested) present high N₂ permeance in the order of 10(-6) mol·m(-2)·s(-1)·Pa(-1) at room temperature. PMID:26875977

  16. Influence of the silver oxidation on the resistive switching in Ag/AgOx/WO3-x/Pt heterostructures

    NASA Astrophysics Data System (ADS)

    Dong, Chun-Ying; Wei, Wen Gang; Zhao, Jing; Zhang, Jian; Zhao, Xu; Chen, Wei

    2015-12-01

    Silver is usually considered as an inert material and is most commonly used as an electrode. In this work, however, we demonstrate that silver can be easily oxidized during preparation. The influence of the silver oxidation on the resistive switching (RS) effect of the Ag/AgOx/WO3-x/Pt heterostructures was systematically investigated. The heterostructure in which the AgOx film was deposited under an oxygen pressure of 5 × 10-4 Pa showed a linear current-voltage relationship (Ohmic contact). The heterostructures in which the AgOx films were deposited under oxygen pressures of 10 and 100 Pa showed a typical interface RS effect with rectification. In combination with the analysis of the dependence of high-resistance-state (HRS) on RESET current and RESET voltage under different compliance currents, we inferred that the electrochemical redox reaction of the silver oxide is responsible for the RS effect in Ag/AgOx/WO3-x/Pt heterostructures.

  17. Controlled Synthesis of Pd/Pt Core Shell Nanoparticles Using Area-selective Atomic Layer Deposition

    PubMed Central

    Cao, Kun; Zhu, Qianqian; Shan, Bin; Chen, Rong

    2015-01-01

    We report an atomic scale controllable synthesis of Pd/Pt core shell nanoparticles (NPs) via area-selective atomic layer deposition (ALD) on a modified surface. The method involves utilizing octadecyltrichlorosilane (ODTS) self-assembled monolayers (SAMs) to modify the surface. Take the usage of pinholes on SAMs as active sites for the initial core nucleation, and subsequent selective deposition of the second metal as the shell layer. Since new nucleation sites can be effectively blocked by surface ODTS SAMs in the second deposition stage, we demonstrate the successful growth of Pd/Pt and Pt/Pd NPs with uniform core shell structures and narrow size distribution. The size, shell thickness and composition of the NPs can be controlled precisely by varying the ALD cycles. Such core shell structures can be realized by using regular ALD recipes without special adjustment. This SAMs assisted area-selective ALD method of core shell structure fabrication greatly expands the applicability of ALD in fabricating novel structures and can be readily applied to the growth of NPs with other compositions. PMID:25683469

  18. Structural optimization of Pt-Pd alloy nanoparticles using an improved discrete particle swarm optimization algorithm

    NASA Astrophysics Data System (ADS)

    Shao, Gui-Fang; Wang, Ting-Na; Liu, Tun-Dong; Chen, Jun-Ren; Zheng, Ji-Wen; Wen, Yu-Hua

    2015-01-01

    Pt-Pd alloy nanoparticles, as potential catalyst candidates for new-energy resources such as fuel cells and lithium ion batteries owing to their excellent reactivity and selectivity, have aroused growing attention in the past years. Since structure determines physical and chemical properties of nanoparticles, the development of a reliable method for searching the stable structures of Pt-Pd alloy nanoparticles has become of increasing importance to exploring the origination of their properties. In this article, we have employed the particle swarm optimization algorithm to investigate the stable structures of alloy nanoparticles with fixed shape and atomic proportion. An improved discrete particle swarm optimization algorithm has been proposed and the corresponding scheme has been presented. Subsequently, the swap operator and swap sequence have been applied to reduce the probability of premature convergence to the local optima. Furthermore, the parameters of the exchange probability and the 'particle' size have also been considered in this article. Finally, tetrahexahedral Pt-Pd alloy nanoparticles has been used to test the effectiveness of the proposed method. The calculated results verify that the improved particle swarm optimization algorithm has superior convergence and stability compared with the traditional one.

  19. Pt- and Pd-decorated MWCNTs for vapour and gas detection at room temperature

    PubMed Central

    Baccar, Hamdi; Clément, Pierrick; Abdelghani, Adnane

    2015-01-01

    Summary Here we report on the gas sensing properties of multiwalled carbon nanotubes decorated with sputtered Pt or Pd nanoparticles. Sputtering allows for an oxygen plasma treatment that removes amorphous carbon from the surface of the carbon nanotubes and creates oxygenated surface defects in which metal nanoparticles nucleate within a few minutes. The decoration with the 2 nm Pt or the 3 nm Pd nanoparticles is very homogeneous. This procedure is performed at the device level (i.e., for carbon nanotubes deposited onto sensor substrates) for many devices in one batch, which illustrates the scalability for the mass production of affordable nanosensors. The response to selected aromatic and non-aromatic volatile organic compounds, as well as pollutant gases has been studied. Pt- and Pd-decorated multiwalled carbon nanotubes show a fully reversible response to the non-aromatic volatile organic compounds tested when operated at room temperature. In contrast, these nanomaterials were not responsive to the aromatic compounds studied (measured at concentrations up to 50 ppm). Therefore, these sensors could be useful in a small, battery-operated alarm detector, for example, which is able to discriminate aromatic from non-aromatic volatile organic compounds in ambient. PMID:25977863

  20. Asymmetric AgPd-AuNR heterostructure with enhanced photothermal performance and SERS activity.

    PubMed

    Zhang, Han; Liu, Zeke; Kang, Xiaolin; Guo, Jun; Ma, Wanli; Cheng, Si

    2016-01-28

    Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts. PMID:26744075

  1. Characterization of Ag-Pd nanocomposite paste for electrochemical migration resistance.

    PubMed

    Kim, Kwang-Seok; Jung, Kwang-Ho; Park, Bum-Geun; Shin, Young-Eui; Jung, Seung-Boo

    2013-11-01

    Direct printing such as inkjet, gravure, and screen printing is an attractive approach for achieving low-cost circuitry in the printed circuit board industry. One of the challenges for direct printing technology, however, is the poor resistance to electrochemical migration (ECM), especially for silver (Ag) which has been widely used in printed electronics. We demonstrate improved resistance to Ag electrochemical migration by adding palladium (Pd) nanoparticles to the Ag nanopaste. Conductive comb-type patterns were fabricated on a bismaleimide-triazine substrate via screen printing. Their ECM characteristics were assessed by water drop test with deionized water. These results showed that the ECM time required for dendritic growth from cathode to anode to cause short-circuit failure was affected by the Pd content and applied voltages: the ECM time of Ag-15wt.% Pd nanopaste was nearly threefold that of Ag nanopaste, and the ECM time decreased by 94.22%, on average, while the applied voltage increased from 3 V to 9 V. PMID:24245303

  2. Asymmetric AgPd-AuNR heterostructure with enhanced photothermal performance and SERS activity

    NASA Astrophysics Data System (ADS)

    Zhang, Han; Liu, Zeke; Kang, Xiaolin; Guo, Jun; Ma, Wanli; Cheng, Si

    2016-01-01

    Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts.Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07333b

  3. Facile synthesis of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide with enhanced electrocatalytic properties

    NASA Astrophysics Data System (ADS)

    Li, Shan-Shan; Zheng, Jie-Ning; Ma, Xiaohong; Hu, Yuan-Yuan; Wang, Ai-Jun; Chen, Jian-Rong; Feng, Jiu-Ju

    2014-05-01

    A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media.A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media. Electronic supplementary information (ESI) available: Experimental section, Fig. S1-S12 and Tables S1 and S2. See DOI: 10.1039/c3nr06808k

  4. Graphene nanosheet-tailored PtPd concave nanocubes with enhanced electrocatalytic activity and durability for methanol oxidation.

    PubMed

    Lu, Yizhong; Jiang, Yuanyuan; Chen, Wei

    2014-03-21

    Here, we demonstrate that graphene oxide (GO) can act as a structure-directing agent for the formation of PtPd alloy concave nanocubes enclosed by high index facets. In the presence of GO, PtPd alloy concave nanocubes could be easily tailored by a simple hydrothermal reaction. In sharp contrast, only cubic PtPd alloy nanocrystals were obtained in the absence of GO. Moreover, compared to the unsupported PtPd nanocubes, the composition ratio of Pt to Pd changed significantly from 1 : 1 to 3 : 1. Due to the exposed high-index facets and the strong interaction between catalysts and graphene support, the as-synthesized PtPd concave nanocubes exhibited enhanced electrocatalytic activity and high durability toward methanol oxidation. The present work highlights the unique role of GO in the formation of metal nanocrystals as not only a catalyst support but also a structure- and/or morphology-directing agent, due to the presence of various functional groups on GO sheets. The present GO-assisted approach provides a new avenue to the synthesis of nanocrystals with high-index facets and initiates new opportunities for the exploration of high-performance graphene-based nanocatalysts. PMID:24519683

  5. Co/Pt and Co/Pd multilayers as new magneto-optical recording media (abstract)

    NASA Astrophysics Data System (ADS)

    Zeper, W. B.; van Kesteren, H. W.; Jacobs, B. A. J.; Spruit, J. H. M.; Carcia, P. F.

    1991-04-01

    In this paper we will discuss Co/Pt and, to a lesser extent, Co/Pd multilayers optimized for magneto-optical storage applications. Perpendicular magnetic anisotropy and square hysteresis loops are achieved for multilayers with a total thickness below about 200 Å if they consist of very thin (≂4 Å) Co layers alternated with 10-20-Å Pt layers. Multilayer made by evaporation show a high coercivity (≳100 kA/m) and have proven to be suitable as magneto-optical recording medium. Recently we showed that Co/Pt layers with high coercivity can be made by sputtering as well, if not Ar but Kr is used as sputter gas.1 We will discuss the properties of Co/Pt multilayers in relation to the preparation technique and will present magneto-optical recording results for both evaporated and sputtered Co/Pt multilayer films. The written domain patterns can be very regular, as observed by scanning magnetic force microscopy, and a CNR as high as 55 dB (1 MHz carrier, 5 m/s, 30 kHz BW) is observed. The good oxidation and corrosion resistance together with increasing Kerr effect towards shorter wavelengths, where higher storage densities are possible, make that Co/Pt multilayers are attractive new magneto-optical recording media.

  6. Deep oxidation of methane on particles derived from YSZ-supported Pd-Pt-(O) coatings synthesized by pulsed filtered cathodic arc

    SciTech Connect

    Horwat, D.; Endrino, J.L.; Boreave, A.; Karoum,R.; Pierson, J.F.; Weber, S.; Anders, A.; Vernoux, Ph.

    2008-12-12

    Methane conversion tests were performed on Pd, PdOy, Pd0.6Pt0.4Oy and Pd0.4Pt0.6Oy thin films deposited on yttria stabilized zirconia (YSZ) substrates. Pt containing films exhibited poor activity and high reducibility. As-deposited Pd and PdOy films showed good activity and transformed, during the cycling process, to particles dispersed on the YSZ substrates. The higher reaction rate of initially PdOy films was explained by a better dispersion of the catalyst. A drop of the reaction rate was observed when the temperature exceeded 735oC and 725oC for initially Pd and PdOy, respectively, which can be associated with the high-temperature reduction of PdO into Pd.

  7. Selective hydrodechlorination of 1,2-dichloroethane to ethylene over Pd-Ag/Al2O3 catalysts prepared by surface reduction

    NASA Astrophysics Data System (ADS)

    Han, Yuxiang; Gu, Guangfeng; Sun, Jingya; Wang, Wenjuan; Wan, Haiqin; Xu, Zhaoyi; Zheng, Shourong

    2015-11-01

    Alumina supported Pd-Ag and (Cu) bimetallic catalysts (denoted as sr-Pd-Ag/Al2O3 or sr-Pd-Cu/Al2O3) with varied Pd/Ag (or Cu) ratios were prepared using the surface reduction method, and the gas-phase catalytic hydrodechlorination of 1,2-dichloroethane over the catalysts were investigated. For comparison, Pd-Ag bimetallic catalysts were prepared by the conventional co-impregnation method (denoted as im-Pd-Ag/Al2O3). The catalysts were characterized by N2 adsorption, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and CO chemisorption. Characterization results indicated that surface reduction led to selective deposition of metallic Ag on the surface of Pd particles, while Pd and Ag just disorderly mixed in the catalyst prepared by impregnation method. Therefore, sr-Pd-Ag/Al2O3 exhibited a higher ethylene selectivity than im-Pd-Ag/Al2O3 for hydrodechlorination of 1,2-dichloroethane at a similar Ag loading amount. Moreover, among sr-Pd-Ag/Al2O3, sr-Pd-Cu/Al2O3 and im-Pd-Ag/Al2O3 catalysts, the ethylene selectivity decreased over these catalysts following the order: sr-Pd-Ag/Al2O3 > sr-Pd-Cu/Al2O3 > im-Pd-Ag/Al2O3. The present results indicate that surface reduction can be used as a potential method to synthesize catalyst with enhanced ethylene selectivity in hydrodechlorination of 1,2-dichloroethane.

  8. Ag-induced spin-reorientation transition of Co ultrathin films on Pt(111)

    NASA Astrophysics Data System (ADS)

    Chen, F. C.; Wu, Y. E.; Su, C. W.; Shern, C. S.

    2002-11-01

    The surface magneto-optical Kerr effect was used to study the magnetic properties of Co ultrathin films deposited on Pt(111). The easy axis of the magnetization changes from the out-of-plane to the in-plane direction after the coverage of Co is larger than 3.5 ML. The spin can reorient to the normal of the surface when the proper thickness of Ag overlayers is deposited on Co/Pt(111) with the in-plane magnetization. The out-of-plane magnetization and its coercivity as a function of Ag coverage were investigated during the spin-reorientation transition. The easy axis of the magnetization can shift back to the in-plane direction after the Ag overlayers are sputtered out. The chemical compositions of the interfaces were measured by Auger electron spectroscopy. The mechanism of the spin-reorientation transition induced by Ag is discussed.

  9. Ore mineralogy of the Serra Pelada Au-Pd-Pt deposit, Carajás, Brazil and implications for ore-forming processes

    NASA Astrophysics Data System (ADS)

    Berni, Gabriel V.; Heinrich, Christoph A.; Lobato, Lydia M.; Wall, Vic

    2016-01-01

    Serra Pelada is a world-class hydrothermal Au-Pd-Pt deposit located at the eastern border of the Amazon craton, northern Brazil. The rocks at Serra Pelada have experienced intense tropical weathering for about 70 Ma, but drill core samples preserve the primary mineralogy and hydrothermal alteration features, with extreme grades of Au, Pd and Pt individually reaching hundreds of parts per million (ppm) by weight. Mineralization at Serra Pelada occurs in hydrothermally altered metasiltstones and dolomitic metasandstones at the hinge zone of a recumbent syncline, comprising zones of hematite, chlorite-carbon, argillic, and siliceous alteration. The main hydrothermal gangue minerals are quartz, kaolinite, sericite, amesite, hematite, monazite, florencite and variable amounts of highly reflective carbonaceous matter. Hydrothermal carbon input is evident from precipitated carbon occurring along crenulation planes and veinlets associated with the precious metals. Ore and accessory minerals include a variety of sulphide, selenide, arsenide, sulphate and oxide minerals, including gold with variable metal contents, palladian gold, fischesserite, sudovikovite, sperrylite, selenian braggite, isomertieite, mertieite-II and secondary Au-Pt-Pd alloys. The composition of fischesserite varies from the ideal formula (Ag3AuSe2) towards a more Ag-rich composition, indicating a disordered solid solution form that is stable only above 260 °C, consistent with the high thermal maturity of associated carbonaceous matter approaching graphite. Primary ore and gangue minerals at Serra Pelada comprise a suite of elements that are best transported in oxidising conditions and precipitated upon reduction. This suggests that fluid mixing between a highly oxidised (metal carrier) and a reduced fluid was a key process for high-grade noble metal precipitation at Serra Pelada.

  10. Ore mineralogy of the Serra Pelada Au-Pd-Pt deposit, Carajás, Brazil and implications for ore-forming processes

    NASA Astrophysics Data System (ADS)

    Berni, Gabriel V.; Heinrich, Christoph A.; Lobato, Lydia M.; Wall, Vic

    2016-08-01

    Serra Pelada is a world-class hydrothermal Au-Pd-Pt deposit located at the eastern border of the Amazon craton, northern Brazil. The rocks at Serra Pelada have experienced intense tropical weathering for about 70 Ma, but drill core samples preserve the primary mineralogy and hydrothermal alteration features, with extreme grades of Au, Pd and Pt individually reaching hundreds of parts per million (ppm) by weight. Mineralization at Serra Pelada occurs in hydrothermally altered metasiltstones and dolomitic metasandstones at the hinge zone of a recumbent syncline, comprising zones of hematite, chlorite-carbon, argillic, and siliceous alteration. The main hydrothermal gangue minerals are quartz, kaolinite, sericite, amesite, hematite, monazite, florencite and variable amounts of highly reflective carbonaceous matter. Hydrothermal carbon input is evident from precipitated carbon occurring along crenulation planes and veinlets associated with the precious metals. Ore and accessory minerals include a variety of sulphide, selenide, arsenide, sulphate and oxide minerals, including gold with variable metal contents, palladian gold, fischesserite, sudovikovite, sperrylite, selenian braggite, isomertieite, mertieite-II and secondary Au-Pt-Pd alloys. The composition of fischesserite varies from the ideal formula (Ag3AuSe2) towards a more Ag-rich composition, indicating a disordered solid solution form that is stable only above 260 °C, consistent with the high thermal maturity of associated carbonaceous matter approaching graphite. Primary ore and gangue minerals at Serra Pelada comprise a suite of elements that are best transported in oxidising conditions and precipitated upon reduction. This suggests that fluid mixing between a highly oxidised (metal carrier) and a reduced fluid was a key process for high-grade noble metal precipitation at Serra Pelada.

  11. Decorated Ag19 on Pt(111) or the "rare gas necklace".

    PubMed

    Schaub, R; Jödicke, H; Brunet, F; Monot, R; Buttet, J; Harbich, W

    2001-04-16

    Ag19 cluster ions are mass selected and deposited on a Pt(111) surface covered by five monolayers of Kr. Almost monodispersed hexagonal shaped Ag islands are observed after Kr evaporation at 125 K. The identification of the island shape and the exact number of atoms has been successful by decorating the clusters with Kr atoms which can be counted by high resolution scanning tunneling microscopy. PMID:11328030

  12. In vitro degradation and biocompatibility of Fe-Pd and Fe-Pt composites fabricated by spark plasma sintering.

    PubMed

    Huang, T; Cheng, J; Zheng, Y F

    2014-02-01

    In order to obtain biodegradable Fe-based materials with similar mechanical properties as 316L stainless steel and faster degradation rate than pure iron, Fe-5 wt.%Pd and Fe-5 wt.%Pt composites were prepared by spark plasma sintering with powders of pure Fe and Pd/Pt, respectively. The grain size of Fe-5 wt.%Pd and Fe-5 wt.%Pt composites was much smaller than that of as-cast pure iron. The metallic elements Pd and Pt were uniformly distributed in the matrix and the mechanical properties of these materials were improved. Uniform corrosion of Fe-Pd and Fe-Pt composites was observed in both electrochemical tests and immersion tests, and the degradation rates of Fe-Pd and Fe-Pt composites were much faster than that of pure iron. It was found that viabilities of mouse fibroblast L-929 cells and human umbilical vein endothelial cells (ECV304) cultured in extraction mediums of Fe-Pd and Fe-Pt composites were close to that of pure iron. After 4 days' culture, the viabilities of L-929 and ECV304 cells in extraction medium of experimental materials were about 80%. The result of direct contact cytotoxicity also indicated that experimental materials exhibited no inhibition on vascular endothelial process. Meanwhile, iron ions released from experimental materials could inhibit proliferation of vascular smooth muscle cells (VSMC), which may be beneficial for hindering vascular restenosis. Furthermore, compared with that of as-cast pure iron, the hemolysis rates of Fe-Pd and Fe-Pt composites were slightly higher, but still within the range of 5%, which is the criteria for good blood compatibility. The numbers of platelet adhered on the surface of Fe-Pd and Fe-Pt composites were lower than that of pure iron, and the morphology of platelets kept spherical. To sum up, the Fe-5 wt.%Pd and Fe-5 wt.%Pt composites exhibited good mechanical properties and degradation behavior, closely approaching the requirements for biodegradable metallic stents. PMID:24411350

  13. Five-fold twinned Pd2NiAg nanocrystals with increased surface Ni site availability to improve oxygen reduction activity.

    PubMed

    Liu, Suli; Zhang, Qinghua; Li, Yafei; Han, Min; Gu, Lin; Nan, Cewen; Bao, Jianchun; Dai, Zhihui

    2015-03-01

    The synthesis of highly active oxygen reduction reaction (ORR) catalysts with good durability and low cost is highly desirable but still remains a significant challenge. In this work, we present the synthesis of five-fold twinned Pd2NiAg nanocrystals (NCs) with a Ni-terminal surface which exhibit excellent electrocatalytic performance for ORR in alkaline media, even better than the performance of the commercial Pt/C catalyst. Using high-angle annular-dark-field imaging together with density functional theory calculations, it is found that the surfaces of the five-fold twinned Pd2NiAg NCs exhibit an unusual valence electron density. The maximum catalytic activity originates from the increased availability of surface Ni sites in five-fold twinned Pd2NiAg NCs and the features of twinned structural defects. This study provides an explanation of the enhanced ORR from the special structure of this novel material, which opens up new avenues for the design of novel classes of electrocatalysts for fuel cells and metal-air batteries. PMID:25626352

  14. One-pot synthesized DNA-templated Ag/Pt bimetallic nanoclusters as peroxidase mimics for colorimetric detection of thrombin.

    PubMed

    Zheng, Cheng; Zheng, Ai-Xian; Liu, Bo; Zhang, Xiao-Long; He, Yu; Li, Juan; Yang, Huang-Hao; Chen, Guonan

    2014-11-01

    We developed a facile one-step approach to synthesize DNA-templated Ag/Pt bimetallic nanoclusters (DNA-Ag/Pt NCs), which possess highly-efficient peroxidase-like catalytic activity. With this finding, an aptamer based sandwich-type strategy is employed to design a label-free colorimetric aptasensor for the protein detection with high sensitivity and selectivity. PMID:25223346

  15. Capability of defective graphene-supported Pd13 and Ag13 particles for mercury adsorption

    NASA Astrophysics Data System (ADS)

    Meeprasert, Jittima; Junkaew, Anchalee; Rungnim, Chompoonut; Kunaseth, Manaschai; Kungwan, Nawee; Promarak, Vinich; Namuangruk, Supawadee

    2016-02-01

    Reactivity of single-vacancy defective graphene (DG) and DG-supported Pdn and Agn (n = 1, 13) for mercury (Hg0) adsorption has been studied using density functional theory calculation. The results show that Pdn binds defective site of DG much stronger than the Agn, while metal nanocluster binds DG stronger than single metal atom. Metal clustering affects the adsorption ability of Pd composite while that of Ag is comparatively less. The binding strength of -8.49 eV was found for Pd13 binding on DG surface, indicating its high stability. Analyses of structure, energy, partial density of states, and d-band center (ɛd) revealed that the adsorbed metal atom or cluster enhances the reactivity of DG toward Hg adsorption. In addition, the Hg adsorption ability of Mn-DG composite is found to be related to the ɛd of the deposited Mn, in which the closer ɛd of Mn to the Fermi level correspond to the higher adsorption strength of Hg on Mn-DG composite. The order of Hg adsorption strength on Mn-DG composite are as follows: Pd13 (-1.68 eV) >> Ag13 (-0.67 eV) ∼ Ag1 (-0.69 eV) > Pd1 (-0.62 eV). Pd13-DG composite is therefore more efficient sorbent for Hg0 removal in terms of high stability and high adsorption reactivity compared to the Ag13. Further design of highly efficient carbon based sorbents should be focused on tailoring the ɛd of deposited metals.

  16. Acetylene trimerization on Ag, Pd and Rh atoms deposited on MgO thin films.

    PubMed

    Judai, Ken; Wörz, Anke S; Abbet, Stéphane; Antonietti, Jean-Marie; Heiz, Ueli; Del Vitto, Annalisa; Giordano, Livia; Pacchioni, Gianfranco

    2005-03-01

    The acetylene trimerization on the group VIII transition metal atoms, Rh and Pd, as well as on Ag atoms supported on MgO thin films has been studied experimentally and theoretically. The three metal atoms with the atomic configurations 4d(8)5s1 (Rh), 4d10s0 (Pd) and 4d(10)5s1 (Ag) behave distinctly differently. The coinage metal atom silver is basically inert for this reaction, whereas Pd is active at 220 and 320 K, and Rh produces benzene in a rather broad temperature range from 350 to ca. 430 K. The origins of these differences are not only the different electronic configurations, leading to a weak interaction of acetylene with silver due to strong Pauli repulsion with the 5s electron but also the different stability and dynamics of the three atoms on the MgO surface. In particular, Rh and Pd atoms interact differently with surface defects like the oxygen vacancies (F centers) and the step edges. Pd atoms migrate already at low temperature exclusively to F centers where the cyclotrimerization is efficiently promoted. The Rh atoms on the other hand are not only trapped on F centers but also at step edges up to about 300 K. Interestingly, only Rh atoms on F centers catalyze the trimerization reaction whereas they are turned inert on the step edges due to strong steric effects. PMID:19791385

  17. Selective Hydrogenation of Phenylacetylene on Bimetallic Cu-Pd and Cu-Pt Catalysts

    NASA Astrophysics Data System (ADS)

    Cladaras, George

    The development of selective catalysts has become a key concept in improving the efficiency of processes. Controlling the product distribution of a reaction can result in fewer by-products and reduce energy requirements for process equipment downstream. The selective hydrogenation of alkynes to alkenes is of major importance to industrial polymerization processes where alkyne/diene impurities can poison the polymerization catalyst and have an unwanted inhibiting effect on the growth of the polymer chain. In many circumstances, bimetallic catalysts have proved to have superior catalytic properties such as greater activity, selectivity or stability compared to their monometallic analogs. A study by the Sykes group (Chemistry, Tufts) in collaboration with our group has shown that in ultra-high vacuum (UHV), the addition of Pd minority species (0.01 ML) onto an otherwise inert Cu(111) single crystal surface can activate the Cu surface for selective hydrogenation reactions. This thesis work is an extension of the surface science study to the preparation of bimetallic catalysts at the nanoscale and their testing in hydrogenation reactions at ambient reaction conditions. The overall aim of this work was to develop single atom alloy Pd-Cu and Pt-Cu catalysts which are highly active and selective for the selective hydrogenation reaction of phenylacetylene to styrene. The bimetallic catalysts were prepared by a colloidal synthesis of Cu nanoparticles immobilized on gamma-alumina support and the precious metals as a minority species were deposited by galvanic replacement. The prepared materials and synthesis technique were characterized with electron microscopy (TEM), UV-Vis spectroscopy, X-Ray diffraction (XRD), temperature programmed reduction (TPR), BET surface area measurements, chemisorption experiments and X-ray photoelectron spectroscopy (XPS). The resulting catalysts can be described as gamma-Al2O3 supported Cu nanoparticles with a narrow size distribution. The Pt/Pd

  18. About contaminant element composition of roadside dust samples from Budapest and Seoul, including Pt and Pd

    NASA Astrophysics Data System (ADS)

    Sager, M.; Chon, H. T.; Marton, L.

    2012-04-01

    Roadside dust was sampled in Seoul megacity /Korea as well as in Budapest and some other places in Hungary, digested with reverse aqua regia in presence of bromine, and analyzed for 29 chemical elements with ICP-OES and ICP-MS methods. In addition to rather traditionally investigated elements, like Pb-Cd-Cr-Ni-As-Sb, newly emerging Pt and Pd from abrasion of automotive catalysts were included in the study. For the analysis of Pd, separation by precipitation with dithizone had to be applied. Principal component analysis was used as a tool to estimate the contribution of various sources. Geogenic element contents were used to estimate geogenic backgrounds und inputs from soils erosion. Seoul is an East Asian densely populated megacity, not far from the seaside, and surrounded by granite rocks. To the contrary, Budapest is a European continental city surrounded mainly by plains formed in the tertiary. Background concentrations were estimated from median concentrations in soils over alluvial deposits from the East of Austria, as well as from Poland. Background concentrations for Seoul were estimated from Shiheung farmland soil, a town close to the megacity. As a result, traffic related contaminations were highly effected by traffic related activities, like stop and go. Pt and Pb levels in roadside dusts from Budapest citiy were in the range of 2-133 μg/kg (av. 62,9 μg/kg), and 88 - 2838 mg/kg (av. 662 mg/kg) respectively. The highest Pt and Pb levels in roadside dust were found at major roads with high traffic volumes. Due to the geo-accumulation index, in all roadside soils sampled in Hungary, Cu-Pb-Zn were enriched, and Cd-Mo and occasionally Ba from Budapest in addition, but As-Co-Cr-Hg-Ni-Tl-V were not. In roadside dusts from Seoul, heavy contaminations of As-Cd-Cu-Mo-Pb-Zn were found, but no significant increase of Co-Cr-Ni-V. The pollution index, which refers to the permissible levels of As-Cd-Cu-Hg-Pb-Sb-Tl-V, indicates heavy pollution for roadside dusts from

  19. Fluctuation spectroscopy of step edges on Pt(111) and Pd(111)

    NASA Astrophysics Data System (ADS)

    Ondrejcek, M.; Swiech, W.; Rajappan, M.; Flynn, C. P.

    2005-08-01

    By step fluctuation spectroscopy, using low-energy electron microscopy (LEEM), we investigate step energies and relaxation on clean Pt(111) and Pd(111) surfaces at temperatures above half the melting temperature Tm . Some effort has been expended to develop accurate procedures for analyzing fluctuations observed as video recordings. The average step stiffnesses are about 210meV/nm and 265meV/nm for Pt and Pd, weakly temperature dependent, and in each case fairly isotropic with mainly a sixfold angular variation. Consequently, the step free energies are highly isotropic. At the lower temperatures, the relaxation rates of fluctuations with wave vector, q , vary as q3 . This is the unambiguous signature of step relaxation by surface diffusion over the terraces. It affords accurate determinations of the surface mass diffusion coefficients Ds=5(×2±1)×10-4exp(-1.2±0.1eV/kBT)cm2/s for Pt(111) and Ds=3(×2.5±1)×10-3exp(-1.15±0.15eV/kBT)cm2/s for Pd(111). At more elevated temperatures the measured rates vary approximately as q2 in both cases. This corresponds to the surface process being short-circuited by a faster flow of bulk vacancies. Known bulk diffusion coefficients for Pt and Pd are consistent with this interpretation. An effective procedure is developed to separate bulk and surface contributions. There is the appearance of universality in the fluctuation processes, which approximates as an homologous dependence on T/Tm . It is observed for Pt(111) at 1400K and above that neighboring steps react to form multisteps that retain capillary characteristics. The stiffnesses of multisteps formed from up to five associated steps have been determined by fluctuation spectroscopy and are employed to discuss the energetics of multistep formation. Clear evidence is found that the multistep free energy contains important contributions from internal degrees of freedom. The kinetics of multistep fluctuations are explained by the same diffusion coefficient Ds determined from

  20. Poly(styrenesulfonic acid)-impregnated alginate capsule for the selective sorption of Pd(II) from a Pt(IV)-Pd(II) binary solution.

    PubMed

    Wei, Wei; Lin, Shuo; Reddy, D Harikishore Kumar; Bediako, John Kwame; Yun, Yeoung-Sang

    2016-11-15

    Poly(styrenesulfonic acid)-impregnated alginate capsule (PSSA-AC) was prepared using a simple fabrication process, and used for selective separation of Pd(II) and Pt(IV) from their mixture. Evaluation of the pH effect revealed that PSSA-AC had good Pd(II) selectivity especially when the pH was between 3 and 5 at which neutral species Pd(OH)2 are present. Experiments on metal penetration through the Ca(2+)-alginate film showed that anionic species hardly penetrate through the alginate film (acting as an ionic barrier). The selective sorption mechanism is proposed as the following steps: (1) selective penetration of the neutral Pd(OH)2 through the ionic barrier (Ca(2+)-alginate shell) and then (2) chelation reaction of the neutral Pd(OH)2 with the SO3(-) groups of PSSA in the core. The maximum Pd(II) uptake was 291.19±17.48mg/g, which was about 32 times higher than that of Pt(IV). The results of the sorption/desorption test indicated that the PSSA-AC has good reusability potential. Even through one cycle of sorption/desorption, Pd(II) and Pt(IV) were successfully separated from their mixture with significantly high purities of 98.65% Pd(II) and 98.71% Pt(IV). This study reports for the first time the feasibility and potential of ionic barrier-based sorbents as selective separation of precious metals which have different speciations. PMID:27399150

  1. Growth of Pt/Cu(100): An Atomistic Modeling Comparison with the Pd/Cu(100) Surface Alloy

    NASA Technical Reports Server (NTRS)

    Demarco, Gustavo; Garces, Jorge E.; Bozzolo, Guillermo

    2002-01-01

    The Bozzolo, Ferrante, and Smith (BFS) method for alloys is applied to the study of Pt deposition on Cu(100). The formation of a Cu-Pt surface alloy is discussed within the framework of previous results for Pd/Cu(100). In spite of the fact that both Pd and Pt share the same basic behavior when deposited on Cu, it is seen that subtle differences become responsible for the differences in growth observed at higher cover-ages. In agreement with experiment, all the main features of Pt/Cu(100) and Pd/Cu(100) are obtained by means of a simple modeling scheme, and explained in terms of a few basic ingredients that emerge from the BFS analysis.

  2. Intracellular surface-enhanced Raman scattering (SERS) with thermally stable gold nanoflowers grown from Pt and Pd seeds

    NASA Astrophysics Data System (ADS)

    Song, Hyon Min; Deng, Lin; Khashab, Niveen M.

    2013-05-01

    SERS provides great sensitivity at low concentrations of analytes. SERS combined with near infrared (NIR)-resonant gold nanomaterials are important candidates for theranostic agents due to their combined extinction properties and sensing abilities stemming from the deep penetration of laser light in the NIR region. Here, highly branched gold nanoflowers (GNFs) grown from Pd and Pt seeds are prepared and their SERS properties are studied. The growth was performed at 80 °C without stirring, and this high temperature growth method is assumed to provide great shape stability of sharp tips in GNFs. We found that seed size must be large enough (>30 nm in diameter) to induce the growth of those SERS-active and thermally stable GNFs. We also found that the addition of silver nitrate (AgNO3) is important to induce sharp tip growth and shape stability. Incubation with Hela cells indicates that GNFs are taken up and reside in the cytoplasm. SERS was observed in those cells incubated with 1,10-phenanthroline (Phen)-loaded GNFs.SERS provides great sensitivity at low concentrations of analytes. SERS combined with near infrared (NIR)-resonant gold nanomaterials are important candidates for theranostic agents due to their combined extinction properties and sensing abilities stemming from the deep penetration of laser light in the NIR region. Here, highly branched gold nanoflowers (GNFs) grown from Pd and Pt seeds are prepared and their SERS properties are studied. The growth was performed at 80 °C without stirring, and this high temperature growth method is assumed to provide great shape stability of sharp tips in GNFs. We found that seed size must be large enough (>30 nm in diameter) to induce the growth of those SERS-active and thermally stable GNFs. We also found that the addition of silver nitrate (AgNO3) is important to induce sharp tip growth and shape stability. Incubation with Hela cells indicates that GNFs are taken up and reside in the cytoplasm. SERS was observed in

  3. Designed synthesis of Au/Ag/Pd trimetallic nanoparticle-based catalysts for Sonogashira coupling reactions.

    PubMed

    Venkatesan, P; Santhanalakshmi, J

    2010-07-20

    Pdnp and Pd containing trimetallic nanoparticles (tnp) are synthesized by chemical method with cetyltrimethylammonium bromide as the capping agent. Compositionally, four different tnp are prepared and the particle sizes are characterized by UV-vis spectra, HR-TEM, and XRD measurements. The catalytic activities of Pdnp and tnp are tested using the Sonogashira C-C coupling reaction. The product yield and recyclability of the recovered catalysts are studied. tnp (1:1:1) exhibited better catalysis than Pdnp, which may be due to the concerted electronic effects of the Au-Ag core onto the Pd shell atoms. PMID:20462280

  4. Cluster Chemistry in Electron-Poor Ae-Pt-Cd Systems (Ae=Ca, Sr, Ba): (Sr,Ba)Pt2Cd4, Ca6Pt8Cd16, and Its Known Antitype Er6Pd16Sb8

    SciTech Connect

    Samal, Saroj L.; Gulo, Fakhili; Corbett, John D.

    2013-02-18

    Three new ternary polar intermetallic compounds, cubic Ca6Pt8Cd16, and tetragonal (Sr, Ba)Pt2Cd4 have been discovered during explorations of the Ae–Pt–Cd systems. Cubic Ca6Pt8Cd16 (Fm-3m, Z = 4, a = 13.513(1) Å) contains a 3D array of separate Cd8 tetrahedral stars (TS) that are both face capped along the axes and diagonally bridged by Pt atoms to generate the 3D anionic network Cd8[Pt(1)]6/2[Pt(2)]4/8. The complementary cationic surface of the cell consists of a face-centered cube of Pt(3)@Ca6 octahedra. This structure is an ordered ternary variant of Sc11Ir4 (Sc6Ir8Sc16), a stuffed version of the close relative Na6Au7Cd16, and a network inverse of the recent Er6Sb8Pd16 (compare Ca6Pt8Cd16). The three groups of elements each occur in only one structural version. The new AePt2Cd4, Ae = Sr, Ba, are tetragonal (P42/mnm,Z = 2, a ≈ 8.30 Å, c ≈ 4.47 Å) and contain chains of edge-sharing Cd4 tetrahedra along c that are bridged by four-bonded Ba/Sr. LMTO-ASA and ICOHP calculation results and comparisons show that the major bonding (Hamilton) populations in Ca6Pt8Cd16 and Er6Sb8Pd16 come from polar Pt–Cd and Pd–Sb interactions, that Pt exhibits larger relativistic contributions than Pd, that characteristic size and orbital differences are most evident for Sb 5s, Pt8, and Pd16, and that some terms remain incomparable, Ca–Cd versus Er–Pd.

  5. Dissolution kinetics of Pd and Pt from automobile catalysts by naturally occurring complexing agents.

    PubMed

    Sebek, Ondřej; Mihaljevič, Martin; Strnad, Ladislav; Ettler, Vojtěch; Ježek, Josef; Stědrý, Robin; Drahota, Petr; Ackerman, Lukáš; Adamec, Vladimír

    2011-12-30

    Powder samples prepared from gasoline (Pt, Pd, Rh, new GN/old GO) and diesel (Pt, new DN/old DO) catalysts and recycled catalyst NIST 2556 were tested using kinetic leaching experiments following 1, 12, 24, 48, 168, 360, 720 and 1440-h interactions with solutions of 20mM citric acid (CA), 20 mM Na(2)P(4)O(7) (NaPyr), 1 g L(-1) NaCl (NaCl), a fulvic acid solution (FA-DOC 50 mg L(-1)) and 20 mM CA at pH 3, 4, 5, 6, 7, 8 and 9. The mobilisation of platinum group elements (PGEs) was fastest in solutions of CA and NaPyr. In the other interactions (NaCl, FA), the release of PGEs was probably followed by immobilisation processes, and the interactions were not found to correspond to the simple release of PGEs into solution. Because of their low concentrations, the individual complexing agents did not have any effect on the speciation of Pd and Pt in the extracts; both metals are present in solution as the complexes Me(OH)(2), Me(OH)(+). Immobilisation can take place through the adsorption of the positively charged hydroxyl complexes or flocculation of fulvic acid, complexing the PGEs on the surface of the extracted catalysts. The calculated normalised bulk released NRi values are similar to the reaction rate highest in the solutions of CA and NaPyr. PMID:22078491

  6. Hydrogenation of Acetylene-Ethylene Mixtures over Pd and Pd-Ag Alloys: First-Principles Based Kinetic Monte Carlo Simulations

    SciTech Connect

    Mei, Donghai; Neurock, Matthew; Smith, C Michael

    2009-10-22

    The kinetics for the selective hydrogenation of acetylene-ethylene mixtures over model Pd(111) and bimetallic Pd-Ag alloy surfaces were examined using first principles based kinetic Monte Carlo (KMC) simulations to elucidate the effects of alloying as well as process conditions (temperature and hydrogen partial pressure). The mechanisms that control the selective and unselective routes which included hydrogenation, dehydrogenation and C-C bond breaking pathways were analyzed using first-principle density functional theory (DFT) calculations. The results were used to construct an intrinsic kinetic database that was used in a variable time step kinetic Monte Carlo simulation to follow the kinetics and the molecular transformations in the selective hydrogenation of acetylene-ethylene feeds over Pd and Pd-Ag surfaces. The lateral interactions between coadsorbates that occur through-surface and through-space were estimated using DFT-parameterized bond order conservation and van der Waal interaction models respectively. The simulation results show that the rate of acetylene hydrogenation as well as the ethylene selectivity increase with temperature over both the Pd(111) and the Pd-Ag/Pd(111) alloy surfaces. The selective hydrogenation of acetylene to ethylene proceeds via the formation of a vinyl intermediate. The unselective formation of ethane is the result of the over-hydrogenation of ethylene as well as over-hydrogenation of vinyl to form ethylidene. Ethylidene further hydrogenates to form ethane and dehydrogenates to form ethylidyne. While ethylidyne is not reactive, it can block adsorption sites which limit the availability of hydrogen on the surface and thus act to enhance the selectivity. Alloying Ag into the Pd surface decreases the overall rated but increases the ethylene selectivity significantly by promoting the selective hydrogenation of vinyl to ethylene and concomitantly suppressing the unselective path involving the hydrogenation of vinyl to ethylidene

  7. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    SciTech Connect

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; Wu, Pu -Wei; Lee, Jyh -Fu

    2014-11-22

    Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1 M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.

  8. High-temperature behavior of a Pd-Ag alloy for porcelain.

    PubMed

    Mackert, J R; Ringle, R D; Fairhurst, C W

    1983-12-01

    The mechanism of formation of nodular material on the surface of a Pd-Ag-based alloy for porcelain during pre-porcelainization heat treatment was investigated using scanning electron microscopy, x-ray diffraction, quantitative metallography, and Auger electron spectroscopy. The nodules were found to form by a Nabarro-Herring creep mechanism driven by the internal oxidation of tin and indium. Implications of this process with regard to porcelain bonding and discoloration are discussed. PMID:6581200

  9. Reaction-driven restructuring of Pt and Pd catalysts: In operando X-ray absorption spectroscopy study

    NASA Astrophysics Data System (ADS)

    Elsen, Annika; Jung, Ulrich; Li, Yuanyuan; Frenkel, Anatoly; Nuzzo, Ralph

    2014-03-01

    The catalyzed hydrogenation of ethylene on supported metal catalysts has been intensively investigated, mainly because this reaction lies at the heart of many industrial processes. Most previous studies have been performed using surface science techniques in UHV. Therefor little is known about the nature of the active state of the catalyst at ambient pressure where the kinetics is very different. We employed operando X-ray absorption spectroscopy (XAS) to correlate the structural changes of SiO2-supported Pt and Pd catalysts with their activity for ethylene hydrogenation. The XAS experiments were performed at the beamlines X19A and X18B, NSLS, BNL. For both catalysts, strong and largely reversible transformations of the metal bonding were identified at about the maximum ethane conversion. The changes were different for Pt/SiO2 and Pd/SiO2 due to the ability of the latter to form bulk hydride, while the former can only adsorb hydrogen on the surface. As a result, Pt/SiO2 undergoes disordering of the surface, leading to a strong reduction of the Pt-Pt coordination number under H2-deficient conditions, while the main effect for Pd/SiO2 is the hydrogen uptake with concomitant increase in Pd-Pd bond length. The correlation between these different kinds of order transitions and differences in rates for these catalysts will be discussed.

  10. Heterogenized Bimetallic Pd-Pt-Fe3O4 Nanoflakes as Extremely Robust, Magnetically Recyclable Catalysts for Chemoselective Nitroarene Reduction.

    PubMed

    Byun, Sangmoon; Song, Yeami; Kim, B Moon

    2016-06-15

    A very simple synthesis of bimetallic Pd-Pt-Fe3O4 nanoflake-shaped alloy nanoparticles (NPs) for cascade catalytic reactions such as dehydrogenation of ammonia-borane (AB) followed by the reduction of nitro compounds (R-NO2) to anilines or alkylamines (R-NH2) in methanol at ambient temperature is described. The Pd-Pt-Fe3O4 NPs were easily prepared via a solution phase hydrothermal method involving the simple one-pot coreduction of potassium tetrachloroplatinate (II) and palladium chloride (II) in polyvinylpyrrolidone with subsequent deposition on commercially available Fe3O4 NPs. The bimetallic Pd-Pt alloy NPs decorated on Fe3O4 NPs provide a unique synergistic effect for the catalysis of cascade dehydrogenation/reduction. Various nitroarene derivatives were reduced to anilines with very specific chemoselectivity in the presence of other reducible functional groups. The bimetallic Pd-Pt-Fe3O4 NPs provide a unique synergistic effect for the catalysis of cascade dehydrogenation/reduction. The nitro reduction proceeded in 5 min with nearly quantitative conversions and yields. Furthermore, the magnetically recyclable nanocatalysts were readily separated using an external magnet and reused up to 250 times without any loss of catalytic activity. A larger scale (10 mmol) reaction was also successfully performed with >99% yield. This efficient, recyclable Pd-Pt-Fe3O4 NPs system can therefore be repetitively utilized for the reduction of various nitro-containing compounds. PMID:27191706

  11. Mobilization, adsorption, and bioavailability of Pt and Pd in coastal sediments: the role of the polychaete, Arenicola marina.

    PubMed

    French, Ben; Turner, Andrew

    2008-05-15

    The biogeochemical behavior of Pt and Pd in coastal sediments has been examined in a series of microcosms, both in the presence and absence of the deposit-feeding invertebrate, Arenicola marina. When metals were introduced to the overlying water column as solutes from acidified standards, A. marina dramatically enhanced their sorption to sediment throughout the core depth (14 cm) compared with an unfaunated control by exposing a greater surface area of particles to more rapidly ventilating contaminated water. After a 10 day incubation period, the assimilation efficiency (AE) by A. marina was about 10% for Pt and 1% for Pd. Calculations based on either partition constants or operational measures of metal bioaccessibility in sediment (using the protein, BSA) suggested that both aqueous and dietary sources of metal were important When Pt and Pd were introduced to the sediment-water interface as components of ground catalytic converter particles, significant subduction was effected by A. marina, and metals were solubilized to a greater extent than in an unfaunated control. AE in these experiments was < 0.1% for Pt and about 1% for Pd, and the most important vector for assimilation appeared to be from the aqueous phase via partial solubilization of metal from catalytic material. The findings of this study improve our understanding of the availability, cycling, and fate of Pt and Pd in contaminated estuaries and coastal waters. PMID:18546687

  12. Anthropogenic platinum group element (Pt, Pd, Rh) concentrations in PM10 and PM2.5 from Kolkata, India.

    PubMed

    Diong, Huey Ting; Das, Reshmi; Khezri, Bahareh; Srivastava, Bijayen; Wang, Xianfeng; Sikdar, Pradip K; Webster, Richard D

    2016-01-01

    This study investigates platinum group elements (PGEs) in the breathable (PM10) and respirable (PM2.5) fractions of air particulates from a heavily polluted Indian metro city. The samples were collected from traffic junctions at the heart of the city and industrial sites in the suburbs during winter and monsoon seasons of 2013-2014. PGE concentrations were determined by inductively coupled plasma-mass spectrometry (ICP-MS). The PGE concentrations in the samples from traffic junctions are within the range of 2.7-111 ng/m(3) for Pd, 0.86-12.3 ng/m(3) for Pt and 0.09-3.13 ng/m(3) for Rh, and from industrial sites are within the range of 3.12-32.3 ng/m(3) for Pd, 0.73-7.39 ng/m(3) for Pt and 0.1-0.69 ng/m(3) for Rh. Pt concentrations were lower in the monsoon compared to winter while Pd concentrations increased during monsoon and Rh stayed relatively unaffected across seasons. For all seasons and locations, concentrations of Pd > Pt > Rh, indicating dominance of Pd-containing exhaust converters. Most of the PGEs were concentrated in the PM2.5 fraction. A strong correlation (R ≥ 0.62) between the PGEs from traffic junction indicates a common emission source viz. catalytic converters, whereas a moderate to weak correlation (R ≤ 0.5) from the industrial sites indicate mixing of different sources like coal, raw materials used in the factories and automobile. A wider range of Pt/Pd, Pt/Rh and Pd/Rh ratios measured in the traffic junction possibly hint towards varying proportions of PGEs used for catalyst productions in numerous rising and established car brands. PMID:27536525

  13. The structure of a commercial dental Ag-Pd-Cu-Au casting alloy.

    PubMed

    Niemi, L; Herø, H

    1984-02-01

    The structure of a commercial dental Ag-Pd-Cu-Au casting alloy has been studied by microprobe and X-ray diffraction analyses after various heat treatments. The composition of phases in equilibrium was established. After being annealed at 400 degrees C, 500 degrees C, and 600 degrees C for seven wk, the alloy consisted of three phases: a Cu- and Pd-rich fee phase (alpha 1) with alpha = 0.372nm, a Ag-rich matrix (alpha 2) with alpha = 0.399nm, and an ordered CsCl-type bcc PdCu phase with alpha = 0.296nm. The PdCu phase was not observed above 600 degrees C, and the proportion of the alpha 1 phase decreased sharply above 700 degrees C. After being annealed at 900 degrees C, the alloy matrix was partly decomposed at the Cu-enriched grain boundaries. The decomposed areas grew into the grain interior during subsequent precipitation hardening. No segregation of Au was detected after casting, and the element was evenly distributed throughout the alloy structure after all heat treatments. PMID:6582096

  14. Screening of electrocatalysts for direct ammonia fuel cell: Ammonia oxidation on PtMe (Me: Ir, Rh, Pd, Ru) and preferentially oriented Pt(1 0 0) nanoparticles

    NASA Astrophysics Data System (ADS)

    Vidal-Iglesias, F. J.; Solla-Gullón, J.; Montiel, V.; Feliu, J. M.; Aldaz, A.

    Ammonia has attracted attention as a possible fuel for direct fuel cells since it is easy to handle and to transport as liquid or as concentrated aqueous solution. However, on noble metal electrodes ammonia oxidation is a sluggish reaction and the electrocatalyst needs to be improved for developing efficient ammonia fuel cells. In this work, ammonia electrooxidation reaction on 3-4-nm bimetallic PtMe (Ir, Rh, Pd, Ru) and on preferentially oriented Pt(1 0 0) nanoparticles is reported. PtMe nanoparticles have been prepared by using water-in-oil microemulsions to obtain a narrow size distribution whereas preferentially oriented Pt nanoparticles have been prepared through colloidal routes. Among all the bimetallic samples tested, only Pt 75Ir 25 and Pt 75Rh 25 nanoparticles show, at the low potential range, an enhancement of the oxidation density current with respect to the behaviour found for pure platinum nanoparticles prepared by the same method. In addition, two Pt(1 0 0) preferentially oriented nanoparticles of different particle size (4 and 9 nm) have been also studied. These oriented nanoparticles show higher current densities than polycrystalline Pt nanoparticles due to the sensitivity of ammonia oxidation toward the presence of surface sites with square symmetry. The reactivity of the different 4-nm nanoparticles parallels well with that expected from bulk PtMe alloys and Pt single crystal electrodes.

  15. Combinatorial PtSnM (M = Fe, Ni, Ru and Pd) nanoparticle catalyst library toward ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Almeida, T. S.; Van Wassen, A. R.; VanDover, R. B.; de Andrade, A. R.; Abruña, H. D.

    2015-06-01

    Electrode arrays containing 91 combinations of Pt-Sn-M (M = Fe, Ni, Pd, and Ru) were prepared by borohydride reduction of aqueous metal salts on carbon paper, and screened by fluorescence assay for activity as ethanol electrooxidation catalysts. Catalysts that showed high activity for this reaction were identified as being Pt(80)Sn(10)Fe(10), Pt(80)Sn(10)Ni(10), Pt(70)Sn(20)Pd(10), and Pt(70)Sn(10)Ru(20) (numbers in parenthesis indicate atomic percent). These were significantly more active than Pt or PtSn catalysts, also present in the electrode arrays. These 4 compositions were synthesized as nanoparticles and characterized physically and electrochemically. X-ray diffraction showed a Pt face-centered cubic (fcc) structure with an average crystallite size of about 2.0 nm for all catalysts. The electrochemical tests for the oxidation of ethanol revealed excellent electrocatalytic activity and single cell (fuel cell) power density for all four catalyst formulations. Fe-containing catalysts exhibited the highest activity (13 A gPt-1) and single-cell performance (50 mW cm-2) followed by Ni- and Pd-containing materials with similar results; electrocatalytic activity around 10 A gPt-1 and power densities of 43 mW cm-2. The lowest performance was observed for the Ru-containing catalyst. However, its single-cell performance (30 mW cm-2) was still comparable to that of the commercial PtSn-Etek electrocatalyst.

  16. Recent Advances in Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction: Scale-up Synthesis Structure and Activity of Pt Shells on Pd Cores

    SciTech Connect

    Sasaki K.; Wang J.X.; Naohara H.; Marinkovic N.; More K.; Inada H.; Adzic R.R.

    2010-03-01

    We have established a scale-up synthesis method to produce gram-quantities of Pt monolayer electrocatalysts. The core-shell structure of the Pt/Pd/C electrocatalyst has been verified using the HAADF-STEM Z-contrast images, STEM/EELS, and STEM/EDS line profile analysis. The atomic structure of this electrocatalyst and formation of a Pt monolayer on Pd nanoparticle surfaces were examined using in situ EXAFS. The Pt mass activity of the Pt/Pd/C electrocatalyst for ORR is considerably higher than that of commercial Pt/C electrocatalysts. The results with Pt monolayer electrocatalysts may significantly impact science of electrocatalysis and fuel-cell technology, as they have demonstrated an exceptionally effective way of using Pt that can resolve problems of other approaches, including electrocatalysts inadequate activity and high Pt content.

  17. Quantum valley Hall states and topological transitions in Pt(Ni, Pd)-decorated silicene: A first-principles study

    SciTech Connect

    Zhao, Bao; Zhang, Jiayong; Wang, Yicheng; Yang, Zhongqin

    2014-12-28

    The electronic states and topological behaviors of Pt(Ni, Pd)-decorated silicene are investigated by using an ab-initio method. All the three kinds of the adatoms prefer hollow sites of the silicene, guaranteeing the Dirac cones unbroken. The Pt(Ni, Pd)-decorated silicene systems all present quantum valley Hall (QVH) states with the gap opened exactly at the Fermi level. The gaps of the QVH states can be increased substantially by applying a positive electric field. Very fascinating phase transitions from QVH to quantum spin Hall (QSH) and then to QVH again are achieved in the Pt/Ni-decorated silicene when a negative electric field is applied. The QSH state in the Pd case with a negative electric field is, however, quenched because of relatively larger Rashba spin-orbit coupling (SOC) than the intrinsic SOC in the system. Our findings may be useful for the applications of silicene-based devices in valleytronics and spintronics.

  18. Multi-walled carbon nanotube supported Pd and Pt nanoparticles with high solution affinity for effective electrocatalysis

    NASA Astrophysics Data System (ADS)

    Ye, Weichun; Hu, Haiyuan; Zhang, Hong; Zhou, Feng; Liu, Weimin

    2010-09-01

    Multi-walled carbon nanotubes (MWCNTs) are easily wrapped with a functional biopolymer—polydopamine (Pdop) through self-polymerization of dopamine in a mild basic solution. The MWCNTs@Pdop exhibits long term dispersivity in water for at least one month. The Pdop has large capacity to coordinate [PdCl 4] 2- and [PtCl 6] 2- that upon reduction transform to corresponding metal nanoparticles. The nanoparticles strongly adhere to Pdop layer and can be used for the electrooxidation of haydrazine and methanol, respectively. Compared to Pd and Pt supported on unmodified MWCNTs, the Pd and Pt nanoparticle decorated on MWCNTs@Pdop exhibit much higher electrocatalytic activity and enhanced stability.

  19. Modeling closure of the Pd-Ag system in iron meteorites

    NASA Astrophysics Data System (ADS)

    Van Orman, J.; Matthes, M.; Fischer-Gödde, M.; Krawczynski, M. J.; Kleine, T.

    2015-12-01

    J.A. Van Orman1, M. Matthes2, M. Fischer-Godde2, M.J. Krawczynski3, T. Kleine21 Case Western Reserve University, Cleveland, OH 44106 (james.vanorman@case.edu) 2 Westfalische Wilhelms-Universitat Muenster, 48149 Muenster, Germany 3 Washington University, St. Louis, MO 63130 The short-lived Pd-107/Ag-107 system can provide constraints on the timing of assembly and cooling of iron meteorite parent bodies, but to interpret the dates derived from this system it is necessary to understand the closure conditions. Palladium is strongly enriched in the metal phases, and sulphide (troilite) is the primary sink for radiogenic silver. Closure of the system hence depends primarily on the transfer of Ag-107 from metal to troilite. Because cation diffusion in troilite is extremely rapid, Ag-107 transfer is likely to be controlled by diffusion through the metal. Sugiura and Hoshino (2003) estimated a closure temperature of ~1100 K for the Pd/Ag system in iron meteorites under the assumption that the diffusion rate of Ag in the metal is similar to that of Ni diffusion in taenite. Here we consider the problem in more detail, utilizing constraints on Ag diffusion in taenite and kamacite from the metallurgical literature to numerically model diffusive exchange between metal and troilite with simultaneous radiogenic ingrowth. The process is complicated by exsolution of the metal into bcc kamacite and fcc taenite phases during cooling. We will discuss approaches to the treatment of this issue and their influence on the derived closure temperatures. Sugiura N., Hoshino H. (2003) Meteorit. Planet. Sci. 38, 117-143.

  20. Ag-Pd-Cu alloy inserted transparent indium tin oxide electrodes for organic solar cells

    SciTech Connect

    Kim, Hyo-Joong; Seo, Ki-Won; Kim, Han-Ki; Noh, Yong-Jin; Na, Seok-In

    2014-09-01

    The authors report on the characteristics of Ag-Pd-Cu (APC) alloy-inserted indium tin oxide (ITO) films sputtered on a glass substrate at room temperature for application as transparent anodes in organic solar cells (OSCs). The effect of the APC interlayer thickness on the electrical, optical, structural, and morphological properties of the ITO/APC/ITO multilayer were investigated and compared to those of ITO/Ag/ITO multilayer electrodes. At the optimized APC thickness of 8 nm, the ITO/APC/ITO multilayer exhibited a resistivity of 8.55 × 10{sup −5} Ω cm, an optical transmittance of 82.63%, and a figure-of-merit value of 13.54 × 10{sup −3} Ω{sup −1}, comparable to those of the ITO/Ag/ITO multilayer. Unlike the ITO/Ag/ITO multilayer, agglomeration of the metal interlayer was effectively relieved with APC interlayer due to existence of Pd and Cu elements in the thin region of the APC interlayer. The OSCs fabricated on the ITO/APC/ITO multilayer showed higher power conversion efficiency than that of OSCs prepared on the ITO/Ag/ITO multilayer below 10 nm due to the flatness of the APC layer. The improved performance of the OSCs with ITO/APC/ITO multilayer electrodes indicates that the APC alloy interlayer prevents the agglomeration of the Ag-based metal interlayer and can decrease the thickness of the metal interlayer in the oxide-metal-oxide multilayer of high-performance OSCs.

  1. In situ spectroscopic ellipsometry during atomic layer deposition of Pt, Ru and Pd

    NASA Astrophysics Data System (ADS)

    Leick, N.; Weber, J. W.; Mackus, A. J. M.; Weber, M. J.; van de Sanden, M. C. M.; Kessels, W. M. M.

    2016-03-01

    The preparation of ultra-thin platinum-group metal films, such as Pt, Ru and Pd, by atomic layer deposition (ALD) was monitored in situ using spectroscopic ellipsometry in the photon energy range of 0.75–5 eV. The metals’ dielectric function was parametrized using a ‘flexible’ Kramers–Kronig consistent dielectric function because it was able to provide accurate curve shape control over the optical response of the metals. From this dielectric function, it was possible to extract the film thickness values during the ALD process. The important ALD process parameters, such as the nucleation period and growth per cycle of Pt, Ru and Pd could be determined from the thickness evolution. In addition to process parameters, the film resistivity in particular could be extracted from the modeled dielectric function. Spectroscopic ellipsometry thereby revealed itself as a feasible and valuable technique to be used in research and development applications, as well as for process monitoring during ALD.

  2. Co/Pt and Co/Pd multilayers as magneto-optical recording materials

    NASA Astrophysics Data System (ADS)

    Hashimoto, S.; Ochiai, Y.

    1990-07-01

    The magneto-optical and magnetic properties of Co/Pt and Co/Pd multilayers for magneto-optical recording materials are described. Thick multilayers do not have an adequate Kerr loop for MO recording because of forming a stripe domain configuration in the remanent magnetization. However, thin films below a few hundred ångström exhibit a perfect square Kerr loop as interpreted by domain theory. The Kerr rotation is enhanced at the ultrathin region by optical interference and multiple reflection, and the enhancement is remarkable especially at wavelengths above 500 nm. The coercivity of the ultrathin films increases to between one and several kOe by the sputtering gas conditions and the under layers of fcc metal atoms, originating from a change in the film morphology and an increase in the perpendicular magnetic anisotropy, respectively. These ultrathin multilayers having large Kerr rotation at shorter wavelengths and high corrosion resistance are promising candidates for high density MO recording. The magneto-optical disks using 2P pre-grooved glass substrate showed carrier-to-noise ratios of 53 and 46 dB at 780 nm for Co/Pt and Co/Pd media, respectively. Regular and clear bit domains were observed and completely erased thermomagnetically.

  3. Ultrathin Co/Pt and Co/Pd new magneto-optical recording media

    NASA Astrophysics Data System (ADS)

    Hashimoto, Shunichi; Matsuda, Hideki; Ochiai, Yoshitaka

    1990-08-01

    Co/Pt and Co/Pd multilayers were prepared by two source dc-magnetron sputtering. Magneto-optical properties of these multilayers were affected by total film thickness, and a perfect squareness of Kerr loop and an enhancement of Kerr rotation angle weresimultaneously achieved when the film thickness was below several hundred angstroms. The improvement of Kerr remanence ratio can be explained by the change in domain structure from a stripe domain to a single domain, d the enhancement of Kerr rotation is due to the optical interference effect with the multiple reflection. The ultrathin films have high corrosion resistance, large Kerr rotation and strong perpendicular magnetic anisotropy even in very thin film thickness. A hermomagnetic writing was successfully made in the magneto-optical disks using these ultrathin media,and the C/N ratio showed 53 dB and 46 dB for Co/Pt and Co/Pd disks,respectively.The figure of merit becomes larger at shorter wavelength, and thus the ultrathin multilayers can be new promising magneto-optical recording media, especially for higher density recording using a shorter wavelength laser.

  4. Rare earth-modified kaolin/NaY-supported Pd-Pt bimetallic catalyst for the catalytic combustion of benzene.

    PubMed

    Zuo, Shufeng; Sun, Xuejie; Lv, Ningning; Qi, Chenze

    2014-08-13

    A new type of porous kaolin/NaY composite (KL-NY) with a large specific surface area and large pore sizes was synthesized through a one-step crystallization process, and rare earth-modified KL-NY-supported Pd-Pt catalysts were studied for benzene combustion. The results indicated that the pore volume and specific surface area of KL-NY after calcination and crystallization were 0.298 cm(3)/g and 365 m(2)/g, respectively, exhibiting appropriate pore structure and good thermal stability. Catalysts with rare earth metals greatly enhanced the activity of Pd/KL-NY, and the addition of Pt and Ce into the Pd catalyst improved the catalytic activity as well as the stability. The catalyst with an optimal Ce content and Pt/Pd molar ratio (0.2%Pd-Pt (6:1)/6%Ce/KL-NY) demonstrated the best activity for the complete oxidation of benzene at 230 °C, and the catalyst above maintained the 100% benzene conversion for 960 h. PMID:25057756

  5. Effects of Annealing Twins on the Grain Growth and Mechanical Properties of Ag-8Au-3Pd Bonding Wires

    NASA Astrophysics Data System (ADS)

    Chuang, Tung-Han; Tsai, Chih-Hsin; Wang, Hsi-Ching; Chang, Che-Cheng; Chuang, Chien-Hsun; Lee, Jun-Der; Tsai, Hsing-Hua

    2012-11-01

    An innovative Ag-8Au-3Pd bonding wire containing a large amount of annealing twins has been produced. In contrast to the apparent grain growth in a conventional Ag-8Au-3Pd wire during aging at 600°C, the grain size of this annealing-twinned Ag alloy wire remains almost unchanged. The high thermal stability of the grain structure leads to a smaller heat-affected zone near the free air ball of this twinned wire. The annealing twins in this material also result in the dual merits of increased tensile strength and elongation with aging time, which is beneficial for the reliability of wire-bonded packages.

  6. Synthesis and Catalytic Activity of Pt Monolayer on Pd Tetrahedral Nanocrystals with CO-adsorption-induced Removal of Surfactants

    SciTech Connect

    Gong K.; Vukmirovic M.B.; Ma C.; Zhu Y.; Adzic R.R.

    2011-11-01

    We synthesized the Pt monolayer shell-Pd tetrahedral core electrocatalysts that are notable for their high activity and stable performance. A small number of low-coordination sites and defects, and high content of the (1 1 1)-oriented facets on Pd tetrahedron makes them a suitable support for a Pt monolayer to obtain an active O{sub 2} reduction reaction (ORR) electrocatalyst. The surfactants, used to control size and shape of Pd tetrahedral nanoparticles, are difficult to remove and cause adverse effects on the ORR. We describe a simple and noninvasive method to synthesize high-purity tetrahedral Pd nanocrystals (TH Pd) by combining a hydrothermal route and CO adsorption-induced removal of surfactants. Poly(vinylpyrrolidone) (PVP), used as a protecting and reducing agent in hydrothermal reactions, is strongly bonded to the surface of the resulting nanocrystals. We demonstrate that PVP was displaced efficiently by adsorbed CO. A clean surface was achieved upon CO stripping at a high potential (1.0 V vs RHE). It played a decisive role in improving the activity of the Pt monolayer/TH Pd electrocatalyst for the ORR. Furthermore, the results demonstrate a versatile method for removal of surfactants from various nanoparticles that severely limited their applications.

  7. Enhanced electrocatalytic activity and stability of Pd3V/C nanoparticles with a trace amount of Pt decoration for the oxygen reduction reaction

    SciTech Connect

    Liu, Sufen; Han, Lili; Zhu, Jing; Xiao, Weiping; Wang, Jie; Liu, Hongfang; Xin, Huolin; Wang, Deli

    2015-09-14

    In this study, carbon supported Pd3V bimetallic alloy nanoparticles (Pd3V/C) have been successfully synthesized via a simple impregnation–reduction method, followed by high temperature treatment under a H2 atmosphere. Electrochemical tests reveal that the half-wave potential of Pd3V/C-500 shifts positively 40 mV compared with Pd/C. However, the catalytic activity of Pd3V/C-500 suffers from serious degradation after 1k cycles. By a spontaneous displacement reaction or co-reduction method, a trace amount of Pt was decorated on the surface or inside of the Pd3V/C nanoparticles. The catalytic activity and stability of the Pd3V@Pt/C and Pt-Pd3V/C catalysts for the oxygen reduction reaction (ORR) are enhanced significantly, and are comparable to commercial Pt/C. In addition, the Pt mass activity of Pd3V@Pt/C and Pt-Pd3V/C improves by factors of 10.9 and 6.5 at 0.80 V relative to Pt/C. Moreover, Pt-decorated Pd3V/C nanoparticles show almost no obvious morphology change after durability tests, because the Pt-rich shell plays an important role in preventing degradation.

  8. Solubility and Dissolution Rate of Ni Base Alloy to Molten Ag-Cu-Pd Brazing Filler

    NASA Astrophysics Data System (ADS)

    Ikeshoji, Toshi-Taka; Watanabe, Yuki; Suzumura, Akio; Yamazaki, Takahisa

    During the brazing process of the rocket engine’s nozzle skirt assembly made from Fe-Ni based super alloy pipes with Pd based brazing filler, the erosion corrosion pits were sometimes engraved on those pipes’ surface. The corrosion is considered to be assisted by the dynamic flow of the molten brazing filler. In order to estimate the amount of erosion corrosion and to prevent it, the solubility and the dissolution rate of Ni to the molten Ag-Cu-Pd brazing filler are measured experimentally. The Ni crucible poured with the Ag-Cu-Pd brazing filler was heated up to 1320K and quenched after the various keeping time. The microstructure of the solidified brazing filler part’s cross sections was observed, and the amount of the dissolved Ni was estimated using the image processing technique. The solubility was about 5.53mass%and the initial dissolution rate was 6.28 × 10-3mass%/s. Using these data, more elaborate dynamic flow simulation will be able to conduct.

  9. PdAgAu alloy with high resistance to corrosion by H2S

    SciTech Connect

    Braun, Fernando; Miller, James B.; Gellman, Andrew J.; Tarditi, Ana M.; Fleutot, Benoit; Kondratyuk, Petro; Cornaglia, Laura M.

    2012-12-01

    PdAgAu alloy films were prepared on porous stainless steel supports by sequential electroless deposition. Two specific compositions, Pd83Ag2Au15 and Pd74Ag14Au12, were studied for their sulfur tolerance. The alloys and a reference Pd foil were exposed to 1000 H2S /H2 at 623 K for periods of 3 and 30 hours. The microstructure, morphology and bulk composition of both nonexposed and H2S-exposed samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). XRD and SEM analysis revealed time-dependent growth of a bulk Pd{sub 4}S phase on the Pd foil during H2S exposure. In contrast, the PdAgAu ternary alloys displayed the same FCC structure before and after H2S exposure. In agreement with the XRD and SEM results, sulfur was not detected in the bulk of either ternary alloy samples by EDS, even after 30 hours of H2S exposure. X-ray photoelectron spectroscopy (XPS) depth profiles were acquired for both PdAgAu alloys after 3 and 30 hours of exposure to characterize sulfur contamination near their surfaces. Very low S 2p and S 2s XPS signals were observed at the top-surfaces of the PdAgAu alloys, and those signals disappeared before the etch depth reached ~ 10 nm, even for samples exposed to H2S for 30 hours. The depth profile analyses also revealed silver and gold segregation to the surface of the alloys; preferential location of Au on the alloys surface may be related to their resistance to bulk sulfide formation. In preliminary tests, a PdAgAu alloy membrane displayed higher initial H{sub 2} permeability than a similarly prepared pure Pd sample and, consistent with resistance to bulk sulfide formation, lower permeability loss in H2S than pure Pd.

  10. Transparent ITO/Ag-Pd-Cu/ITO multilayer cathode use in inverted organic solar cells

    SciTech Connect

    Kim, Hyo-Joong; Kim, Han-Ki; Lee, Hyun Hwi; Kal, Jinha; Hahn, Jungseok

    2015-10-15

    The characteristics of transparent ITO/Ag-Pd-Cu (APC)/ITO multilayer cathodes were investigated for use in inverted organic solar cells (IOSCs). The insertion of an APC interlayer into the ITO film effectively led to crystallization of the top ITO layer, unlike that in the Ag interlayer, and resulted in a low sheet resistance of 6.55 Ohm/square and a high optical transmittance of 84.14% without post annealing. In addition, the alloying of the Pd and Cu elements into Ag prevented agglomeration and oxidization of the metal interlayer and led to more stable ITO/APC/ITO films under ambient conditions. The microstructure and interfacial structure of the transparent ITO/APC/ITO cathode in the IOSCs were examined in detail by synchrotron X-ray scattering and high resolution transmission electron microscopy. Furthermore, we suggested a possible mechanism to explain the lower PCE of the IOSCs with an ITO/APC/ITO cathode than that of a reference IOSC with a crystalline ITO cathode using the external quantum efficiency of the IOSCs.

  11. Transparent ITO/Ag-Pd-Cu/ITO multilayer cathode use in inverted organic solar cells

    NASA Astrophysics Data System (ADS)

    Kim, Hyo-Joong; Lee, Hyun Hwi; Kal, Jinha; Hahn, Jungseok; Kim, Han-Ki

    2015-10-01

    The characteristics of transparent ITO/Ag-Pd-Cu (APC)/ITO multilayer cathodes were investigated for use in inverted organic solar cells (IOSCs). The insertion of an APC interlayer into the ITO film effectively led to crystallization of the top ITO layer, unlike that in the Ag interlayer, and resulted in a low sheet resistance of 6.55 Ohm/square and a high optical transmittance of 84.14% without post annealing. In addition, the alloying of the Pd and Cu elements into Ag prevented agglomeration and oxidization of the metal interlayer and led to more stable ITO/APC/ITO films under ambient conditions. The microstructure and interfacial structure of the transparent ITO/APC/ITO cathode in the IOSCs were examined in detail by synchrotron X-ray scattering and high resolution transmission electron microscopy. Furthermore, we suggested a possible mechanism to explain the lower PCE of the IOSCs with an ITO/APC/ITO cathode than that of a reference IOSC with a crystalline ITO cathode using the external quantum efficiency of the IOSCs.

  12. Microstructure and anodic polarization behavior of experimental Ag-18Cu-15Pd-12Au alloy in aqueous sulfide solution.

    PubMed

    Endo, Kazuhiko; Ohno, Hiroki; Asakura, Shukuji

    2003-05-01

    The anodic corrosion behavior of an experimental Ag-15Pd-18Cu-12Au alloy in 0.1% Na(2)S solution in relation to its microstructure was investigated using potentiodynamic and potentiostatic polarization techniques with analyses of corrosion products by X-ray diffractometry, Auger electron spectroscopy, and X-ray photoelectron spectroscopy. The role of Pd in improvement of the corrosion resistance was also investigated. In the potential/current density curve, three distinct current peaks, at -520 mV (peak I), -425 mV (peak II) and -175 mV (peak III), were observed. The Ag-rich alpha(2) matrix with coarse Cu and Pd-rich lamellae was the most corrosion-susceptible region, and this region was preferentially corroded at peak I with the formation of granular deposits of Ag(2)S. A small amount of Ag-Cu mixed sulfide deposited on the Cu and Pd-rich coarse particles and dissolution of Ag as AgO(-) might have occurred in parallel with Ag(2)S formation at peak II. Enrichment of Pd on the alloy surface occurred at peak III due to preferential dissolution of Ag and Cu. A high level of corrosion resistance was attained with the formation of a thin Pd-rich sulfide film, which enhanced the passivity of the alloy in an alkaline sulfide solution. It was found that passivity is an important phenomenon not only for base metal alloys but also for noble metal alloys to maintain high levels of resistance to corrosion and tarnishing in sulfide environments. PMID:15348446

  13. Direct inelastic scattering of oriented NO from Ag(111) and Pt(111)

    NASA Astrophysics Data System (ADS)

    Tenner, Manfred G.; Kuipers, Edgar W.; Kleyn, Aart W.; Stolte, Steven

    1991-04-01

    A pulsed supersonic and cold oriented beam of NO molecules is incident upon the (111) face of clean Ag and Pt single crystal surfaces. The steric effect in the scattered density distributions is determined by a quadrupole mass spectrometer. It is found that the steric effect in the peak in the distribution of direct inelastically scattered molecules depends linearly on the reflection angle. In all circumstances O-end collisions lead to scattering angles more inclined towards the surface than N-end collisions. For the Pt(111) surface a much stronger steric effect is measured than for the Ag(111) surface. The steric effect seems to scale with the incident normal velocity. These strong steric effects can be explained by the larger trapping probability for the N-end orientation and a leverage effect due to the high trapping probability.

  14. Bimetallic PtM (M=Pd, Ir) nanoparticle decorated multi-walled carbon nanotube enzyme-free, mediator-less amperometric sensor for H₂O₂.

    PubMed

    Chen, Kuan-Jung; Chandrasekara Pillai, K; Rick, John; Pan, Chun-Jern; Wang, Shih-Han; Liu, Chung-Chiun; Hwang, Bing-Joe

    2012-03-15

    A new highly catalytic and intensely sensitive amperometric sensor based on PtM (where M=Pd, Ir) bimetallic nanoparticles (NPs) for the rapid and accurate estimation of hydrogen peroxide (H(2)O(2)) by electrooxidation in physiological conditions is reported. PtPd and PtIr NPs-decorated multiwalled carbon nanotube nanocatalysts (PtM/MWCNTs) were prepared by a modified Watanabe method, and were characterized by XRD, TEM, ICP, and XAS. The sensors were constructed by immobilizing PtM/MWCNTs nanocatalysts in a Nafion film on a glassy carbon electrode. Both PtPd/MWCNTs and PtIr/MWCNTs assemblies catalyzed the electrochemical oxidation of H(2)O(2). Cyclic voltammetry characterization measurements revealed that both the PtM (M=Pd, Ir)/MWCNTs/GCE possessed similar electrochemical surface areas (∼0.55 cm(2)), and electron transfer rate constants (∼1.23 × 10(-3)cms(-1)); however, the PtPd sensor showed a better performance in H(2)O(2) sensing than did the PtIr counterpart. Explanations were sought from XAS measurements to explain the reasons for differences in sensor activity. When applied to the electrochemical detection of H(2)O(2), the PtPd/MWCNTs/GC electrode exhibited a low detection limit of 1.2 μM with a wide linear range of 2.5-125 μM (R(2)=0.9996). A low working potential (0V (SCE)), fast amperometric response (<5s), and high sensitivity (414.8 μA mM(-1)cm(-2)) were achieved at the PtPd/MWCNTs/GC electrode. In addition, the PtPd/MWCNTs nanocatalyst sensor electrode also exhibited excellent reproducibility and stability. Along with these attractive features, the sensor electrode also displayed very high specificity to H(2)O(2) with complete elimination of interference from UA, AA, AAP and glucose. PMID:22236778

  15. Ultrasonic-assisted synthesis of Pd-Pt/carbon nanotubes nanocomposites for enhanced electro-oxidation of ethanol and methanol in alkaline medium.

    PubMed

    Yang, Guohai; Zhou, Yazhou; Pan, Horng-Bin; Zhu, Chengzhou; Fu, Shaofang; Wai, Chien M; Du, Dan; Zhu, Jun-Jie; Lin, Yuehe

    2016-01-01

    Herein, a facile ultrasonic-assisted strategy was proposed to fabricate the Pd-Pt alloy/multi-walled carbon nanotubes (Pd-Pt/CNTs) nanocomposites. A good number of Pd-Pt alloy nanoparticles with an average of 3.4 ± 0.5 nm were supported on sidewalls of CNTs with uniform distribution. The composition of the Pd-Pt/CNTs nanocomposites could also be easily controlled, which provided a possible approach for the preparation of other architectures with anticipated properties. The Pd-Pt/CNTs nanocomposites were extensively studied by electron microscopy, induced coupled plasma atomic emission spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, and applied for the ethanol and methanol electro-oxidation reaction in alkaline medium. The electrochemical results indicated that the nanocomposites had better electrocatalytic activities and stabilities, showing promising applications for fuel cells. PMID:26384899

  16. Supersaturation-controlled surface structure evolution of Pd@Pt core-shell nanocrystals: enhancement of the ORR activity at a sub-10 nm scale

    NASA Astrophysics Data System (ADS)

    Qi, Kun; Zheng, Weitao; Cui, Xiaoqiang

    2016-01-01

    Here, we designed and implemented a facile strategy for controlling the surface evolution of Pd@Pt core-shell nanostructures by simply adjusting the volume of OH- to control the reducing ability of ascorbic acid and finally manipulating the supersaturation in the reaction system. The surface structure of the obtained Pd@Pt bimetallic nanocrystals transformed from a Pt {111} facet-exposed island shell to a conformal Pt {100} facet-exposed shell by increasing the pH value. The as-prepared well aligned Pd@Pt core-island shell nanocubes present both significantly enhanced electrocatalytic activity and favorable long-term stability toward the oxygen reduction reaction in alkaline media.Here, we designed and implemented a facile strategy for controlling the surface evolution of Pd@Pt core-shell nanostructures by simply adjusting the volume of OH- to control the reducing ability of ascorbic acid and finally manipulating the supersaturation in the reaction system. The surface structure of the obtained Pd@Pt bimetallic nanocrystals transformed from a Pt {111} facet-exposed island shell to a conformal Pt {100} facet-exposed shell by increasing the pH value. The as-prepared well aligned Pd@Pt core-island shell nanocubes present both significantly enhanced electrocatalytic activity and favorable long-term stability toward the oxygen reduction reaction in alkaline media. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07940c

  17. Newly-designed complex ternary Pt/PdCu nanoboxes anchored on three-dimensional graphene framework for highly efficient ethanol oxidation.

    PubMed

    Hu, Chuangang; Cheng, Huhu; Zhao, Yang; Hu, Yue; Liu, Yong; Dai, Liming; Qu, Liangti

    2012-10-23

    Newly-designed ternary Pt/PdCu nanoboxes on three-dimensional graphene framework (Pt/PdCu/3DGF) have been fabricated via a dual solvothermal strategy. This structurally well-defined Pt/PdCu/3DGF system possesses an approximately 4-fold improvement in catalytic activity for ethanol oxidation in alkaline media over the commercial 20% Pt/C catalyst as normalized by the total mass of active metals, showing the great potential for direct fuel cell applications. PMID:22886893

  18. Mesoporous TiN as a noncarbon support of Ag-rich PtAg nanoalloy catalysts for oxygen reduction reaction in alkaline media.

    PubMed

    Cui, Zhiming; Yang, Minghui; Chen, Hao; Zhao, Mengtian; DiSalvo, Francis J

    2014-12-01

    There has been growing interest in noncarbon supports for fuel cell reactions, especially for the oxygen reduction reaction (ORR) in alkaline media. Herein, we report a robust mesoporous titanium nitride (TiN) which is not only kinetically stable in alkaline media, but also electrochemically stable in the potential range of fuel cell operation. This binary nitride exhibits an order of magnitude higher electronic conductivity than carbon black. Bimetallic Ag-rich PtAg nanoalloy is selected as the catalyst for the ORR in alkaline media due to their superior activity and relatively low cost. TiN-supported Pt1 Ag9 nanoalloy catalysts are synthesized by a new and efficient approach with KEt3 BH as reducing agent and THF as solvent. Pt1 Ag9 /TiN exhibits much higher mass activity and durability for the ORR in alkaline media than Pt1 Ag9 /C, Pt/C and Ag/C catalysts, suggesting that mesoporous TiN is a very promising support in alkaline media. PMID:25320003

  19. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt3M (M=Pt, Ru, Sn, Re, Rh, and Pd)

    PubMed Central

    Xu, Zhen-Feng; Wang, Yixuan

    2011-01-01

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt3M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt3Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol. PMID:22102920

  20. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt(3)M (M=Pt, Ru, Sn, Re, Rh, and Pd).

    PubMed

    Xu, Zhen-Feng; Wang, Yixuan

    2011-10-27

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt(3)M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt(3)Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol. PMID:22102920

  1. Structural and magnetic phase transitions in CeCu6 -xTx (T =Ag ,Pd )

    NASA Astrophysics Data System (ADS)

    Poudel, L.; de la Cruz, C.; Payzant, E. A.; May, A. F.; Koehler, M.; Garlea, V. O.; Taylor, A. E.; Parker, D. S.; Cao, H. B.; McGuire, M. A.; Tian, W.; Matsuda, M.; Jeen, H.; Lee, H. N.; Hong, T.; Calder, S.; Zhou, H. D.; Lumsden, M. D.; Keppens, V.; Mandrus, D.; Christianson, A. D.

    2015-12-01

    The structural and the magnetic properties of CeCu6 -xAgx (0 ≤x ≤0.85 ) and CeCu6 -xPdx (0 ≤x ≤0.4 ) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu6 -xAgx and CeCu6 -xPdx as a function of Ag/Pd composition are reported. The end member, CeCu6, undergoes a structural phase transition from an orthorhombic (P n m a ) to a monoclinic (P 21/c ) phase at 240 K. In CeCu6 -xAgx , the structural phase transition temperature (Ts) decreases linearly with Ag concentration and extrapolates to zero at xS ≈0.1 . The structural transition in CeCu6 -xPdx remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu6 -xAgx and CeCu6 -xPdx , exhibit a magnetic quantum critical point (QCP), at x ≈0.2 and x ≈0.05 , respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ10 δ2), where δ1˜0.62 ,δ2˜0.25 ,x =0.125 for CeCu6 -xPdx and δ1˜0.64 ,δ2˜0.3 ,x =0.3 for CeCu6 -xAgx . The magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.

  2. A comparative study on the bond strength of porcelain to the millingable Pd-Ag alloy

    PubMed Central

    Hong, Jun-Tae

    2014-01-01

    PURPOSE The porcelain fused to gold has been widely used as a restoration both with the natural esthetics of the porcelain and durability and marginal fit of metal casting. However, recently, due to the continuous rise in the price of gold, an interest towards materials to replace gold alloy is getting higher. This study compared the bond strength of porcelain to millingable palladium-silver (Pd-Ag) alloy, with that of 3 conventionally used metal-ceramic alloys. MATERIALS AND METHODS Four types of metal-ceramic alloys, castable nonprecious nickel-chrome alloy, castable precious metal alloys containing 83% and 32% of gold, and millingable Pd-Ag alloy were used to make metal specimens (n=40). And porcelain was applied on the center area of metal specimen. Three-point bending test was performed with universal testing machine. The bond strength data were analyzed with a one-way ANOVA and post hoc Scheffe's tests (α=.05). RESULTS The 3-point bending test showed the strongest (40.42 ± 5.72 MPa) metal-ceramic bond in the nonprecious Ni-Cr alloy, followed by millingable Pd-Ag alloy (37.71 ± 2.46 MPa), precious metal alloy containing 83% of gold (35.89 ± 1.93 MPa), and precious metal alloy containing 32% of gold (34.59 ± 2.63 MPa). Nonprecious Ni-Cr alloy and precious metal alloy containing 32% of gold showed significant difference (P<.05). CONCLUSION The type of metal-ceramic alloys affects the bond strength of porcelain. Every metal-ceramic alloy used in this study showed clinically applicable bond strength with porcelain (25 MPa). PMID:25352959

  3. Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction

    SciTech Connect

    Xie, Shuifen; Choi, Sang; Lu, Ning; Roling, Luke T.; Herron, Jeffrey A.; Zhang, Lei; Park, Jinho; Wang, Jinguo; Kim, Moon J.; Xie, Zhaoxiong; Mavrikakis, Manos; Xia, Younan

    2014-06-11

    An effective strategy for reducing the Pt content while retaining the activity of a Pt-based catalyst is to deposit the Pt atoms as ultrathin skins of only a few atomic layers thick on nanoscale substrates made of another metal. During deposition, however, the Pt atoms often take an island growth mode because of a strong bonding between Pt atoms. Here we report a versatile route to the conformal deposition of Pt as uniform, ultrathin shells on Pd nanocubes in a solution phase. The introduction of the Pt precursor at a relatively slow rate and high temperature allowed the deposited Pt atoms to spread across the entire surface of a Pd nanocube to generate a uniform shell. The thickness of the Pt shell could be controlled from one to six atomic layers by varying the amount of Pt precursor added into the system. Compared to a commercial Pt/C catalyst, the Pd@PnL (n = 1-6) core-shell nanocubes showed enhancements in specific activity and durability toward the oxygen reduction reaction (ORR). Density functional theory (DFT) calculations on model (100) surfaces suggest that the enhancement in specific activity can be attributed to the weakening of OH binding through ligand and strain effects, which, in turn, increases the rate of OH hydrogenation. A volcano-type relationship between the ORR specific activity and the number of Pt atomic layers was derived, in good agreement with the experimental results. Both theoretical and experimental studies indicate that the ORR specific activity was maximized for the catalysts based on Pd@Pt2-3L nanocubes. Because of the reduction in Pt content used and the enhancement in specific activity, the Pd@Pt1L nanocubes showed a Pt mass activity with almost three-fold enhancement relative to the Pt/C catalyst.

  4. Nitriding-induced texture, ordering and coercivity enhancement in FePtAgB nanocomposite magnets

    NASA Astrophysics Data System (ADS)

    Crisan, O.; Vasiliu, F.; Palade, P.; Mercioniu, I.

    2016-03-01

    FePt system attracts currently a great deal of interest for applications as future RE free permanent magnets. Among the key issues to be solved one may count the decreasing of the ordering temperature and improvement of magnetic behavior. For that purpose we have studied the effect of a nitriding post-synthesis procedure on the FePtAgB melt spun ribbons, aimed at refining the microstructure and enhancing the magnetic performances. Deep structural characterization by transmission electron microscopy, electron diffraction, energy dispersive X-ray spectroscopy and X-ray diffraction allowed us to observe the morphology and to correctly assign and identify the nature of the main granular phases observed. Nitriding procedure is shown to strongly enhance the (001) texturing and the degree of ordering of the L10 FePt phase, as well as largely increase of coercivity, compared to the as-cast state. These changes are interpreted in terms of Ag segregation towards intergranular region associated to N diffusion and creation of vacancies that favor consistently the process of ordering the FePt grains into the L10 tetragonal phase.

  5. Mechanism of Electromigration in Ag-Alloy Bonding Wires with Different Pd and Au Content

    NASA Astrophysics Data System (ADS)

    Chuang, Tung-Han; Lin, Hsin-Jung; Wang, Hsi-Ching; Chuang, Chien-Hsun; Tsai, Chih-Hsin

    2015-02-01

    The mechanism of electromigration in Ag-alloy wires containing different amounts of Pd and Au has been studied. Thinning and thickening accompanying grain growth were observed in worn bonding wire after current stress. The mean time-to-failure of bonding wires stressed with different current densities is highly dependent on their electrical resistivity, and wire temperature increases during current stress, owing to the Joule effect. An indirect method is proposed for in situ assessment of the temperatures of these fine wires under current stress. A mode of failure of these bonding wires was deduced by kinetic analysis. This mode can be correlated with atomic diffusion in the wire.

  6. Hemichelation, a way to stabilize electron-unsaturated complexes: the case of T-shaped Pd and Pt metallacycles.

    PubMed

    Werlé, Christophe; Bailly, Corinne; Karmazin-Brelot, Lydia; Le Goff, Xavier-Frédéric; Ricard, Louis; Djukic, Jean-Pierre

    2013-11-27

    A rational method of synthesis of stable neutral T-shaped 14 electron Pd and Pt complexes is proposed. It takes advantage of the ambiphilic character of the tricarbonyl(η(6)-indenyl)chromium anion, of which the main property is to behave as a hemichelating ligand, that is a nonconventional heteroditopic ligand capable of chelating a metal center by way of covalent and noncovalent bonding, thus preserving its unsaturated valence shell. The reaction of the in situ formed tricarbonyl(η(6)-2-methylindenyl)chromium anion with a series of Pd and Pt metallacycles afforded new air-stable and persistent synfacial heterobimetallic complexes in which the metallacycle binds the indenyl fragment via its metal in an η(1) fashion, leaving the fourth coordination site at the chelated metal virtually vacant. The structures of eight of these novel complexes are disclosed, and their bonding features are investigated by an array of theoretical methods based on the density functional theory (NBO, EDA, ETS-NOCV, AIM, NCI region analysis). Theory shows that the formation of these unusual structures of bimetallic synfacial η(1)-indenyl-Pd/Pt complexes is driven thermodynamically by attractive Coulombic occlusion of the fourth vacant coordination site at Pd/Pt centers by the Cr(CO)3 moiety. PMID:24182317

  7. Distribution of Pd clusters on ultrathin, epitaxial TiOx films on Pt3Ti(111)

    PubMed Central

    Breinlich, Christian; Buchholz, Maria; Pertram, Tobias; Becker, Conrad; Wandelt, Klaus

    2015-01-01

    Summary Scanning tunnelling microscopy (STM) was used to investigate the nucleation and growth of palladium clusters on two different, ultrathin, epitaxial, titania films grown on a Pt3Ti(111) surface. The first oxide phase, z'-TiOx, is anisotropic and consists of parallel stripes separated by trenches. Defects (i.e., oxygen vacancies) in this structure are confined to these trenches and act as nucleation sites. Therefore, the Pd clusters are mostly arranged in unidirectional rows along the trenches, creating a template effect. The second phase, w'-TiOx, exhibits a hexagonal, long range, (7 × 7)R21.8°, Moiré-type superstructure with fewer and shallower defects, making the template effect less discernible. PMID:26665071

  8. Phase Structure and Site Preference Behavior of Ternary Alloying Additions to PdTi and PtTi Shape-Memory Alloys

    NASA Technical Reports Server (NTRS)

    Bozzolo, Guillermo; Mosca, Hugo O.; Noebe, Ronald D.

    2006-01-01

    The phasc structure and concentration dependence of the lattice parameter and energy of formation of ternary Pd-'I-X and Pt-Ti-X alloys for a large number of ternary alloying additions X (X = Na, Mg, Al, Si, Sc. V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Cd, Hf, Ta, W, Re, Os, Ir) are investigated with an atomistic modeling approach. In addition, a detailed description of the site preference behavior of such additions showing that the elements can be grouped according to their absolute preference for a specific site, regardless of concentration, or preference for available sites in the deficient sublattice is provided.

  9. Domain configurations in Co/Pd and L10-FePt nanowire arrays with perpendicular magnetic anisotropy

    NASA Astrophysics Data System (ADS)

    Ho, Pin; Tu, Kun-Hua; Zhang, Jinshuo; Sun, Congli; Chen, Jingsheng; Liontos, George; Ntetsikas, Konstantinos; Avgeropoulos, Apostolos; Voyles, Paul M.; Ross, Caroline A.

    2016-02-01

    Perpendicular magnetic anisotropy [Co/Pd]15 and L10-FePt nanowire arrays of period 63 nm with linewidths 38 nm and 27 nm and film thickness 27 nm and 20 nm respectively were fabricated using a self-assembled PS-b-PDMS diblock copolymer film as a lithographic mask. The wires are predicted to support Néel walls in the Co/Pd and Bloch walls in the FePt. Magnetostatic interactions from nearest neighbor nanowires promote a ground state configuration consisting of alternating up and down magnetization in adjacent wires. This was observed over ~75% of the Co/Pd wires after ac-demagnetization but was less prevalent in the FePt because the ratio of interaction field to switching field was much smaller. Interactions also led to correlations in the domain wall positions in adjacent Co/Pd nanowires. The reversal process was characterized by nucleation of reverse domains, followed at higher fields by propagation of the domains along the nanowires. These narrow wires provide model system for exploring domain wall structure and dynamics in perpendicular anisotropy systems.Perpendicular magnetic anisotropy [Co/Pd]15 and L10-FePt nanowire arrays of period 63 nm with linewidths 38 nm and 27 nm and film thickness 27 nm and 20 nm respectively were fabricated using a self-assembled PS-b-PDMS diblock copolymer film as a lithographic mask. The wires are predicted to support Néel walls in the Co/Pd and Bloch walls in the FePt. Magnetostatic interactions from nearest neighbor nanowires promote a ground state configuration consisting of alternating up and down magnetization in adjacent wires. This was observed over ~75% of the Co/Pd wires after ac-demagnetization but was less prevalent in the FePt because the ratio of interaction field to switching field was much smaller. Interactions also led to correlations in the domain wall positions in adjacent Co/Pd nanowires. The reversal process was characterized by nucleation of reverse domains, followed at higher fields by propagation of the

  10. Pt, Au, Pd and Ru Partitioning Between Mineral and Silicate Melts: The Role of Metal Nanonuggets

    NASA Technical Reports Server (NTRS)

    Malavergne, V.; Charon, E.; Jones, J.; Agranier, A.; Campbell, A.

    2012-01-01

    The partition coefficients of Pt and other Pt Group Elements (PGE) between metal and silicate D(sub Metal-Silicate) and also between silicate minerals and silicate melts D(sub Metal-Silicate) are among the most challenging coefficients to obtain precisely. The PGE are highly siderophile elements (HSE) with D(sub Metal-Silicate) >10(exp 3) due to the fact that their concentrations in silicates are very low (ppb to ppt range). Therefore, the analytical difficulty is increased by the possible presence of HSE-rich-nuggets in reduced silicate melts during experiments). These tiny HSE nuggets complicate the interpretation of measured HSE concentrations. If the HSE micro-nuggets are just sample artifacts, then their contributions should be removed before calculations of the final concentration. On the other hand, if they are produced during the quench, then they should be included in the analysis. We still don't understand the mechanism of nugget formation well. Are they formed during the quench by precipitation from precursor species dissolved homogeneously in the melts, or are they precipitated in situ at high temperature due to oversaturation? As these elements are important tracers of early planetary processes such as core formation, it is important to take up this analytical and experimental challenge. In the case of the Earth for example, chondritic relative abundances of the HSE in some mantle xenoliths have led to the concept of the "late veneer" as a source of volatiles (such as water) and siderophiles in the silicate Earth. Silicate crystal/liquid fractionation is responsible for most, if not all, the HSE variation in the martian meteorite suites (SNC) and Pt is the element least affected by these fractionations. Therefore, in terms of reconstructing mantle HSE abundances for Mars, Pt becomes a very important player. In the present study, we have performed high temperature experiments under various redox conditions in order to determine the abundances of Pt, Au

  11. Capping effect in magnetic properties of Ag ultra-thin films on Co/Pt(1 1 1)

    NASA Astrophysics Data System (ADS)

    Wu, Y. E.; Su, C. W.; Chen, F. C.; Shern, C. S.; Chen, R. H.

    2002-02-01

    Magneto-optical Kerr effect was used to study the changes of the magnetic property for Ag ultra-thin films deposited on Co/Pt (1 1 1) surface. The perpendicular magnetic anisotropy has a significant enhancement when the system is annealed and the Co-Pt alloy is formed. The magnetization disappears at lower temperatures, and appears at higher temperature after 1 ML Ag/1 ML Co/Pt (1 1 1) ultra-thin film was annealed at 710 K. This magnetization is reversible. The thermal energy triggering the motion of the magnetic domain walls is the possible mechanism for the larger magnetization at high temperature.

  12. Surface mobility of Ag on Pd(100) measured by specular helium scattering

    NASA Astrophysics Data System (ADS)

    Félix, C.; Vandoni, G.; Harbich, W.; Buttet, J.; Monot, R.

    1996-12-01

    We study the deposition and the very first steps of nucleation and growth of Ag on Pd(100) with thermal energy atom scattering. This technique is a very sensitive and nonperturbing probe to surface point defects, which permits an in situ and in-time monitoring of the deposition. The intention of this paper is to give a detailed description of the approach used in our work. The form of the specularly reflected helium signal as a function of coverage and surface temperature is compared to a theoretical curve, which is computed by solving a system of rate equations that describe the formation and destruction of clusters during the deposition process. The analysis of the experimental data gives two main results. The diffusion parameters (activation barrier Ed=0.37+/-0.03 eV and preexponential factor ν0=8×109 s-1) have been extracted for the system Ag on Pd(100). We find furthermore that all silver atoms impinging on a zone of 6.1 Å around an adatom on the surface are captured by it at surface temperatures well below the onset of thermally activated mobility. The origin of this phenomenon is discussed and tentatively assigned to a combined effect of transient and neighbor driven mobility.

  13. EFFECT OF IMPURITIES ON THE PERFORMANCE OF A Pd-Ag DIFFUSER

    SciTech Connect

    Morgan, G.

    2010-12-16

    A commercially fabricated diffuser purchased from Johnson-Matthey, Inc. was evaluated for performance characterization testing at the Savannah River National Laboratory (SRNL). Different impurities are often present in the feed streams of the process diffusers, but the effect of these impurities on the diffuser performance is currently unknown. Various impurities were introduced into the feed stream of the diffuser at various levels ranging from 0.5% to 10% of the total flow in order to determine the effect that these impurities have on the permeation of hydrogen through the palladium-silver membrane. The introduction of various impurities into the feed stream of the diffuser had a minimal effect on the overall permeation of hydrogen through the Pd-Ag membrane. Of the four impurities introduced into the feed stream, carbon monoxide (CO) was the only impurity that showed any evidence of causing a reduction in the amount of hydrogen permeating through the Pd-Ag membrane. The hydrogen permeation returned to its baseline level after the CO was removed from the feed stream. There were no lasting effects of the CO exposure on the ability of the membrane to effectively separate hydrogen from the non-hydrogen species in the gas stream under the conditions tested.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  15. Pd/Ag coated fiber Bragg grating sensor for hydrogen monitoring in power transformers.

    PubMed

    Ma, G M; Jiang, J; Li, C R; Song, H T; Luo, Y T; Wang, H B

    2015-04-01

    Compared with conventional DGA (dissolved gas analysis) method for on-line monitoring of power transformers, FBG (fiber Bragg grating) hydrogen sensor represents marked advantages over immunity to electromagnetic field, time-saving, and convenience to defect location. Thus, a novel FBG hydrogen sensor based on Pd/Ag (Palladium/Silver) along with polyimide composite film to measure dissolved hydrogen concentration in large power transformers is proposed in this article. With the help of Pd/Ag composite coating, the enhanced performance on mechanical strength and sensitivity is demonstrated, moreover, the response time and sensitivity influenced by oil temperature are solved by correction lines. Sensitivity measurement and temperature calibration of the specific hydrogen sensor have been done respectively in the lab. And experiment results show a high sensitivity of 0.055 pm/(μl/l) with instant response time about 0.4 h under the typical operating temperature of power transformers, which proves a potential utilization inside power transformers to monitor the health status by detecting the dissolved hydrogen concentration. PMID:25933889

  16. Surface mobility of Ag on Pd(100) measured by specular helium scattering

    SciTech Connect

    Felix, C.; Vandoni, G.; Harbich, W.; Buttet, J.; Monot, R.

    1996-12-01

    We study the deposition and the very first steps of nucleation and growth of Ag on Pd(100) with thermal energy atom scattering. This technique is a very sensitive and nonperturbing probe to surface point defects, which permits an {ital in} {ital situ} and in-time monitoring of the deposition. The intention of this paper is to give a detailed description of the approach used in our work. The form of the specularly reflected helium signal as a function of coverage and surface temperature is compared to a theoretical curve, which is computed by solving a system of rate equations that describe the formation and destruction of clusters during the deposition process. The analysis of the experimental data gives two main results. The diffusion parameters (activation barrier {ital E}{sub {ital d}}=0.37{plus_minus}0.03 eV and preexponential factor {nu}{sub 0}=8{times}10{sup 9} s{sup {minus}1}) have been extracted for the system Ag on Pd(100). We find furthermore that all silver atoms impinging on a zone of 6.1 A around an adatom on the surface are captured by it at surface temperatures well below the onset of thermally activated mobility. The origin of this phenomenon is discussed and tentatively assigned to a combined effect of transient and neighbor driven mobility. {copyright} {ital 1996 The American Physical Society.}

  17. Pd/Ag coated fiber Bragg grating sensor for hydrogen monitoring in power transformers

    NASA Astrophysics Data System (ADS)

    Ma, G. M.; Jiang, J.; Li, C. R.; Song, H. T.; Luo, Y. T.; Wang, H. B.

    2015-04-01

    Compared with conventional DGA (dissolved gas analysis) method for on-line monitoring of power transformers, FBG (fiber Bragg grating) hydrogen sensor represents marked advantages over immunity to electromagnetic field, time-saving, and convenience to defect location. Thus, a novel FBG hydrogen sensor based on Pd/Ag (Palladium/Silver) along with polyimide composite film to measure dissolved hydrogen concentration in large power transformers is proposed in this article. With the help of Pd/Ag composite coating, the enhanced performance on mechanical strength and sensitivity is demonstrated, moreover, the response time and sensitivity influenced by oil temperature are solved by correction lines. Sensitivity measurement and temperature calibration of the specific hydrogen sensor have been done respectively in the lab. And experiment results show a high sensitivity of 0.055 pm/(μl/l) with instant response time about 0.4 h under the typical operating temperature of power transformers, which proves a potential utilization inside power transformers to monitor the health status by detecting the dissolved hydrogen concentration.

  18. Hydrazine reduction of metal ions to porous submicro-structures of Ag, Pd, Cu, Ni, and Bi

    SciTech Connect

    Wang Yue; Shi Yongfang; Chen Yubiao; Wu Liming

    2012-07-15

    Porous submicro-structures of Ag, Pd, Cu, Ni, and Bi with high surface area have been prepared by the reduction of hydrazine in glycerol-ethanol solution at room temperature or 120-180 Degree-Sign C. Phase purity, morphology, and specific surface area have been characterized. The reactions probably undergo three different mechanisms: simple reduction for Ag and Pd, coordination-then-reduction for Cu and Ni, and hydrolysis-then-reduction for Bi. The reductant hydrazine also plays an important role to the formation of the porous submicro-structure. The reaction temperature influences the size of the constituent particles and the overall architecture of the submicro-structure so as to influence the surface area value. The as-prepared porous metals have shown the second largest surface area ever reported, which are smaller than those made by the reduction of NaBH{sub 4}, but larger than those made by hard or soft template methods. - Graphical abstract: Porous submicro-structures of Ag, Pd, Cu, Ni, and Bi with high surface area have been prepared by the reduction of hydrazine in the glycerol-ethanol solution at room temperature or 120-180 Degree-Sign C. The reactions undergo different mechanisms: simple reduction for Ag and Pd, coordination-then-reduction for Cu and Ni, and hydrolysis-then-reduction for Bi. Highlights: Black-Right-Pointing-Pointer Syntheses of porous Ag, Pd, Cu, Ni, and Bi with high surface area. Black-Right-Pointing-Pointer Ag and Pd undergo simple reduction. Black-Right-Pointing-Pointer Cu and Ni undergo coordination-then-reduction. Black-Right-Pointing-Pointer Bi undergoes hydrolysis-then-reduction. Black-Right-Pointing-Pointer The as-prepared metals have shown the second largest surface area ever reported.

  19. Microscopic Investigation of Chemoselectivity in Ag-Pt-Fe3O4 Heterotrimer Formation: Mechanistic Insights and Implications for Controlling High-Order Hybrid Nanoparticle Morphology.

    PubMed

    Hodges, James M; Morse, James R; Williams, Mary Elizabeth; Schaak, Raymond E

    2015-12-16

    Three-component hybrid nanoparticle heterotrimers, which are important multifunctional constructs that underpin diverse applications, are commonly synthesized by growing a third domain off of a two-component heterodimer seed. However, because heterodimer seeds expose two distinct surfaces that often can both support nucleation and growth, selectively targeting one particular surface is critical for exclusively accessing a desired configuration. Understanding and controlling nucleation and growth therefore enables the rational formation of high-order hybrid nanoparticles. Here, we report an in-depth microscopic investigation that probes the chemoselective addition of Ag to Pt-Fe3O4 heterodimer seeds to form Ag-Pt-Fe3O4 heterotrimers. We find that the formation of the Ag-Pt-Fe3O4 heterotrimers initiates with indiscriminate Ag nucleation onto both the Pt and Fe3O4 surfaces of Pt-Fe3O4, followed by surface diffusion and coalescence of Ag onto the Pt surface to form the Ag-Pt-Fe3O4 product. Control experiments reveal that the size of the Ag domain of Ag-Pt-Fe3O4 correlates with the overall surface area of the Pt-Fe3O4 seeds, which is consistent with the coalescence of Ag through a surface-mediated process and can also be exploited to tune the size of the Ag domain. Additionally, we observe that small iron oxide islands on the Pt surface of the Pt-Fe3O4 seeds, deposited during the formation of Pt-Fe3O4, define the morphology of the Ag domain, which in turn influences its optical properties. These results provide unprecedented microscopic insights into the pathway by which Ag-Pt-Fe3O4 heterotrimer nanoparticles form and uncover new design guidelines for the synthesis of high-order hybrid nanoparticles with precisely targeted morphologies and properties. PMID:26599998

  20. Homogeneity and elemental distribution in self-assembled bimetallic Pd-Pt aerogels prepared by a spontaneous one-step gelation process.

    PubMed

    Oezaslan, M; Liu, W; Nachtegaal, M; Frenkel, A I; Rutkowski, B; Werheid, M; Herrmann, A-K; Laugier-Bonnaud, C; Yilmaz, H-C; Gaponik, N; Czyrska-Filemonowicz, A; Eychmüller, A; Schmidt, T J

    2016-07-27

    Multi-metallic aerogels have recently emerged as a novel and promising class of unsupported electrocatalyst materials due to their high catalytic activity and improved durability for various electrochemical reactions. Aerogels can be prepared by a spontaneous one-step gelation process, where the chemical co-reduction of metal precursors and the prompt formation of nanochain-containing hydrogels, as a preliminary stage for the preparation of aerogels, take place. However, detailed knowledge about the homogeneity and chemical distribution of these three-dimensional Pd-Pt aerogels at the nano-scale as well as at the macro-scale is still unclear. Therefore, we used a combination of spectroscopic and microscopic techniques to obtain a better insight into the structure and elemental distribution of the various Pd-rich Pd-Pt aerogels prepared by the spontaneous one-step gelation process. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) in combination with energy-dispersive X-ray spectroscopy (EDX) were employed in this work to uncover the structural architecture and chemical composition of the various Pd-rich Pd-Pt aerogels over a broad length range. The Pd80Pt20, Pd60Pt40 and Pd50Pt50 aerogels showed heterogeneity in the chemical distribution of the Pt and Pd atoms inside the macroscopic nanochain-network. The features of mono-metallic clusters were not detected by EXAFS or STEM-EDX, indicating alloyed nanoparticles. However, the local chemical composition of the Pd-Pt alloys strongly varied along the nanochains and thus within a single aerogel. To determine the electrochemically active surface area (ECSA) of the Pd-Pt aerogels for application in electrocatalysis, we used the electrochemical CO stripping method. Due to their high porosity and extended network structure, the resulting values of the ECSA for the Pd-Pt aerogels were higher than that for

  1. Colorimetric detection of the flux of hydrogen peroxide released from living cells based on the high peroxidase-like catalytic performance of porous PtPd nanorods.

    PubMed

    Ge, Shenguang; Liu, Weiyan; Liu, Haiyun; Liu, Fang; Yu, Jinghua; Yan, Mei; Huang, Jiadong

    2015-09-15

    One-dimensional PtPd porous nanorods (PtPd PNRs) were successfully synthesized through a bromide-induced galvanic replacement reaction between Pd nanowires and K2PtCl6. The PtPd PNRs were porous and alloy-structured with Pt/Pd atomic ratio up to 1:1 which were demonstrated by spectroscopic methods. We had also proved that the nanorods could function as peroxidase mimetic for the detection of H2O2, with the detection limit of 8.6 nM and the linear range from 20 nM to 50 mM. The result demonstrated that PtPd PNRs exhibited much higher affinity to H2O2 over other peroxidase mimetics due to synergistically integrating highly catalytic activity of two metals. On the basis of the peroxidase-like activity, the PtPd PNRs were used as a signal transducer to develop a novel and simple colorimetric method for the study of the flux of H2O2 released from living cell. By using 3,3,5,5-tetramethylbenzidine as substrate, the H2O2 concentration could be distinguished by naked-eye observation without any instrumentation or complicated design. The method developed a new platform for a reliable collection of information on cellular reactive oxygen species release. And the nanomaterial could be used as a power tool for a wide range of potential applications in biotechnology and medicine. PMID:25982545

  2. First study on anthropogenic Pt, Pd, and Rh levels in soils from major avenues of São Paulo City, Brazil.

    PubMed

    Ribeiro, A P; Figueiredo, A M G; Sarkis, J E S; Hortellani, M A; Markert, B

    2012-12-01

    Over the last years, investigations on the increase of platinum (Pt), palladium (Pd), and rhodium (Rh) levels in urban environments of big cities all over the world - especially to catalytic converters emissions - have been grown up enormously. São Paulo City is the 6th largest megacity in the world having about 20 million inhabitants and an ever increasing seven million motor vehicle fleet. In spite of this, there has never been an investigation regarding Pt, Pd, and Rh levels in the city. In the present study, Pt, Pd, and Rh concentrations were determined in soils adjacent to seven main high-density traffic avenues in the metropolitan region of São Paulo City. Inductively coupled plasma mass spectrometry was employed - after ultrasound-assisted aqua regia leaching - as analytical technigue. The results showed concentration levels up to 378 ng g(-1) for Pd, 208 ng g(-1) for Pt, and 0.2 to 45 ng g(-1) for Rh. These levels are much higher than those considered for the geochemical background of soils, indicating a catalytic converter source. Due to the different Pt/Pd/Rh ratio in Brazilian automobile catalytic converters, lower levels of Pt/Pd ratios compared with other similar studies were observed. The obtained results are the first data for monitoring Pt, Pd, and Rh pollution in São Paulo City soils. PMID:22322405

  3. Structural and magnetic properties of X12Y (X, Y=Fe, Co, Ni, Ru, Rh, Pd, and Pt) nanoalloys

    NASA Astrophysics Data System (ADS)

    Aguilera-Granja, F.; Longo, R. C.; Gallego, L. J.; Vega, A.

    2010-05-01

    We perform extensive ab initio density-functional calculations to investigate the structures and magnetic moments of the binary clusters X12Y (X, Y=Fe, Co, Ni, Ru, Rh, Pd, and Pt). Although all the binary clusters Fe12Y, Co12Y, Ru12Y, and Rh12Y, plus Ni12Y (Y=Rh, Pd, and Pt) and Pt12Y (Y=Ru, Rh, and Pd), retain, with more or less distortions, the structures of the corresponding pure X13 clusters, the remaining binary clusters (i.e., a significant number of 12 of all the 42 cases) adopt geometries different from those of the corresponding pure clusters. Independent of the peculiarities of each family of binary clusters, the binding energies of all the binary clusters X12Ru are bigger than those of the pure X13 clusters, while the binding energies of all the binary clusters X12Pd are smaller. The clusters investigated exhibit a variety of magnetic behaviors. In the case of Ni12Rh, we predict a remarkable magnetic cooperative phenomenon that can be attributed to electronic effects associated to the chemical environment through Ni-Rh hybridization.

  4. Domain configurations in Co/Pd and L10-FePt nanowire arrays with perpendicular magnetic anisotropy.

    PubMed

    Ho, Pin; Tu, Kun-Hua; Zhang, Jinshuo; Sun, Congli; Chen, Jingsheng; Liontos, George; Ntetsikas, Konstantinos; Avgeropoulos, Apostolos; Voyles, Paul M; Ross, Caroline A

    2016-03-01

    Perpendicular magnetic anisotropy [Co/Pd]15 and L10-FePt nanowire arrays of period 63 nm with linewidths 38 nm and 27 nm and film thickness 27 nm and 20 nm respectively were fabricated using a self-assembled PS-b-PDMS diblock copolymer film as a lithographic mask. The wires are predicted to support Néel walls in the Co/Pd and Bloch walls in the FePt. Magnetostatic interactions from nearest neighbor nanowires promote a ground state configuration consisting of alternating up and down magnetization in adjacent wires. This was observed over ∼75% of the Co/Pd wires after ac-demagnetization but was less prevalent in the FePt because the ratio of interaction field to switching field was much smaller. Interactions also led to correlations in the domain wall positions in adjacent Co/Pd nanowires. The reversal process was characterized by nucleation of reverse domains, followed at higher fields by propagation of the domains along the nanowires. These narrow wires provide model system for exploring domain wall structure and dynamics in perpendicular anisotropy systems. PMID:26883011

  5. Fabrication of catalytically active Au/Pt/Pd trimetallic nanoparticles by rapid injection of NaBH{sub 4}

    SciTech Connect

    Zhang, Haijun; Lu, Lilin; Cao, Yingnan; Du, Shuang; Cheng, Zhong; Zhang, Shaowei

    2014-01-01

    Graphical abstract: The synthesis and characterization of 2.0 nm-diameter Au/Pt/Pd nanoparticles are reported. The catalytic activity for glucose oxidation of the nanoparticles is several times higher than that of Au nanoparticles with nearly same size. - Highlights: • PVP-protected Au/Pt/Pd trimetallic nanoparticles (TNPs) of 2.0 nm in diameter were prepared. • The catalytic activity of TNPs is several times higher than that of Au nanoparticles. • Negatively charged Au atoms in the TNPs were confirmed by DFT calculation. - Abstract: Au/Pt/Pd trimetallic nanoparticles (TNPs) with an alloyed structure and an average diameter of about 2.0 nm were prepared via reducing the corresponding ions with rapidly injected NaBH{sub 4}, and characterized by UV–vis, TEM and HR-TEM. The catalytic activity of as-prepared TNPs for the aerobic glucose oxidation is several times higher than that of Au monometallic nanoparticles with about the same average size, which could be attributed to the catalytically active sites provided by the negatively charged Au atoms as a result of the electron donation from the neighboring Pd atoms. This was well supported by the electron density calculations based on the density functional theory.

  6. A green method to prepare Pd-Ag nanoparticles supported on reduced graphene oxide and their electrochemical catalysis of methanol and ethanol oxidation

    NASA Astrophysics Data System (ADS)

    Li, Lingzhi; Chen, Mingxi; Huang, Guanbo; Yang, Nian; Zhang, Li; Wang, Huan; Liu, Yu; Wang, Wei; Gao, Jianping

    2014-10-01

    Bimetallic palladium-silver nanoparticles (NPs) supported on reduced oxide graphene (RGO) with different Pd/Ag ratios (Pd-Ag/RGO) were prepared by an easy green method which did not use any additional reducing agents or a dispersing agent. During the process, simultaneous redox reactions between AgNO3, K2PdCl4 and graphene oxide (GO) led to bimetallic Pd-Ag NPs. The morphology and composition of the Pd-Ag/RGO were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis and Raman spectroscopy. Cyclic voltammetry and chronoamperometry were used to investigate the electrochemical activities and stabilities of these Pd-Ag/RGO catalysts for the electro-oxidation of methanol and ethanol in alkaline media. Among the different Pd/Ag ratios, the Pd-Ag (1:1)/RGO had the best catalytic activities and stability. So it is a promising catalyst for direct alcohol fuel cell applications.

  7. Deviations from one-electron behavior in the Ag and Pd M4,5-VV Auger spectra of AgcPd1-c alloys

    NASA Astrophysics Data System (ADS)

    Mariot, J.-M.; Hague, C. F.; Dufour, G.

    1981-04-01

    A systematic investigation of the Ag and Pd M4,5-VV Auger spectra in the pure metals and in the AgcPd1-c(0.1<=c<=0.9) alloys is presented. The shape of the Auger spectra is discussed in relation to the values of the effective Coulomb interaction Ueff between the two holes present in the final state of the Auger transition and of the width W of the one-electron local densities of states as obtained from Lβ2,15 soft-x-ray emission bands. The Auger spectra of Ag in the metal and the alloys have a pronounced quasiatomic character, as can be expected from the Ueff2W ratio which is found to be close to unity. The Auger spectrum of pure Pd (Ueff2W~0.4) can be explained in terms of an atomic model in which strong band effects are present. For alloys with low-Pd content where Pd forms an impurity state, it is shown that final states other than the localized [4d2] two-hole state have to be invoked to explain the line shape.

  8. Pd@Pt core-shell concave decahedra: A class of catalysts for the oxygen reduction reaction with enhanced activity and durability

    SciTech Connect

    Wang, Xue; Vera, Madeline; Chi, Miaofang; Xia, Younan; Luo, Ming; Huang, Hongwen; Ruditskiy, Aleksey; Park, Jinho; Bao, Shixiong; Liu, Jingyue; Howe, Jane; Xie, Zhaoxiong

    2015-11-13

    Here, we report a facile synthesis of multiply twinned Pd@Pt core shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200 degrees C, naturally generating a core shell structure covered by concave facets. The nonuniformity in the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm2pt) and mass (1.60 A/mg/2pt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm2pt and 0.32 A/mgpt, respectively). After 10 000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgpt, more than twice that of the pristine Pt/C catalyst.

  9. In situ XAS studies of Pt{sub x}Pd{sub 1-x} nanoparticles under thermal annealing

    SciTech Connect

    Bernardi, F.; Morais, J.; Alves, M. C. M.

    2009-01-29

    In this work, we have studied Pt{sub x}Pd{sub 1-x}(x = 1, 0.7 or 0.5) nanoparticles subjected to H{sub 2} reduction and sulfidation under H{sub 2}S atmosphere, both at 300 deg. C. The system was studied by in-situ x-ray absorption spectroscopy (in-situ XAS). We observed that the efficiency of sulfidation is directly proportional to the quantity of Pd atoms in the nanoparticle, provided the reduction process has been achieved.

  10. Joint contributions of Ag ions and oxygen vacancies to conducting filament evolution of Ag/TaO{sub x}/Pt memory device

    SciTech Connect

    Chung, Yu-Lung; Cheng, Wen-Hui; Chen, Wei-Chih; Jhan, Sheng-An; Chen, Jen-Sue; Jeng, Jiann-Shing

    2014-10-28

    The electroforming and resistive switching behaviors in the Ag/TaO{sub x}/Pt trilayer structure are investigated under a continual change of temperatures between 300 K and 100 K to distinguish the contributions of Ag ions and oxygen vacancies in developing of conducting filaments. For either electroforming or resistive switching, a significantly higher forming/set voltages is needed as the device is operated at 100 K, as compared to that observed when operating at 300 K. The disparity in forming/set voltages of Ag/TaO{sub x}/Pt operating at 300 K and 100 K is attributed to the contribution of oxygen vacancies, in addition to Ag atoms, in formation of conducting filament at 100 K since the mobilities of oxygen vacancies and Ag ions become comparable at low temperature. The presence of oxygen vacancy segment in the conducting filament also modifies the reset current from a gradually descending behavior (at 300 K) to a sharp drop (at 100 K). Furthermore, the characteristic set voltage and reset current are irreversible as the operation temperature is brought from 100 K back to 300 K, indicating the critical role of filament constituents on the switching behaviors of Ag/oxide/Pt system.

  11. A green approach to ethyl acetate: quantitative conversion of ethanol through direct dehydrogenation in a Pd-Ag membrane reactor.

    PubMed

    Zeng, Gaofeng; Chen, Tao; He, Lipeng; Pinnau, Ingo; Lai, Zhiping; Huang, Kuo-Wei

    2012-12-01

    Pincers do the trick: The conversion of ethanol to ethyl acetate and hydrogen was achieved using a pincer-Ru catalyst in a Pd-Ag membrane reactor. Near quantitative conversions and yields could be achieved without the need for acid or base promoters or hydrogen acceptors (see scheme). PMID:23136053

  12. Green Synthesis of Ag and Pd Nanospheres, Nanowires, and Nanorods Using Vitamin B2: Catalytic Polymerisation of Aniline and Pyrrole

    EPA Science Inventory

    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 hydro...

  13. Granular L1{sub 0} FePt-B and FePt-B-Ag (001) thin films for heat assisted magnetic recording

    SciTech Connect

    Granz, Steven D.; Barmak, Katayun; Kryder, Mark H.

    2012-04-01

    A comparison was made of FePt-B and FePt-B-Ag thin films having different volume contents of boron, which were RF sputtered with in-situ heating at 425-575 deg. C onto Si substrates with 20 nm thick (002) MgO. By introducing boron into FePt and varying the sputtering conditions, films with grain sizes ranging from 2.5 to 10 nm were produced. The boron promoted columnar growth, but made ordering more difficult. However, by adding Ag into FePt-B, ordering improved while coercivity increased from 7 to 11 kOe with no significant impact on the microstructure. We obtained films with grain sizes down to 2.5 nm with center-to-center spacing of 3.1 nm. The reduced grain size, columnar microstructure and increase in ordering and coercivity by adding Ag into the FePt-B thin films are favorable for application in heat assisted magnetic recording.

  14. Interfacial nanodroplets guided construction of hierarchical Au, Au-Pt, and Au-Pd particles as excellent catalysts

    PubMed Central

    Ma, Aijing; Xu, Jie; Zhang, Xuehua; Zhang, Bin; Wang, Dayang; Xu, Haolan

    2014-01-01

    Interfacial nanodroplets were grafted to the surfaces of self-sacrificed template particles in a galvanic reaction system to assist the construction of 3D Au porous structures. The interfacial nanodroplets were formed via direct adsorption of surfactant-free emulsions onto the particle surfaces. The interfacial nanodroplets discretely distributed at the template particle surfaces and served as soft templates to guide the formation of porous Au structures. The self-variation of footprint sizes of interfacial nanodroplets during Au growth gave rise to a hierarchical pore size distribution of the obtained Au porous particles. This strategy could be easily extended to synthesize bimetal porous particles such as Au-Pt and Au-Pd. The obtained porous Au, Au-Pt, and Au-Pd particles showed excellent catalytic activity in catalytic reduction of 4-nitrophenol. PMID:24797697

  15. Effect of copper content on Pt-Pd-CuO/{gamma}-alumina catalysts for motorcycle soot conversion

    SciTech Connect

    Chien, C.C.; Huang, T.J.

    1995-06-01

    Catalytic combustion of motorcycle soot particulates over {gamma}-alumina-supported CuO, Pt, Pd, Pt-CuO, and Pd-CuO catalysts was studied. The catalyst coated with motorcycle soots was placed in a flow reactor to perform temperature-programmed oxidation. Results indicated that the CuO catalyst was quite effective for the catalytic combustion. The high activity of the CuO catalyst could be illustrated by a redox mechanism and an induced particle-motion mechanism. A higher copper content enhanced the reducibility of the copper oxide and induced a higher activity for catalytic combustion until the copper oxide content reached 5 wt%. A redispersion phenomenon of the CuO species was observed and was consistent with the induced particle-motion mechanism. Additionally, the effect of the noble metal additive was to promote the activity of the CuO species by a mechanism including dissociative adsorption and spillover of oxygen.

  16. Interfacial nanodroplets guided construction of hierarchical Au, Au-Pt, and Au-Pd particles as excellent catalysts.

    PubMed

    Ma, Aijing; Xu, Jie; Zhang, Xuehua; Zhang, Bin; Wang, Dayang; Xu, Haolan

    2014-01-01

    Interfacial nanodroplets were grafted to the surfaces of self-sacrificed template particles in a galvanic reaction system to assist the construction of 3D Au porous structures. The interfacial nanodroplets were formed via direct adsorption of surfactant-free emulsions onto the particle surfaces. The interfacial nanodroplets discretely distributed at the template particle surfaces and served as soft templates to guide the formation of porous Au structures. The self-variation of footprint sizes of interfacial nanodroplets during Au growth gave rise to a hierarchical pore size distribution of the obtained Au porous particles. This strategy could be easily extended to synthesize bimetal porous particles such as Au-Pt and Au-Pd. The obtained porous Au, Au-Pt, and Au-Pd particles showed excellent catalytic activity in catalytic reduction of 4-nitrophenol. PMID:24797697

  17. Crystalline monolayer surface of liquid Au-Cu-Si-Ag-Pd: Metallic glass former

    SciTech Connect

    Mechler, S; Yahel, E; Pershan, P S; Meron, M; Lin, B

    2012-02-06

    It is demonstrated by means of x-ray synchrotron reflectivity and diffraction that the surface of the liquid phase of the bulk metallic glass forming alloy Au49Cu26.9Si16.3Ag5.5Pd2.3 consists of a two-dimensional crystalline monolayer phase for temperatures of up to about 50 K above the eutectic temperature. The present alloy as well as glass forming Au82Si18 and Au-Si-Ge alloys containing small amounts of Ge are the only metallic liquids to exhibit surface freezing well above the melting temperature. This suggests that the phenomena of surface freezing in metallic liquids and glass forming ability are related and probably governed by similar physical properties.

  18. Ti/Pd/Ag Contacts to n-Type GaAs for High Current Density Devices

    NASA Astrophysics Data System (ADS)

    Huo, Pengyun; Rey-Stolle, Ignacio

    2016-06-01

    The metallization stack Ti/Pd/Ag on n-type Si has been readily used in solar cells due to its low metal/semiconductor specific contact resistance, very high sheet conductance, bondability, long-term durability, and cost-effectiveness. In this study, the use of Ti/Pd/Ag metallization on n-type GaAs is examined, targeting electronic devices that need to handle high current densities and with grid-like contacts with limited surface coverage (i.e., solar cells, lasers, or light emitting diodes). Ti/Pd/Ag (50 nm/50 nm/1000 nm) metal layers were deposited on n-type GaAs by electron beam evaporation and the contact quality was assessed for different doping levels (from 1.3 × 1018 cm-3 to 1.6 × 1019 cm-3) and annealing temperatures (from 300°C to 750°C). The metal/semiconductor specific contact resistance, metal resistivity, and the morphology of the contacts were studied. The results show that samples doped in the range of 1018 cm-3 had Schottky-like I- V characteristics and only samples doped 1.6 × 1019 cm-3 exhibited ohmic behavior even before annealing. For the ohmic contacts, increasing annealing temperature causes a decrease in the specific contact resistance ( ρ c,Ti/Pd/Ag ~ 5 × 10-4 Ω cm2). In regard to the metal resistivity, Ti/Pd/Ag metallization presents a very good metal conductivity for samples treated below 500°C ( ρ M,Ti/Pd/Ag ~ 2.3 × 10-6 Ω cm); however, for samples treated at 750°C, metal resistivity is strongly degraded due to morphological degradation and contamination in the silver overlayer. As compared to the classic AuGe/Ni/Au metal system, the Ti/Pd/Ag system shows higher metal/semiconductor specific contact resistance and one order of magnitude lower metal resistivity.

  19. In situ measurements of change in work function of Pt, Pd and Au surfaces during desorption of oxygen by using photoemission yield spectrometer in air

    NASA Astrophysics Data System (ADS)

    Yamashita, Daisuke; Ishizaki, Atsushi

    2016-02-01

    We investigated the change in work function of Pt, Pd and Au surfaces during desorption of oxygen by using a photoemission yield spectrometer with an open counter. Oxygen coverage was formed by UV/ozone treatment, and then continuous change in work function with exposure to air was observed at various temperatures. Work function of Pt, Pd and Au surfaces decreased during desorption of oxygen, and finally returned to the initial value of untreated surfaces. Furthermore, temperature dependence on the change in work function was found. These characteristics were explained using chemical kinetics scheme. The exponential decay of work function was well reproduced by the first-order reaction rate equation, and it was confirmed that the order of rate constant, kr, is kr(Au) < kr(Pd) < kr(Pt). The activation energy was estimated to be 36, 38 and 28 kJ/mol for Pt, Pd, Au, respectively.

  20. A novel reverse rectifying effects and negative differential resistance in asymmetric X-biphenyl-X (X=Pt, Pd, Pb) molecular junctions

    NASA Astrophysics Data System (ADS)

    Parashar, Sweta; Srivastava, Pankaj

    2016-04-01

    We investigate the electronic transport properties of asymmetric biphenyl systems for X-electrodes (X=Pt, Pd, Pb) using non-equilibrium Green's function approach combined with density functional theory. The asymmetry in such systems is constructed by coupling biphenyl molecule to Pt, Pd, Pb electrode materials through dithiocarboxylate anchoring group on the left side and thiol group on the right side. Interestingly, novel reverse rectifying behaviors are observed for Pt and Pd electrode case. This is due to stronger d-orbital characteristics of Pt and Pd electrodes which produces intense transmission peak near the Fermi level. However, negative differential resistance is realized in case of Pb electrode. These observed distinct features for different electrodes are important for next generation nanoscale devices.

  1. Highly-branched mesoporous Au-Pd-Pt trimetallic nanoflowers blooming on reduced graphene oxide as an oxygen reduction electrocatalyst.

    PubMed

    Huang, Liang; Han, Yujie; Dong, Shaojun

    2016-07-01

    Herein, we develop a one-pot, two surfactant-assisted synthesis of highly-branched mesoporous Au-Pd-Pt trimetallic nanoflowers blooming on rGO with superior electrochemical performance for the ORR. Similarly to the interaction between Pluronic F127 and hexadecylpyridinium chloride (HDPC), this method may be extended to other nonionic/ionic surfactants to synthesize all-metal branched porous nanoparticles, and shows promising applications in electrochemistry and catalysis. PMID:27306642

  2. Ultrasensitive detection of superoxide anion released from living cells using a porous Pt-Pd decorated enzymatic sensor.

    PubMed

    Zhu, Xiang; Liu, Tingting; Zhao, Hongli; Shi, Libo; Li, Xiaoqing; Lan, Minbo

    2016-05-15

    Considering the critical roles of superoxide anion (O2(∙-)) in pathological conditions, it is of great urgency to establish a reliable and durable approach for real-time determination of O2(∙-). In this study, we propose a porous Pt-Pd decorated superoxide dismutase (SOD) sensor for qualitative and quantitative detection O2(∙-). The developed biosensor exhibits a fast, selective and linear amperometric response upon O2(∙-) in the concentration scope of 16 to 1,536 μM (R(2)=0.9941), with a detection limit of 0.13 μM (S/N=3) and a low Michaelis-Menten constant of 1.37 μM which indicating a high enzymatic activity and affinity to O2(∙-). Inspiringly, the proposed sensor possesses an ultrahigh sensitivity of 1270 μA mM(-1)cm(-2). In addition, SOD/porous Pt-Pd sensor exhibits excellent anti-interference property, reproducibility and long-term storage stability. Beyond our expectation, the trace level of O2(∙-) released from living cells has also been successfully captured. These satisfactory results are mainly ascribed to (1) the porous interface with larger surface area and more active sites to provide a biocompatible environment for SOD (2) the specific biocatalysis of SOD towards O2(∙-) and (3) porous Pt-Pd nanomaterials fastening the electron transfer. The superior electrochemical performance makes SOD/porous Pt-Pd sensor a promising candidate for monitoring the dynamic changes of O2(∙-)in vivo. PMID:26745791

  3. Pt and Pd catalyzed oxidation of Li2O2 and DMSO during Li-O2 battery charging.

    PubMed

    Gittleson, Forrest S; Ryu, Won-Hee; Schwab, Mark; Tong, Xiao; Taylor, André D

    2016-05-01

    Rechargeable Li-O2 and Li-air batteries require electrode and electrolyte materials that synergistically promote long-term cell operation. In this study, we investigate the role of noble metals Pt and Pd as catalysts in the Li-O2 oxidation process and their compatibility with dimethyl sulfoxide (DMSO) based electrolytes. We identify a basis for low potential Li2O2 evolution followed by oxidative decomposition of the electrolyte to form carbonate side products. PMID:27111589

  4. Pt and Pd catalyzed oxidation of Li2O2 and DMSO during Li–O2 battery charging

    DOE PAGESBeta

    Gittleson, Forrest S.; Ryu, Won-Hee; Schwab, Mark; Tong, Xiao; Taylor, André D.

    2016-01-01

    Rechargeable Li-O2 and Li-air batteries require electrode and electrolyte materials that synergistcally promote long-term cell operation. We investigate the role of noble metals Pt and Pd as catalysts for the Li-O2 oxidation process and their compatibility with a dimethyl sulfoxide (DMSO) based electrolyte. Lastly, we identify a basis for low potential Li2O2 evolution followed by oxidative decomposition of the electrolyte to form carbonate side products.

  5. Lattice thermal conductivity of disordered NiPd and NiPt alloys

    NASA Astrophysics Data System (ADS)

    Alam, Aftab; Mookerjee, Abhijit

    2006-05-01

    Numerical calculations of lattice thermal conductivity are reported for the binary alloys NiPd and NiPt. The present work is a continuation of an earlier paper by us (Alam and Mookerjee 2005 Phys. Rev. B 72 214207), which developed a theoretical framework for the calculation of configuration-averaged lattice thermal conductivity and thermal diffusivity in disordered alloys. The formulation was based on the augmented space theorem (Mookerjee 1973 J. Phys. C: Solid State Phys. 6 L205) combined with a scattering diagram technique. In this paper we shall show the dependence of the lattice thermal conductivity on a series of variables like phonon frequency, temperature and alloy composition. The temperature dependence of κ(T) and its relation to the measured thermal conductivity is discussed. The concentration dependence of κ appears to justify the notion of a minimum thermal conductivity as discussed by Kittel, Slack and others (Kittel 1948 Phys. Rev. 75 972, Brich and Clark 1940 Am. J. Sci. 238 613; Slack 1979 Solid State Physics vol 34, ed H Ehrenreich, F Seitz and D Turnbull (New York: Academic) p 1). We also study the frequency and composition dependence of the thermal diffusivity averaged over modes. A numerical estimate of this quantity gives an idea about the location of the mobility edge and the fraction of states in the frequency spectrum which is delocalized.

  6. Thermomechanical behavior of NiTiPdPt high temperature shape memory alloy springs

    NASA Astrophysics Data System (ADS)

    Nicholson, D. E.; Padula, S. A., II; Noebe, R. D.; Benafan, O.; Vaidyanathan, R.

    2014-12-01

    Transformation strains in high temperature shape memory alloys (HTSMAs) are generally smaller than for conventional NiTi alloys and can be purposefully limited in cases where stability and repeatability at elevated temperatures are desired. Yet such alloys can still be used in actuator applications that require large strokes when used in the form of springs. Thus there is a need to understand the thermomechanical behavior of shape memory alloy spring actuators, particularly those consisting of alternative alloys. In this work, a modular test setup was assembled with the objective of acquiring stroke, stress, temperature, and moment data in real time during joule heating and forced convective cooling of Ni19.5Ti50.5Pd25Pt5 HTSMA springs. The spring actuators were subjected to both monotonic axial loading and thermomechanical cycling. The role of rotational constraints (i.e., by restricting rotation or allowing for free rotation at the ends of the springs) on stroke performance was also assessed. Finally, recognizing that evolution in the material microstructure can result in changes in HTSMA spring geometry, the effect of material microstructural evolution on spring performance was examined. This was done by taking into consideration the changes in geometry that occurred during thermomechanical cycling. This work thus provides insight into designing with HTSMA springs and predicting their thermomechanical performance.

  7. The role of water in the adsorption of oxygenated aromatics on Pt and Pd.

    PubMed

    Yang, Jin; Dauenhauer, Paul J; Ramasubramaniam, Ashwin

    2013-01-01

    Catalytic processing of biomass-derived oxygenates to valuable chemical products will contribute to a sustainable future. To provide insight into the conversion of processed sugars and lignin monomers, we present density functional theory studies of adsorption of phloroglucinol, a potentially valuable biomass derivative, on Pt(111) and Pd(111) surfaces. A comprehensive study of adsorption geometries and associated energies indicates that the bridge site is the most preferred adsorption site for phloroglucinol, with binding energies in the range of 2-3 eV in the vapor phase. Adsorption of phloroglucinol on these metal surfaces occurs via hybridization between the carbon p(z) orbitals and the metal d(z(2)) and d(yz) orbitals. With explicit solvent, hydrogen bonds are formed between phloroglucinol and water molecules thereby decreasing binding of phloroglucinol to the metal surfaces relative to the vapor phase by 20-25%. Based on these results, we conclude that solvent effects can significantly impact adsorption of oxygenated aromatic compounds derived from biomass and influence catalytic hydrogenation and hydrodeoxygenation reactions as well. PMID:22941861

  8. Allylic amination reactivity of Ni, Pd, and Pt heterobimetallic and monometallic complexes.

    PubMed

    Carlsen, Ryan W; Ess, Daniel H

    2016-06-14

    Transition metal heterobimetallic complexes with dative metal-metal interactions have the potential for novel fast reactivity. There are few studies that both compare the reactivity of different metal centers in heterobimetallic complexes and compare bimetallic reactivity to monometallic reactivity. Here we report density-functional calculations that show the reactivity of [Cl2Ti(N(t)BuPPh2)2M(II)(η(3)-methallyl)] heterobimetallic complexes for allylic amination follows M = Ni > Pd > Pt. This reactivity trend was not anticipated since the amine addition transition state involves M(II) to M(0) reduction and this could disadvantage Ni. Comparison of heterobimetallic complexes to the corresponding monometallic (CH2)2(N(t)BuPPh2)2M(II)(η(3)-methallyl) complexes reveals that this reactivity trend is due to the bimetallic interaction and that the bimetallic interaction significantly lowers the barrier height for amine addition by >10 kcal mol(-1). The impact of the early transition metal center on the amination addition barrier height depends on the late transition metal center. The lowest barrier heights for this reaction occur when late and early transition metal centers are from the same periodic table row. PMID:26893287

  9. Pd@Pt core-shell concave decahedra: A class of catalysts for the oxygen reduction reaction with enhanced activity and durability

    DOE PAGESBeta

    Wang, Xue; Vera, Madeline; Chi, Miaofang; Xia, Younan; Luo, Ming; Huang, Hongwen; Ruditskiy, Aleksey; Park, Jinho; Bao, Shixiong; Liu, Jingyue; et al

    2015-11-13

    Here, we report a facile synthesis of multiply twinned Pd@Pt core shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200 degrees C, naturally generating a core shell structure covered by concave facets. The nonuniformity inmore » the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm2pt) and mass (1.60 A/mg/2pt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm2pt and 0.32 A/mgpt, respectively). After 10 000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgpt, more than twice that of the pristine Pt/C catalyst.« less

  10. Band bending at Al, In, Ag, and Pt interfaces with CdTe and ZnTe (110)

    NASA Technical Reports Server (NTRS)

    Wahi, A. K.; Miyano, K.; Carey, G. P.; Chiang, T. T.; Lindau, I.

    1990-01-01

    UV and X-ray photoelectron spectroscopic methods are presently used to study the band-bending behavior and interfacial chemistry of Al, In, Ag, and Pt overlayers on vacuum-cleaved p-CdTe and p-ZnTe (110). All four metals are found to yield Schottky barriers on CdTe and ZnTe. The metal-induced gap states model prediction of a difference in barrier heights for two semiconductors which is dependent on their band lineup is borne out by the results for Ag, Pt, and Al, but not for In. Reaction and intermixing for Al, Ag, and Pt overlayers on CdTe and ZnTe indicate that these interfaces are not ideal.

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

    PubMed

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

    2003-01-01

    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 (POW) as a measure of bioaccumulation, in this study a simple shaking method was performed in order to investigate the effects of different complexing agents (-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. -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. PMID:12683977

  12. Water-Free Proton Conduction in Discotic Pyridylpyrazolate-based Pt(II) and Pd(II) Metallomesogens.

    PubMed

    Cuerva, Cristián; Campo, José A; Cano, Mercedes; Sanz, Jesús; Sobrados, Isabel; Diez-Gómez, Virginia; Rivera-Calzada, Alberto; Schmidt, Rainer

    2016-07-18

    In this work we report on water-free proton conductivity in liquid-crystal pyridylpyrazolate-based Pt(II) and Pd(II) complexes [M(pz(R(n,n)py))2] (pz(R(n,n)py) = 3-(3,5-dialkyloxyphenyl)-5-(pyridin-2-yl)pyrazolate, R(n,n) = C6H3(OCnH2n+1)2; n = 4, 12, 16, M = Pd; n = 12, M = Pt) with potential application as electrolyte materials in proton exchange membrane fuel cells. The columnar ordering of the complexes in the liquid-crystalline phase opens nanochannels, which are used for fast proton exchange as detected by impedance spectroscopy and NMR. The NMR spectra indicate that the proton conduction mechanism is associated with a novel C-H···N proton transfer, which persists above the clearing point of the material. The highest conductivity of ∼0.5 μS cm(-1) at 180 °C with an activation energy of 1.2 eV is found for the Pt(II) compound in the mesophase. The Pd(II) complexes with different chain length (n = 4, 12, and 16) show lower conductivity but smaller activation energies, in the range of 0.74-0.93 eV. PMID:27362555

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

    PubMed

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

    2002-10-01

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

  14. Resistive switching of Ag/In2O3/Pt heterostructures for non volatile memory applications

    NASA Astrophysics Data System (ADS)

    Mistry, Bhaumik V.; Joshi, U. S.; Pinto, R.

    2012-06-01

    Resistance switching properties of nanostructured In2O3 films grown on Pt bottom electrode have been investigated for non volatile memory applications. Ag/In2O3/Pt/Ti/SiO2/Si heterostructures were fabricated by pulsed laser deposition and e-beam evaporation techniques. Polycrystalline growth of oxides In2O3 was confirmed by grazing incidence X-ray diffraction, where as AFM show nanostructured growth with smooth surface morphology. Two terminal I-V characteristics showed reproducible hysteresis with a sharp resistive switching, suggesting two distinct resistance states in the film and bipolar type switching. Typical resistance switching ratio (Ron/Roff) of the order of 72% has been estimated at room temperature. The mechanism of the observed resistance switching is analyzed by space charge limited current (SCLS) and the Schottky-like barrier formation at Ag/In2O3 interface in the off states, where as, Pool-Frankel type conduction mechanism seems valid in the on state.

  15. Supersaturation-controlled surface structure evolution of Pd@Pt core-shell nanocrystals: enhancement of the ORR activity at a sub-10 nm scale.

    PubMed

    Qi, Kun; Zheng, Weitao; Cui, Xiaoqiang

    2016-01-21

    Here, we designed and implemented a facile strategy for controlling the surface evolution of Pd@Pt core-shell nanostructures by simply adjusting the volume of OH(-) to control the reducing ability of ascorbic acid and finally manipulating the supersaturation in the reaction system. The surface structure of the obtained Pd@Pt bimetallic nanocrystals transformed from a Pt {111} facet-exposed island shell to a conformal Pt {100} facet-exposed shell by increasing the pH value. The as-prepared well aligned Pd@Pt core-island shell nanocubes present both significantly enhanced electrocatalytic activity and favorable long-term stability toward the oxygen reduction reaction in alkaline media. PMID:26693587

  16. Catalytic Properties Dominated by Electronic Structures in PdZn, NiZn, and PtZn Intermetallic Compounds

    NASA Astrophysics Data System (ADS)

    Nozawa, Kazuki; Endo, Naruki; Kameoka, Satoshi; Tsai, An Pang; Ishii, Yasushi

    2011-06-01

    The catalytic functions of Pd are completely modified by alloying with Zn, and PdZn exhibits comparable catalytic selectivity to Cu in the steam reforming of methanol (SRM). We perform theoretical and experimental studies to confirm our previous argument that the position of the d-band is a significant factor determining catalytic properties. First-principles slab calculations for M--Zn (M = Pd, Ni, Pt) reveal that the bond breaking on the surface leads to some reduction in the d-bandwidth, but that the position of the d-band for stable surfaces remains essentially unchanged from that of the bulk. The origin of the dramatic change in the electronic structure caused by alloying is theoretically demonstrated. Our previous argument is experimentally examined not only in SRM, but also in elemental reactions such as CO and H2 adsorptions. Magnetic measurements also indicate the importance of the d-band position in SRM.

  17. Synthesis, Characterization, and Antibacterial Studies of Pd(II) and Pt(II) Complexes of Some Diaminopyrimidine Derivatives

    PubMed Central

    Ajibade, Peter A.; Idemudia, Omoruyi G.

    2013-01-01

    Pd(II) and Pt(II) complexes of trimethoprim and pyrimethamine were synthesized and characterized by elemental analysis, UV-Vis, FTIR, and NMR spectroscopy. The complexes are formulated as four coordinate square planar species containing two molecules of the drugs and two chloride or thiocyanate ions. The coordination of the metal ions to the pyrimidine nitrogen atom of the drugs was confirmed by spectroscopic analyses. The complexes were screened for their antibacterial activities against eight bacterial isolates. They showed varied activities with the active metal complexes showing more enhanced inhibition than either trimethoprim or pyrimethamine. The Pd(II) complexes of pyrimethamine showed unique inhibitory activities against P. aeruginosa and B. pumilus, and none of the other complexes or the drugs showed any activity against these bacteria isolates. The MIC and MBC determinations revealed that these Pd(II) complexes are the most active. Structure activity relationship showed that Pt(II) complexes containing chloride ions are more active, while for Pd(II) complexes containing thiocyanate ions showed more enhanced activity than those containing chloride ions. PMID:23573071

  18. Tuneable reactivity with PPh3 and SnX2 of four- and five-coordinate Pd(II) and Pt(II) complexes containing polyphosphines.

    PubMed

    Fernández-Anca, Damián; García-Seijo, M Inés; García-Fernández, M Esther

    2013-07-28

    The reactivity of the unusual d(8) trigonal-bipyramidal systems [MX(PP3)]X (X = Cl: M = Pd(1a), Pt(2a); X = Br: M = Pd(3a), Pt(4a); X = I: M = Pd(5a), Pt(6a); PP3 = tris[2-(diphenylphosphino)ethyl]phosphine) in CHCl3-CH3OH, the square-pyramidal compounds [MCl(NP3)]Cl (M = Pd(7a); Pt(8a); NP3 = tris[2-(diphenylphosphino)ethyl]amine) in CD3OD-DMF and the distorted square-planar mononuclear [MX(PNP)]X (M = Pd: X = Cl(10a); M = Pt: X = I(10b); PNP = bis[2-(diphenylphosphino)ethyl]amine) and the heteronuclear [PdAu2X4(PP3)] [X = I(9a), Cl(14a), Br(15a)] and [MAuX2(PP3)]X [M = Pd: X = Cl(16a); M = Pt: X = Cl(17a), Br(18a)] species in CDCl3 with PPh3 + SnX2 has been explored to establish the factors that influence the nature of the products. With the mononuclear precursors the course of the reaction is strongly dependent on the tripodal or linear arrangement of the polydentate ligand and in the former case on the halogen. Thus, while for chlorides (1a-2a, 7a-8a) and bromides (3a-4a) the reaction led to the trigonal-bipyramidal compounds [M(SnCl3)(AP3)][SnCl3] [A = P: M = Pd(1), Pt(2); A = N: M = Pd(7), Pt(8)], [MBr(PP3)][SnBr3] [M = Pd(4), Pt(6)] containing M-Sn and M-Br bonds, respectively, for iodides (5a-6a) resulted in the unknown neutral square-planar compounds [MI2(PP(PO)2)(SnI2)2] [M = Pd(9) and Pt(10)] bearing two dangling P=O-SnI2 units and P2MI2 environments. However, complexes of the type [PtCl(PP2PO)X]X' [X = SnCl2, X' = [SnCl3](-)(11)] and [M(PP(PO)2)2X4]X'2 [X = SnCl2, X' = [SnCl3](-): M = Pd(12), Pt(13)] showing P=O-SnCl2 arms were obtained by direct reaction of [PtCl(PP2PO)]Cl (11a) and [M(PP(PO)2)2]Cl2 [M = Pd(12a), Pt(13a)] with SnCl2 in CH3OH. Although complex 9 was also prepared by interaction of the heteronuclear iodide 9a with PPh3 + SnI2 in CDCl3, the use of the neutral and ionic heteronuclear chlorides and bromides (14a-18a) as starting materials afforded the distorted square-planar ionic systems [MAuX'(PP3)(PPh3)][SnX3]2 [M = Pd: X = Cl, X' = Sn

  19. Phase Evolution in the Pd-Ag-CuO Air Braze Filler Metal Alloy System

    SciTech Connect

    Darsell, Jens T.; Weil, K. Scott

    2006-08-01

    Palladium was added as a ternary component to a series of copper oxide-silver alloys in an effort to increase the use temperature of these materials for potential ceramic air brazing applications. Phase equilibria in the ternary Pd-Ag-CuO system were investigated via differential scanning calorimetry (DSC) and a series of quenching experiments. Presented here are the latest findings on this system and a construction of the corresponding ternary phase diagram for low-to-moderate additions of palladium. The analysis included samples with higher palladium additions than were studied in the past, as well as an analysis of the composition-temperature trends in the Ag-CuO miscibility gap with palladium addition. It was found that the addition of palladium increases the solidus and liquidus and caused three phase zones to appear as expected by the phase rule. Furthermore, the palladium additions cause the miscibility gap boundary extending from the former binary eutectic to shift to lower silver-to-copper ratios.

  20. Cu, Pt, and Pd complexes of the 3-deoxy-1,2-bis(thiosemicarbazone) derived from D-glucose.

    PubMed

    Horton, D; Varela, O

    2000-09-22

    3-Deoxy-D-erythro-hexos-2-ulose bis(thiosemicarbazone) (1) acts as a tetradentate ligand of the N2S2 type which forms stable coordination complexes with metal(II) cations. The Cu(II), Pt(II), and Pd(II) chelates (2, 4, and 6, respectively) of 1 were synthesized and characterized by elemental analysis and NMR spectroscopy. The NMR spectra of the Pt complex (4) showed the coupling of H-1 and C-1, C-2 of the bis(thiosemicarbazone) with 195Pt (33.7% naturally occurring), which supports the structure proposed for the chelate. The complexes 2, 4, and 6 were acetylated to give the corresponding tri-O-acetyl derivatives 3, 5, and 7. Elimination of Cu(II) from 3 with hydrogen sulfide afforded 8, the tri-O-acetyl derivative of 1. Preliminary studies have shown antiviral activity of chelates 2, 4, and 6 against poliovirus type 1. PMID:11072850

  1. Tuning magnetotransport in PdPt/Y{sub 3}Fe{sub 5}O{sub 12}: Effects of magnetic proximity and spin-orbit coupling

    SciTech Connect

    Zhou, X.; Ma, L.; Shi, Z.; Zhou, S. M.; Guo, G. Y.; Hu, J.; Wu, R. Q.

    2014-07-07

    We report that anisotropic magnetoresistance (AMR) and anomalous Hall conductivity (AHC) in the Pd{sub 1−x}Pt{sub x}/Y{sub 3}Fe{sub 5}O{sub 12} (YIG) bilayers could be tuned by varying the Pt concentration (x) and also temperature (T). In particular, the AHC at low T changes its sign when x increases from 0 to 1, agreeing with the negative and positive AHC predicted by our ab initio calculations for the magnetic proximity (MP)-induced ferromagnetic Pd and Pt, respectively. The AMR ratio is enhanced by ten times when x increases from 0 to 1. Furthermore, the AMR of PdPt/YIG bilayers shows similar T-dependence as the magnetic susceptibility of the corresponding bulk Pd/Pt, also indicating the MP effect as the origin of the AMR. The present work demonstrates that the alloying of Pt and Pd not only offers tunable spin-orbit coupling but also is useful to reveal the nature of the AMR and AHC in Pt/YIG bilayers, which are useful for spintronics applications.

  2. Green Synthesis of Ag and Pd Nanospheres, Nanowires, and Nanorods Using Vitamin B 2 : Catalytic Polymerisation of Aniline and Pyrrole

    DOE PAGESBeta

    Nadagouda, Mallikarjuna N.; Varma, Rajender S.

    2008-01-01

    Formore » the first time, we report green chemistry approach using vitamin B 2 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 ( NaBH 4 ) or hydroxylamine hydrochloride and any special capping or dispersing agent. Vitamin B 2 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.« less

  3. CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO2 Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al2O3

    PubMed Central

    Goto, Tomoyo; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

    2015-01-01

    The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO2 and Pt/α-Al2O3 catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO2, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H2, while H2 combustion was activated by repeated exposure to H2 gas during the periodic gas test. Selective CO sensing of the micro-TGS against H2 was attempted using a double catalyst structure with 0.3–30 wt% Pt/α-Al2O3 as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al2O3 catalyst, by cancelling out the combustion heat from the AuPtPd/SnO2 catalyst. In addition, the AuPtPd/SnO2 and 0.3 wt% Pt/α-Al2O3 double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H2. PMID:26694397

  4. Nano-assemblies consisting of Pd/Pt nanodendrites and poly (diallyldimethylammonium chloride)-coated reduced graphene oxide on glassy carbon electrode for hydrogen peroxide sensors.

    PubMed

    Zhang, Yanyan; Zhang, Cong; Zhang, Di; Ma, Min; Wang, Weizhen; Chen, Qiang

    2016-01-01

    Non-enzymatic hydrogen peroxide (H2O2) sensors were fabricated on the basis of glassy carbon (GC) electrode modified with palladium (Pd) core-platinum (Pt) nanodendrites (Pt-NDs) and poly (diallyldimethylammonium chloride) (PDDA)-coated reduced graphene oxide (rGO). A facile wet-chemical method was developed for preparing Pd core-Pt nanodendrites. In this approach, the growth of Pt NDs was directed by Pd nanocrystal which could be regarded as seed. The PDDA-coated rGO could form uniform film on the surface of GC electrode, which provided a support for Pd core- Pt NDs adsorption by self-assembly. The morphologies of the nanocomposites were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction (spectrum). Electrocatalytic ability of the nanocomposites was evaluated by cyclic voltammetry and chronoamperometric methods. The sensor fabricated by Pd core-Pt NDs/PDDA-rGO/GCE exhibited high sensitivity (672.753 μA mM(-1) cm(-2)), low detection limit (0.027 μM), wider linear range (0.005-0.5mM) and rapid response time (within 5s). Besides, it also exhibited superior reproducibility, excellent anti-interference performance and long-term stability. The present work could afford a viable method and efficient platform for fabricating all kinds of amperometric sensors and biosensors. PMID:26478428

  5. Pumice-supported Pd-Pt bimetallic catalysts: Synthesis, structural characterization, and liquid-phase hydrogenation of 1,3-cyclooctadiene

    SciTech Connect

    Deganello, G.; Duca, D.; Liotta, L.F.; Martorana, A.; Venezia, M.; Benedetti, A.; Fagherazz, G.

    1995-01-01

    A series of pumice-supported palladium-platinum bimetallic catalysts were prepared and investigated by X-ray scattering (WAXS and SAXS) and XPS techniques. An alloy Pd-Pt was formed. The less abundant metal was found to segregate to the surface. The catalysts were tested in the liquid-phase hydrogenation of 1,3-cyclooctadiene to cyclooctene, and compared with similarly prepared pumice-supported palladium and platinum catalysts and other supported Pd-Pt catalysts reported in the literature. The addition of platinum reduces the activity and the selectivity of the palladium catalysts. Differences between the activity of these pumice-supported catalysts and the activity of previously described Pd and Pd-Pt catalysts on other supports, are attributed to the presence, in the latter, of diffusional processes. 50 refs., 4 figs. 2 tabs.

  6. Novel PdAgCu ternary alloy as promising materials for hydrogen separation membranes: Synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Tarditi, Ana M.; Cornaglia, Laura M.

    2011-01-01

    The use of the sequential electroless plating method allowed us to obtain the PdAgCu ternary alloy on top of dense stainless steel (SS) 316 L disks. The XRD analysis indicated that initially the nucleation of the two phases of the alloy (FCC and BCC) takes place, but the FCC/BCC ratio increases with the annealing time at 500 °C in H 2 stream. After 162 h, the film contained only the FCC phase, which presents promising properties to be applied in the synthesis of hydrogen selective membranes. SEM cross-section results showed that a dense, continuous, defect-free film was deposited on top of the SS support, and the EDS data indicated that no significant gradient was present on the thickness of the film. XPS and LEIS allowed us to determine that Cu and Ag surface segregation takes place after annealing up to 500 °C/5 days. In the top-most surface layer, Ag enrichment takes place as determined by ARXPS experiments which can be the result of the lower surface tension of Ag compared to that of Cu and Pd. Increasing the annealing temperature results in an increase of the Ag surface segregation while the Cu concentration in the top-most surface layer decreases.

  7. The effect of nanoparticles size on photocatalytic and antimicrobial properties of Ag-Pt/TiO2 photocatalysts

    NASA Astrophysics Data System (ADS)

    Zielińska-Jurek, Anna; Wei, Zhishun; Wysocka, Izabela; Szweda, Piotr; Kowalska, Ewa

    2015-10-01

    Ag-Pt-modified TiO2 nanocomposites were synthesized using the sol-gel method. Bimetallic modified TiO2 nanoparticles exhibited improved photocatalytic activity under visible-light irradiation, better than monometallic Ag/TiO2 and Pt/TiO2 nanoparticles (NPs). All modified powders showed localized surface plasmon resonance (LSPR) in visible region. The photocatalysts' characteristics by X-ray diffractometry (XRD), scanning transmission electron microscopy (STEM), diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption (BET method for specific surface area) showed that sample with the highest photocatalytic activity had anatase structure, about 93 m2/g specific surface area, maximum plasmon absorption at ca. 420 nm and contained small NPs of silver of 6 nm and very fine platinum NPs of 3 nm. The photocatalytic activity was estimated by measuring the decomposition rate of phenol in 0.2 mM aqueous solution under Vis and UV/vis light irradiation. It was found that size of platinum was decisive for the photocatalytic activity under visible light irradiation, i.e., the smaller Pt NPs were, the higher was photocatalytic activity. While, antimicrobial activities, estimated for bacteria Escherichia coli and Staphylococcus aureus, and pathogenic fungi belonging to Candida family, were only observed for photocatalysts containing silver, i.e., Ag/TiO2 and Ag-Pt/TiO2 nanocomposites.

  8. [Fatigue properties of dental alloys. 12% Au-Pd-Ag alloy and type III gold alloy].

    PubMed

    Kato, H

    1989-12-01

    Usually the mechanical properties of dental alloys are determined from the values obtained through static tests of their tensile strength, hardness, etc. Generally, high tensile strength and ductility are preferred. However, when small stresses within proportional limits are applied repeatedly (even though not amounting to destructive forces in static tests), they may cause rupture in the alloy or, at least, cause it to lose its original mechanical properties. This phenomenon is called metal fatigue. It is estimated that the intraoral stress loads received by dental restorations during mastication or during insertion and removal of appliances are repeated more than 3 x 10(5) times/year. From this standpoint, it may be more appropriate to estimate the fracture strength of such dental alloys based on the fatigue properties of the restorative materials used for clasps, bars, and fixed bridges. For this reason, it is necessary to obtain data through fatigue tests on the fatigue strength and the fatigue endurance limits of dental alloys, and it is important to find a correlation between these data and the static data on tensile strengths and ductility obtained by tensile tests. Two alloys are used in these experiments. Both wrought specimens and cast specimens of 12% Au-Pd-Ag and Type III gold alloy were prepared for the fatigue tests. The size of the rectangular wrought specimens was 3 x 4 x 110 mm. The 12% Au-Pd-Ag alloy was heated to 800 degrees C for 15 minutes, quenched, and reheated to 400 degrees C for 20 minutes and quenched again according to the manufacturer's instructions for heat treatment. The Type III gold alloy was heated to 700 degrees C for 10 minutes, quenched, and reheated to 350 degrees C for 20 minutes and quenched again. The cylindrical cast specimens were 60 mm long and 2 mm in diameter. They were invested by conventional methods and cast in a centrifugal casting machine, Thermotrol Model 2500. The four point bending test for the wrought specimen

  9. Leaching of Au, Ag, and Pd from waste printed circuit boards of mobile phone by iodide lixiviant after supercritical water pre-treatment

    SciTech Connect

    Xiu, Fu-Rong; Qi, Yingying; Zhang, Fu-Shen

    2015-07-15

    Highlights: • We report a novel process for recovering Au, Ag, and Pd from waste PCBs. • The effect of SCWO on the leaching of Au, Ag, and Pd in waste PCBs was studied. • SCWO was highly efficient for enhancing the leaching of Au, Ag, and Pd. • The optimum leaching parameters for Au, Ag, and Pd in iodine–iodide were studied. - Abstract: Precious metals are the most attractive resources in waste printed circuit boards (PCBs) of mobile phones. In this work, an alternative process for recovering Au, Ag, and Pd from waste PCBs of mobile phones by supercritical water oxidation (SCWO) pre-treatment combined with iodine–iodide leaching process was developed. In the process, the waste PCBs of mobile phones were pre-treated in supercritical water, then a diluted hydrochloric acid leaching (HL) process was used to recovery the Cu, whose leaching efficiency was approximately 100%, finally the resulting residue was subjected to the iodine–iodide leaching process for recovering the Au, Ag, and Pd. Experimental results indicated that SCWO pre-treatment temperature, time, and pressure had significant influence on the Au, Ag, and Pd leaching from (SCWO + HL)-treated waste PCBs. The optimal SCWO pre-treatment conditions were 420 °C and 60 min for Au and Pd, and 410 °C and 30 min for Ag. The optimum dissolution parameters for Au, Pd, and Ag in (SCWO + HL)-treated PCBs with iodine–iodide system were leaching time of 120 min (90 min for Ag), iodine/iodide mole ratio of 1:5 (1:6 for Ag), solid-to-liquid ratio (S/L) of 1:10 g/mL (1:8 g/mL for Ag), and pH of 9, respectively. It is believed that the process developed in this study is environment friendly for the recovery of Au, Ag, and Pd from waste PCBs of mobile phones by SCWO pre-treatment combined with iodine–iodide leaching process.

  10. Amperometric biosensor of SnO2 thin film modified by Pd, In and Ag nanostructure synthesized by CSP method

    NASA Astrophysics Data System (ADS)

    Hassan, Marwa Abdul Muhsien; Hateef, Areej Adnan; Majeed, Aseel Mustafa Abdul; Al-Jabiry, Ali Jasim Mohammed; Jameel, Sabah; Hussian, Haidar Abdul Razaq Abdul

    2013-10-01

    Palladium, Indium and Silver-doped SnO2 thin film was deposited by chemical spray pyrolysis on ITO and porous silicon substrates to be a fast MgSO4·7H2O amperometric biosensor. The prepared SnO2 films were doped by dipping in palladium chloride PdCl2, indium chloride, InCl3 and silver nitrides AgNO3 dissolved in ethanol C2H5OH. The structural and optical properties of the prepared films were studied. The sensitivity behaviors of SnO2, SnO2: Pd, SnO2: In and SnO2: Ag based on the amperometric biosensor to MgSO4·7H2O salts were investigated at room temperature with different doping.

  11. Synthesis of Ag/Pd nanoparticles via reactive micelles as templates and its application to electroless copper deposition.

    PubMed

    Yang, Chia-Cheng; Wan, Chi-Chao; Wang, Yung-Yun

    2004-11-15

    Ag/Pd nanoparticles have been synthesized with a reactive alcohol-type surfactant, sodium dodecyl sulfate (SDS), without the presence of an external reducing agent. Both UV-vis absorption spectra and X-ray diffraction patterns for the bimetallic and physical mixtures of individual nanoparticles revealed the formation of a bimetallic structure. Based on this method, an ordered 3D grapelike nanostructure was formed, possibly due to transformation of the liquid crystal phase of the micelles. Data from the energy-dispersive X-ray analysis show that the composition of bimetallic nanoparticle is approximately equal to the feeing solution. Furthermore, the Ag/Pd nanoparticles exhibit distinct catalyst for electroless copper deposition and may be a substitute for the conventional palladium system, which is expensive and unstable in operation. PMID:15464808

  12. Graphene/nano-porous silicon and graphene/bimetallic silicon nanostructures (Pt-M, M: Pd, Ru, Rh), efficient electrocatalysts for the hydrogen evolution reaction.

    PubMed

    Ensafi, Ali A; Jafari-Asl, Mehdi; Rezaei, Behzad

    2015-10-01

    In this work nano-porous silicon flour (Nano-PSiF) was synthesized first and then there was an investigation into its electrocatalytic activity for the electrochemical hydrogen evolution reaction (HER). The results showed that Nano-PSiF has good electrocatalytic activity for the HER when compared with PSiF. In the second section, Pt and Pt-M (M = Pd, Rh, Ru) bimetallic silicon nanostructures were prepared by a direct reduction of the metal (Pt, Pt-Pd, Pt-Rh and Pt-Ru) on the surface of the PSiF by a galvanic exchange mechanism. The electrocatalytic activity of the bimetallic silicon nanostructures (Pt-M/PSiF) were evaluated for the HER. The results showed that all of the Pt-M/PSiFs have excellent electrocatalytic activity for the HER in a 0.5 mol L(-1) H2SO4 solution. For the Pt/PSiF, the Tafel slope of Pt/PSiF was 46.9 mV dec(-1), indicating its excellent electrocatalytic activity for the HER and it is comparable with commercial Pt/C. On the other hand, the bimetallic silicon nanostructures showed better electrocatalytic activity than Pt/PSiF for the HER (lower Tafel slope, and higher α). Finally, exfoliated graphene oxide was electro-deposited on the surface of a glassy carbon electrode (eRGO/GCE) and used as a sub-layer for the Pt-M/PSiF. Then, the electrocatalytic activities of the bimetallic silicon nanostructures on the eRGO/GCE were investigated for the HER. The results showed that there was a higher electrocatalytic activity for Pt-M/PSiF-eRGO/GCE when compared with Pt-M/PSiF-GCE. PMID:26304782

  13. Pd-Cu(2)O and Ag-Cu(2)O hybrid concave nanomaterials for an effective synergistic catalyst.

    PubMed

    Li, Lingling; Chen, Xiaobin; Wu, Yuen; Wang, Dingsheng; Peng, Qing; Zhou, Gang; Li, Yadong

    2013-10-11

    Palladium and silver salts were combined with Cu2 O octadecahedra in concave heterostructures. The formation of concave faces involved selective oxidative etching of Cu2 O on the {100} faces and in situ growth of Pd/Ag on different sites. The structures showed superior catalytic activities to both single domains and their mixtures in a model Sonogashira-type organic reaction. PMID:24038721

  14. Study of the state of Ag and Pd in silver-palladium catalysts on a titanium dioxide substrate by IR spectroscopy of adsorbed CO

    NASA Astrophysics Data System (ADS)

    Kovalenko, N. A.; Sen'ko, T. L.; Petkevich, T. S.; Egiazarov, Yu. G.

    2007-01-01

    We have used IR spectroscopy of adsorbed CO to study the effect of the method for preparation of silver-palladium catalysts on a TiO2 substrate and exposure to an oxidizing or reducing gaseous atmosphere on the state of Ag and Pd centers. We have shown that as a result of the metal-support interaction, the reducibility of the Ag and Pd particles is increased, which leads to a change in their adsorption and catalytic properties.

  15. Study on deposition technique and properties of Pd/Ag alloy film sensor supported on ceramic substrate

    NASA Astrophysics Data System (ADS)

    Geng, Z. T.; He, Q.; Jin, C. G.

    2016-07-01

    Developing high-quality hydrogen sensitive material is the core part of hydrogen sensor, whose performance is determined by the sensitive response, reproducibility and recovery of hydrogen material etc. In order to overcome the defects of hydrogen embrittlement in previous hydrogen sensor which were based on the pure palladium, sliver as the second component added to the palladium was studied. Using photochemical etching technology to produce a bent metal mask, the mask is put on the ceramic substrate. Firstly, the thin film of Ta2O5 as a transition layer grew on the ceramic substrate. Then, a series of Pd/Ag alloy film sensors were prepared, and each performance characterization of Pd/Ag alloy film was studied. Testing results indicated that the thin film had a good linear output performance at 0∼⃒30% hydrogen concentration range, and demonstrates a high responsiveness and good repeatability. With temperature increasing, the strength of the responsive signal of the Pd/Ag alloy film decreases and its responsive time was also shortened.

  16. Computational molecular characterization of the flavonoid Morin and its Pt(II), Pd(II) and Zn(II) complexes.

    PubMed

    Payán-Gómez, Sergio A; Flores-Holguín, Norma; Pérez-Hernández, Antonino; Piñón-Miramontes, Manuel; Glossman-Mitnik, Daniel

    2011-05-01

    In this work, we make use of a model chemistry within density functional theory (DFT) recently presented, which is called M05-2X, to calculate the molecular structure of the flavonoid Morin and its Pt(II), Pd(II) and Zn(II) complexes, as well to predict their IR and UV-Vis spectra, the dipole moment and polarizability, the free energy of solvation in different solvents as an indication of solubility, the HOMO and LUMO orbitals, and the chemical reactivity parameters that arise from Conceptual DFT. The calculated values are compared with the available experimental data for these molecules. PMID:20628776

  17. Spin Crossover in Fe(II)-M(II) Cyanoheterobimetallic Frameworks (M = Ni, Pd, Pt) with 2-Substituted Pyrazines.

    PubMed

    Kucheriv, Olesia I; Shylin, Sergii I; Ksenofontov, Vadim; Dechert, Sebastian; Haukka, Matti; Fritsky, Igor O; Gural'skiy, Il'ya A

    2016-05-16

    Discovery of spin-crossover (SCO) behavior in the family of Fe(II)-based Hofmann clathrates has led to a "new rush" in the field of bistable molecular materials. To date this class of SCO complexes is represented by several dozens of individual compounds, and areas of their potential application steadily increase. Starting from Fe(2+), square planar tetracyanometalates M(II)(CN)4(2-) (M(II) = Ni, Pd, Pt) and 2-substituted pyrazines Xpz (X = Cl, Me, I) as coligands we obtained a series of nine new Hofmann clathrate-like coordination frameworks. X-ray diffraction reveals that in these complexes Fe(II) ion has a pseudo-octahedral coordination environment supported by four μ4-tetracyanometallates forming its equatorial coordination environment. Depending on the nature of X and M, axial positions are occupied by two 2X-pyrazines (X = Cl and M(II) = Ni (1), Pd (2), Pt (3); X = Me and M(II) = Ni (4), Pd (5)) or one 2X-pyrazine and one water molecule (X = I and M(II) = Ni (7), Pd (8), Pt (9)), or, alternatively, two distinct Fe(II) positions with either two pyrazines or two water molecules (X = Me and M(II) = Pt (6)) are observed. Temperature behavior of magnetic susceptibility indicates that all compounds bearing FeN6 units (1-6) display cooperative spin transition, while Fe(II) ions in N5O or N4O2 surrounding are high spin (HS). Structural changes in the nearest Fe(II) environment upon low-spin (LS) to HS transition, which include ca. 10% Fe-N distance increase, lead to the cell expansion. Mössbauer spectroscopy is used to characterize the spin state of all HS, LS, and intermediate phases of 1-9 (see abstract figure). Effects of a pyrazine substituent and M(II) nature on the hyperfine parameters in both spin states are established. PMID:27120049

  18. Site preference of ternary alloying additions to NiTi: Fe, Pt, Pd, Au, Al, Cu, Zr and Hf

    NASA Technical Reports Server (NTRS)

    Bozzolo, Guillermo; Noebe, Ronald D.; Mosca, Hugo O.

    2004-01-01

    Atomistic modeling of the site substitution behavior of Pd in NiTi (J. Alloys and Comp. (2004), in press) has been extended to examine the behavior of several other alloying additions, namely, Fe, Pt, Au, Al, Cu, Zr and Hf in this important shape memory alloy. It was found that all elements, to a varying degree, displayed absolute preference for available sites in the deficient sublattice. How- ever, the energetics of the different substitutional schemes, coupled with large scale simulations indicate that the general trend in all cases is for the ternary addition to want to form stronger ordered structures with Ti.

  19. Optic fiber hydrogen sensor based on high-low reflectivity Bragg gratings and WO3-Pd-Pt multilayer films

    NASA Astrophysics Data System (ADS)

    Dai, Jixiang; Yang, Minghong; Li, Zhi; Wang, Gaopeng; Huang, Chujia; Qi, Chongjie; Dai, Yutang; Wen, Xiaoyan; Cheng, Cheng; Guo, Huiyong

    2015-09-01

    A novel optic fiber hydrogen sensor is proposed in this paper. Two Bragg gratings with different reflectivity were written in single mode fiber with phase mask method by 248 nm excimer laser. The end-face of singe mode fiber was deposited with WO3-Pd-Pt multilayer films as sensing element. The peak intensity of low reflectivity FBG is employed for hydrogen characterization, while that of high reflectivity FBG is used as reference. The experimental results show the hydrogen sensor still has good repeatability when the optic intensity in the fiber is only 1/3 of its initial value. The hydrogen sensor has great potential in measurement of hydrogen concentration.

  20. Unusual transport and highly anisotropic thermopower in PtCoO2 and PdCoO2

    SciTech Connect

    Ong, Khuong P; Singh, David J; Wu, Ping

    2010-01-01

    We show, using Boltzmann transport calculations and analysis of experimental data, that hexagonal PdCoO2 and PtCoO2 have a highly unusual metallic transport. The in-plane transport is typical of a very good metal, with high conductivity and low positive thermopower. The c-axis transport is completely different, with 2 orders of magnitude lower, but still coherent, conductivity and remarkably a very large negative thermopower. This large anisotropy of the thermopower provides an opportunity for investigating transport in a highly unusual regime using bulk materials.

  1. Magnetization suppression in Co/Pd and CoCrPt by nitrogen ion implantation for bit patterned media fabrication

    NASA Astrophysics Data System (ADS)

    Sato, Kenji; Ajan, Antony; Aoyama, Nobuhide; Tanaka, Tsutomu; Miyaguchi, Yusuke; Tsumagari, Kanako; Morita, Tadashi; Nishihashi, Tsutomu; Tanaka, Atsushi; Uzumaki, Takuya

    2010-06-01

    We propose a bit patterned media fabrication method based on low energy nitrogen ion implantation. Nitrogen ion implantation of fcc-Co/Pd multilayer or hcp-CoCrPt single layer suppresses their magnetizations at room temperature. Ion implantation reduces the Curie temperature from 600 to 400 K (or lower) as a result of lattice expansion and reduced exchange interaction between the magnetic atoms in the magnetic layer. We have made media with magnetic dots of 190 to 30 nm in diameter by nitrogen ion doping through resist patterns. Writing and reading of the signal from individual dots were performed with a commercial perpendicular magnetic recording head.

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

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  3. Enhanced Selectivity to H2 Formation in Decomposition of HCOOH on the Ag19@Pd60 Core-Shell Nanocluster from First-Principles.

    PubMed

    Cho, Jinwon; Lee, Sangheon; Han, Jonghee; Yoon, Sung Pil; Nam, Suk Woo; Choi, Sun Hee; Hong, Seong-Ahn; Lee, Kwan-Young; Ham, Hyung Chul

    2015-10-01

    In this study, using spin-polarized density functional theory calculation we examined the origin of enhanced catalytic activity toward H2 production from HCOOH in Ag19@Pd60 core-shell nanoclusters (a 79-atom truncated octahedral cluster models). First, we find that the Pd monolayer shell on the Ag core can greatly enhance the selectivity to H2 formation via HCOOH decomposition compared to the pure Pd79 cluster by substantially reducing the binding energy of key intermediate HCOO and in turn the barrier for dehydrogenation. This activity enhancement is related to the modification of d states in the Pd monolayer shell by the strong ligand effect between Ag core and Pd shell, rather than the tensile strain effect by Ag core. In particular, the absence of dz2-r2 density of states near the Fermi level in the Pd monolayer shell (which originated from the substantial charge transfer from Ag to Pd) is the main reason for the increased H2 production from HCOOH decomposition. PMID:26726494

  4. Electrochemical immunosensor for detecting the spore wall protein of Nosema bombycis based on the amplification of hemin/G-quadruplex DNAzyme concatamers functionalized Pt@Pd nanowires.

    PubMed

    Wang, Qin; Song, Yue; Chai, Yaqin; Pan, Guoqing; Li, Tian; Yuan, Yali; Yuan, Ruo

    2014-10-15

    In this work, an ultrasensitive electrochemical immunosensor for detecting the Pebrine disease related spore wall protein of Nosema bombycis (SWP N.b) was fabricated based on the amplification of hemin/G-quadruplex functionalized Pt@Pd nanowires (Pt@PdNWs). The synthesized Pt@PdNWs possessed large surface area, which could effectively improve the immobilization amount of hemin/G-quadruplex DNAzyme concatamers produced via hybridization chain reaction (HCR). In the presence of SWP N.b, the hemin/G-quadruplex labeled Pt@PdNWs bioconjugations was captured on electrode surface and thus obtained electrochemical signal. After the addition of NADH into the electrolytic cell, hemin/G-quadruplex firstly acted as an NADH oxidase to locally produce H2O2 in the presence of dissolved O2. Then, the generated H2O2 would be quickly reduced via hemin/G-quadruplex as a horseradish peroxidase mimicking (HRP-mimicking) DNAzyme, which finally promoted the self-redox reaction of hemin/G-quadruplex and a greatly enhanced electrochemical signal was obtained. Furthermore, Pt@PdNWs with excellent electrocatalytic performance could also amplify electrochemical signal. With these amplification factors, the electrochemical immunosensor exhibited a wide linear range from 0.001 ng mL(-1) to 100 ng mL(-1) with a detection limit (LOD) of 0.24 pg mL(-1), providing a new promise for the diagnosis of Pebrine disease. PMID:24787126

  5. Electrochemical immunosensor for detecting typical bladder cancer biomarker based on reduced graphene oxide-tetraethylene pentamine and trimetallic AuPdPt nanoparticles.

    PubMed

    Ma, Hongmin; Zhang, Xiaoyue; Li, Xiaojian; Li, Rongxia; Du, Bin; Wei, Qin

    2015-10-01

    A highly sensitive electrochemical immunosensor for detection of typical bladder cancer biomarker-nuclear matrix protein 22 (NMP22) was developed by using reduced graphene oxide-tetraethylene pentamine (rGO-TEPA) and trimetallic AuPdPt nanoparticles (NPs). rGO-TEPA was used as the ideal material for signal amplification and AuPdPt NPs immobilization due to its excellent conductivity and large surface area. An effective platform was constructed for antibodies anchoring by using AuPdPt NPs, which kept the antibodies' high stability and bioactivity. Moreover, AuPdPt NPs could accelerate the electron transfer and enhance the signal response, which assisted by the synergistic effect of the three different metals (Au, Pd and Pt). The proposed immunosensor showed satisfied performance such as simple fabrication, low detection limits (0.01 U/mL), wide linear range (from 0.040 to 20 U/mL), short analysis time (2 min), high stability and selectivity in the detection of NMP22. Furthermore, the proposed immunosensor was employed to test real urine samples with satisfactory results. PMID:26078131

  6. Co/Pt and Co/Pd multilayers as a new class of magneto-optical recording materials

    NASA Astrophysics Data System (ADS)

    Zeper, W. B.; Greidanus, Franciscus J. A. M.; van Kesteren, H. W.; Jacobs, Ben A. J.; Spruit, J. H. M.; Carcia, Peter F.

    1990-08-01

    In this paper we give an overview of the magnetic and magneto-optical properties of Co/Pt and, to a less extent, Co/Pd multilayers as optimized for magneto-optical storage applications. The Co layers should be very thin, i.e. about 4 A , and the Pt layers about 10-20 A to achieve a 100 % remanent layer with perpendicular magnetic anisotropy and high coercivity (80-100 kA/m). Furthermore, the hysteresis loop becomes rectangular for total film thicknesses below about 20 nm. We measured the optical properties as a function of the wavelength of the light and calculated the figure of merit at three wavelengths (820, 633 and 410 nm) for various disk structures. Optimal figures of merit are obtained for film thicknesses below 20 nm, i.e. thicknesses that are optimum for the magnetic properties. The figure of merit at A. = 820 am for Co/Pt is comparable to that of GdTbFe and increases towards shorter wavelengths which favor higher-density recording. We discuss the recording performance using Lorentz images of the written domain patterns. Very regularly shaped domains can be written at normal writing conditions, i.e. at a laser power of 5-10 mW and fields of 25 kA/m. The highest carrier-to-noise ratio measured for Co/Pt is 51 dB (375 kHz carrier, 1.4 m/s, 10 kHz bandwidth). Aging experiments in dry oxygen-nitrogen atmosphere showed that Co/Pt multilayers are chemically stable up to 1 50 °C . Finally, no change in carrier-to-noise ratio is observed for Co/Pt multilayers with a Curie temperature below 300 °C after 2x104 write/read/erase cycles.

  7. Multi-functional ultrathin PdxCu1-x and Pt~PdxCu1-x one-dimensional nanowire motifs for various small molecule oxidation reactions

    SciTech Connect

    Liu, Haiqing; Wong, Stanislaus S.; Adzic, Radoslav R.

    2015-11-18

    Developing novel electrocatalysts for small molecule oxidation processes, including formic acid oxidation (FAOR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR), denoting the key anodic reactions for their respective fuel cell configurations, is a significant and relevant theme of recent efforts in the field. Herein, in this report, we demonstrated a concerted effort to couple and combine the benefits of small size, anisotropic morphology, and tunable chemical composition in order to devise a novel “family” of functional architectures. In particular, we have fabricated not only ultrathin 1-D Pd1–xCux alloys but also Pt-coated Pd1–xCux (i.e., Pt~Pd1–xCux; herein the ~ indicates an intimate association, but not necessarily actual bond formation, between the inner bimetallic core and the Pt outer shell) core–shell hierarchical nanostructures with readily tunable chemical compositions by utilizing a facile, surfactant-based, wet chemical synthesis coupled with a Cu underpotential deposition technique. Our main finding is that our series of as-prepared nanowires are functionally flexible. More precisely, we demonstrate that various examples within this “family” of structural motifs can be tailored for exceptional activity with all 3 of these important electrocatalytic reactions. In particular, we note that our series of Pd1–xCux nanowires all exhibit enhanced FAOR activities as compared with not only analogous Pd ultrathin nanowires but also commercial Pt and Pd standards, with Pd9Cu representing the “optimal” composition. Moreover, our group of Pt~Pd1–xCux nanowires consistently outperformed not only commercial Pt NPs but also ultrathin Pt nanowires by several fold orders of magnitude for both the MOR and EOR reactions in alkaline media. As a result, the variation of the MOR and EOR performance with

  8. Structural analysis of polymer-protected Pd/Pt bimetallic clusters as dispersed catalysts by using extended x-ray absorption fine structure spectroscopy

    SciTech Connect

    Toshima, Naoki; Harada, Masafumi; Yonezawa, Tetsu; Kushihashi, Kakuta; Asakura, Kiyotaka )

    1991-09-19

    Extended X-ray absorption fine structure (EXAFS) was applied to the determination of the structure of colloidal dispersions of the poly (N-vinyl-2-pyrrolidone)-protected palladium/platinum bimetallic clusters, which work as the catalysts for selective partial hydrogenation of 1,3-cyclooctadiene to cyclooctene. The catalytic activity was found to depend on the structure of the bimetallic clusters. The EXAFS data on the Pd/Pt (4/1) bimetallic clusters, which are the most active catalysts, indicate a Pt core structure, in which the 42 Pd atoms are on the surface of the cluster particle and 13 Pt atoms are at the center of the particle, forming a core. In contrast, the Pd/Pt (1/1) bimetallic clusters are suggested to have a modified Pt core structure, in which 28 Pt atoms connect directly with each other, being located both in the core and on the surface, and 27 Pd atoms form three islands on the surface of the cluster particle. These bimetallic clusters work as active catalysts for selective hydrogenation of olefins, selective partial hydrogenation of diene to monoene, and visible light-induced hydrogen generation from water.

  9. Determination of the compositions of the DIGM zone in nanocrystalline Ag/Au and Ag/Pd thin films by secondary neutral mass spectrometry.

    PubMed

    Molnár, Gábor Y; Shenouda, Shenouda S; Katona, Gábor L; Langer, Gábor A; Beke, Dezső L

    2016-01-01

    Alloying by grain boundary diffusion-induced grain boundary migration is investigated by secondary neutral mass spectrometry depth profiling in Ag/Au and Ag/Pd nanocrystalline thin film systems. It is shown that the compositions in zones left behind the moving boundaries can be determined by this technique if the process takes place at low temperatures where solely the grain boundary transport is the contributing mechanism and the gain size is less than the half of the grain boundary migration distance. The results in Ag/Au system are in good accordance with the predictions given by the step mechanism of grain boundary migration, i.e., the saturation compositions are higher in the slower component (i.e., in Au or Pd). It is shown that the homogenization process stops after reaching the saturation values and further intermixing can take place only if fresh samples with initial compositions, according to the saturation values, are produced and heat treated at the same temperature. The reversal of the film sequence resulted in the reversal of the inequality of the compositions in the alloyed zones, which is in contrast to the above theoretical model, and explained by possible effects of the stress gradients developed by the diffusion processes itself. PMID:27335738

  10. Determination of the compositions of the DIGM zone in nanocrystalline Ag/Au and Ag/Pd thin films by secondary neutral mass spectrometry

    PubMed Central

    Molnár, Gábor Y; Shenouda, Shenouda S; Katona, Gábor L; Langer, Gábor A

    2016-01-01

    Summary Alloying by grain boundary diffusion-induced grain boundary migration is investigated by secondary neutral mass spectrometry depth profiling in Ag/Au and Ag/Pd nanocrystalline thin film systems. It is shown that the compositions in zones left behind the moving boundaries can be determined by this technique if the process takes place at low temperatures where solely the grain boundary transport is the contributing mechanism and the gain size is less than the half of the grain boundary migration distance. The results in Ag/Au system are in good accordance with the predictions given by the step mechanism of grain boundary migration, i.e., the saturation compositions are higher in the slower component (i.e., in Au or Pd). It is shown that the homogenization process stops after reaching the saturation values and further intermixing can take place only if fresh samples with initial compositions, according to the saturation values, are produced and heat treated at the same temperature. The reversal of the film sequence resulted in the reversal of the inequality of the compositions in the alloyed zones, which is in contrast to the above theoretical model, and explained by possible effects of the stress gradients developed by the diffusion processes itself. PMID:27335738

  11. Enhancement of magneto-optical Kerr effect for Co ultra-thin film on Pt(1 1 1) with Ag buffer layer

    NASA Astrophysics Data System (ADS)

    Ho, H. Y.; Tzeng, C. L.; Su, C. W.; Shern, C. S.

    2004-11-01

    The magnetic properties of Co/1 ML Ag/Pt(1 1 1) have been monitored by magneto-optical Kerr effect. We find that the magnetization easy axis changes its direction from the out-of-plane to the in-plane when dCo⩾2 ML. In the annealing studies of 1 ML Co/1 ML Ag/Pt(1 1 1), the result shows that the enhancement in perpendicular magnetic anisotropy is strongly related to the formation of Co-Pt alloy. The atomic exchange between Co and Ag cause the increase of the coercivity. The possible mechanisms of the enhancement in perpendicular magnetic anisotropy and coercivity are discussed.

  12. Bis(thiosemicarbazonato) chelates of Co(II), Ni(II), Cu(II), Pd(II) and Pt(II)

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Singh, R.

    1985-01-01

    Bis chelates of Co(II), Ni(II), Cu(II), Pd(II) and Pt(II) with the enolic form of diethyl ketone and methyl n-propyl thiosemicarbazones were synthesized and characterized by elemental analyses, magnetic moments, i.r. and electronic and electron spin resonance spectral studies. All the complexes were found to have the composition ML 2 [where M = Co(II), Ni(II), Cu(II), Pd(ii) and Pt(II) and L = thiosemicarbazones of diethyl ketone and methyl n-propyl ketone]. Co(II) and Cu(II) complexes are paramagnetic and may have polymeric six-coordinate octahedral and square planar geometries, respectively. The Ni(II), Pd(II) and Pt(II) complexes are diamagnetic and may have square planar geometries. Pyridine adducts (ML 2·2Py) of Ni(II) and Cu(II) complexes were also prepared and characterized.

  13. Isothermal nucleation and growth kinetics of Pd/Ag alloy phase via in-situ time-resolved high-temperature x-ray diffraction (HTXRD) analysis

    SciTech Connect

    Ayturk, Mahmut Engin; Payzant, E Andrew; Speakman, Scott A; Ma, Yi Hua

    2008-01-01

    Among several different approaches to form Pd/Ag alloys for hydrogen separation applications, ex-situ studies carried by conventional X-ray point scanning detectors might fail to reveal the key aspects of the phase transformation between Pd and Ag metals. In this respect, in-situ time-resolved high temperature X-ray diffraction (HTXRD) was employed to study the Pd/Ag alloy phase nucleation and growth kinetics. By the use of linear position sensitive detectors, advanced optics and profile fitting with the use of JADE-6.5 software, isothermal phase evolution of the Pd/Ag alloy at 500 C, 550 C and 600 C under hydrogen atmosphere were quantified to elucidate the mechanistic details of the Pd/Ag alloy phase nucleation and growth pattern. Analysis of the HTXRD data by the Avrami model indicated that the nucleation of the Pd/Ag alloy phase was instantaneous where the growth mechanism was through diffusion-controlled one-dimensional thickening of the Pd/Ag alloy layer. The value of the Avrami exponent, n, was found to increase with temperature with the values of 0.34, 0.39 and 0.67 at 500oC, 550oC and 600oC, respectively. In addition, parabolic rate law analysis suggested that the nucleation of the Pd/Ag alloy phase was through a heterogeneous nucleation mode, in which the nucleation sites were defined as the non-equilibrium defects. The cross-sectional SEI micrographs indicated that the Pd/Ag alloy phase growth was strongly dependent upon the deposition morphology of the as-synthesized Pd and Ag layers formed by the electroless plating. Based on the Avrami model and the parabolic rate law, the estimated activation energies for the phase transformation were 236.5 and 185.6 kJ/mol and in excellent agreement with the literature values (183-239.5 kJ/mol).

  14. Exploring the spin states of 90Zr populated by (p,p'), (p,d), and (p,t) reactions

    NASA Astrophysics Data System (ADS)

    Ota, S.; Burke, J. T.; Casperson, R. J.; Escher, J. E.; Hughes, R. O.; Ressler, J. J.; Scielzo, N. D.; Thompson, I. J.; Austin, R. A. E.; Abromeit, B.; Foley, N. J.; McCleskey, E.; McCleskey, M.; Park, H. I.; Saastamoinen, A.; Ross, T. J.

    2016-06-01

    The 90Zr nucleus was produced by three different reactions: 90Zr(p,p'), 91Zr(p,d), and 92Zr(p,t), and the spin-parity (Jπ) population of the 90Zr states produced by these reactions was studied to investigate the surrogate reaction approach, which aims at indirectly determining cross sections for compound-nuclear reactions involving unstable targets such as 89Zr(n,γ). Discrete γ-rays, associated with the de-excitation of 90Zr and 89Zr, were measured in coincidence with light ions at 90Zr excitation energies extending above the neutron separation energy. Low-lying states populated by (p,d) and (p,t) reactions agreed well with the previous measurements. The measured γ transition systematics were used to gain insights into the Jπ distribution of 90Zr around the neutron separation energy and it was found that the (p,p') reaction preferentially produces lower J states than (p,d) and (p,t) reactions in the studied energy region.

  15. Prediction of Reliable Metal-PH₃ Bond Energies for Ni, Pd, and Pt in the 0 and +2 Oxidation States

    SciTech Connect

    Craciun, Raluca; Vincent, Andrew J.; Shaughnessy, Kevin H.; Dixon, David A.

    2010-06-21

    Phosphine-based catalysts play an important role in many metal-catalyzed carbon-carbon bond formation reactions yet reliable values of their bond energies are not available. We have been studying homogeneous catalysts consisting of a phosphine bonded to a Pt, Pd, or Ni. High level electronic structure calculations at the CCSD(T)/complete basis set level were used to predict the M-PH₃ bond energy (BE) for the 0 and +2 oxidation states for M=Ni, Pd, and Pt. The calculated bond energies can then be used, for example, in the design of new catalyst systems. A wide range of exchange-correlation functionals were also evaluated to assess the performance of density functional theory (DFT) for these important bond energies. None of the DFT functionals were able to predict all of the M-PH3 bond energies to within 5 kcal/mol, and the best functionals were generalized gradient approximation functionals in contrast to the usual hybrid functionals often employed for main group thermochemistry.

  16. Final Technical Report: First Principles Investigations for the Ensemble Effects of PdAu and PtAu Bimetallic Nanocatalysts

    SciTech Connect

    Ruqian Wu

    2012-05-18

    Bimetallic surfaces with tunable chemical properties have attracted broad attention in recent years due to their ample potential for heterogeneous catalysis applications. The local chemical properties of constituents are strongly altered from their parent metals by 'ligand effect', a term encompassing the influences of charge transfer, orbital rehybridization and lattice strain. In comparison to the aforementioned, the 'ensemble effect' associated with particular arrangements of the active constituents have received much less attention, despite their notable importance towards the determination of reactivity and selectivity of bimetallic catalysts. We performed theoretical studies for understanding the ensemble effects on bimetallic catalysis: (i) simulations for the formation of different ensembles on PdAu and PtAu nanoclusters; (ii) studies of the size, shape, and substrate dependence of their electronic properties; and (iii) simulations for model reactions such as CO oxidation, methanol, ethylene and water dehydrogenation on PdAu and PtAu nanoclusters. In close collaboration with leading experimental groups, our theoretical research elucidated the fundamentals of Au based bimetallic nanocatalysts.

  17. Leaching of Au, Ag, and Pd from waste printed circuit boards of mobile phone by iodide lixiviant after supercritical water pre-treatment.

    PubMed

    Xiu, Fu-Rong; Qi, Yingying; Zhang, Fu-Shen

    2015-07-01

    Precious metals are the most attractive resources in waste printed circuit boards (PCBs) of mobile phones. In this work, an alternative process for recovering Au, Ag, and Pd from waste PCBs of mobile phones by supercritical water oxidation (SCWO) pre-treatment combined with iodine-iodide leaching process was developed. In the process, the waste PCBs of mobile phones were pre-treated in supercritical water, then a diluted hydrochloric acid leaching (HL) process was used to recovery the Cu, whose leaching efficiency was approximately 100%, finally the resulting residue was subjected to the iodine-iodide leaching process for recovering the Au, Ag, and Pd. Experimental results indicated that SCWO pre-treatment temperature, time, and pressure had significant influence on the Au, Ag, and Pd leaching from (SCWO+HL)-treated waste PCBs. The optimal SCWO pre-treatment conditions were 420°C and 60min for Au and Pd, and 410°C and 30min for Ag. The optimum dissolution parameters for Au, Pd, and Ag in (SCWO+HL)-treated PCBs with iodine-iodide system were leaching time of 120min (90min for Ag), iodine/iodide mole ratio of 1:5 (1:6 for Ag), solid-to-liquid ratio (S/L) of 1:10g/mL (1:8g/mL for Ag), and pH of 9, respectively. It is believed that the process developed in this study is environment friendly for the recovery of Au, Ag, and Pd from waste PCBs of mobile phones by SCWO pre-treatment combined with iodine-iodide leaching process. PMID:25802060

  18. Preparation of Pt Ag alloy nanoisland/graphene hybrid composites and its high stability and catalytic activity in methanol electro-oxidation

    PubMed Central

    2011-01-01

    In this article, PtAg alloy nanoislands/graphene hybrid composites were prepared based on the self-organization of Au@PtAg nanorods on graphene sheets. Graphite oxides (GO) were prepared and separated to individual sheets using Hummer's method. Graphene nano-sheets were prepared by chemical reduction with hydrazine. The prepared PtAg alloy nanomaterial and the hybrid composites with graphene were characterized by SEM, TEM, and zeta potential measurements. It is confirmed that the prepared Au@PtAg alloy nanorods/graphene hybrid composites own good catalytic function for methanol electro-oxidation by cyclic voltammograms measurements, and exhibited higher catalytic activity and more stability than pure Au@Pt nanorods and Au@AgPt alloy nanorods. In conclusion, the prepared PtAg alloy nanoislands/graphene hybrid composites own high stability and catalytic activity in methanol electro-oxidation, so that it is one kind of high-performance catalyst, and has great potential in applications such as methanol fuel cells in near future. PMID:21982417

  19. Preparation of Pt Ag alloy nanoisland/graphene hybrid composites and its high stability and catalytic activity in methanol electro-oxidation.

    PubMed

    Feng, Lili; Gao, Guo; Huang, Peng; Wang, Xiansong; Zhang, Chunlei; Zhang, Jiali; Guo, Shouwu; Cui, Daxiang

    2011-01-01

    In this article, PtAg alloy nanoislands/graphene hybrid composites were prepared based on the self-organization of Au@PtAg nanorods on graphene sheets. Graphite oxides (GO) were prepared and separated to individual sheets using Hummer's method. Graphene nano-sheets were prepared by chemical reduction with hydrazine. The prepared PtAg alloy nanomaterial and the hybrid composites with graphene were characterized by SEM, TEM, and zeta potential measurements. It is confirmed that the prepared Au@PtAg alloy nanorods/graphene hybrid composites own good catalytic function for methanol electro-oxidation by cyclic voltammograms measurements, and exhibited higher catalytic activity and more stability than pure Au@Pt nanorods and Au@AgPt alloy nanorods. In conclusion, the prepared PtAg alloy nanoislands/graphene hybrid composites own high stability and catalytic activity in methanol electro-oxidation, so that it is one kind of high-performance catalyst, and has great potential in applications such as methanol fuel cells in near future. PMID:21982417

  20. Preparation of Pt Ag alloy nanoisland/graphene hybrid composites and its high stability and catalytic activity in methanol electro-oxidation

    NASA Astrophysics Data System (ADS)

    Feng, Lili; Gao, Guo; Huang, Peng; Wang, Xiansong; Zhang, Chunlei; Zhang, Jiali; Guo, Shouwu; Cui, Daxiang

    2011-10-01

    In this article, PtAg alloy nanoislands/graphene hybrid composites were prepared based on the self-organization of Au@PtAg nanorods on graphene sheets. Graphite oxides (GO) were prepared and separated to individual sheets using Hummer's method. Graphene nano-sheets were prepared by chemical reduction with hydrazine. The prepared PtAg alloy nanomaterial and the hybrid composites with graphene were characterized by SEM, TEM, and zeta potential measurements. It is confirmed that the prepared Au@PtAg alloy nanorods/graphene hybrid composites own good catalytic function for methanol electro-oxidation by cyclic voltammograms measurements, and exhibited higher catalytic activity and more stability than pure Au@Pt nanorods and Au@AgPt alloy nanorods. In conclusion, the prepared PtAg alloy nanoislands/graphene hybrid composites own high stability and catalytic activity in methanol electro-oxidation, so that it is one kind of high-performance catalyst, and has great potential in applications such as methanol fuel cells in near future.

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

    NASA Astrophysics Data System (ADS)

    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

  2. Thermodynamic and transport properties of single-crystalline UM Ga5 (M=Fe,Co,Ni,Ru,Rh,Pd,Os,Ir,Pt)

    NASA Astrophysics Data System (ADS)

    Moreno, N. O.; Bauer, E. D.; Sarrao, J. L.; Hundley, M. F.; Thompson, J. D.; Fisk, Z.

    2005-07-01

    We report the results of magnetic susceptibility, specific heat, and electrical resistivity measurements on UMGa5 (M=Fe,Co,Ni,Ru,Rh,Pd,Os,Ir,Pt) single crystals. Antiferromagnetic ordering was observed for M=Ni , Pd, and Pt, with ordering temperatures TN=80K , 28K , and 23.5K , respectively. For the UMGa5 compounds with transition metals from the Fe and Co columns, itinerant paramagnetic behavior is observed. The evolution of this behavior is discussed in terms of f -ligand interaction with an emphasis on the role played by f-d hybridization.

  3. DFT study of Hg adsorption on M-substituted Pd(1 1 1) and PdM/γ-Al2O3(1 1 0) (M = Au, Ag, Cu) surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Jiancheng; Yu, Huafeng; Geng, Lu; Liu, Jianwen; Han, Lina; Chang, Liping; Feng, Gang; Ling, Lixia

    2015-11-01

    The adsorption of Hgn (n = 1-3) on the Au-, Ag-, Cu-substituted Pd(1 1 1) surfaces as well as the PdM/γ-Al2O3(1 1 0) (M = Au, Ag, Cu) surfaces has been investigated using spin-polarized density functional theory calculations. It is found that M-substituted Pd(1 1 1) surfaces show as good Hg adsorption capacity as the perfect Pd(1 1 1) at low Hg coverage, while the Hg adsorption capacity is only slightly weakened at high Hg coverage. On the basis of stepwise adsorption energies analysis, it is concluded that M-substituted Pd(1 1 1) surfaces can contribute to the binding of Hg atom on the surfaces at high Hg coverage. The electronic properties of the second metal atoms are the main factor contributes to the Hg adsorption capacity. Gas phase Pd2 shows better Hg adsorption capacity than Pd2/γ-Al2O3, while PdM/γ-Al2O3 can adsorb Hg more efficiently than bare PdM clusters. It suggests that the γ-Al2O3 support can enhance the activity of PdM for Hg adsorption and reduces the activity of Pd2. It is also found that Pd is the main active composition responsible for the interaction of mercury with the surface for PdM/γ-Al2O3 sorbent. Taking Hg adsorption capacity and economic costs into account, Cu addition is a comparatively good candidate for Hg capture.

  4. Facile Synthesis of Ag Nanorods with No Plasmon Resonance Peak in the Visible Region by Using Pd Decahedra of 16 nm in Size as Seeds.

    PubMed

    Luo, Ming; Huang, Hongwen; Choi, Sang-Il; Zhang, Chao; da Silva, Robson Rosa; Peng, Hsin-Chieh; Li, Zhi-Yuan; Liu, Jingyue; He, Zhike; Xia, Younan

    2015-10-27

    This article describes a seed-mediated approach to the synthesis of Ag nanorods with thin diameters and tunable aspect ratios. The success of this method is built upon our recent progress in the synthesis of Pd decahedra as uniform samples, together with controllable sizes. When used as a seed, the Pd decahedron could direct the deposition of Ag atoms along the 5-fold axis to generate a nanorod, with its diameter being determined by the lateral dimension of the seed. We were able to generate Ag nanorods with uniform diameters down to 20 nm. Under the conditions we used for growth, symmetry breaking occurred as the Ag atoms were only deposited along one side of the Pd decahedral seed to generate a Ag nanorod with the Pd seed being positioned at one of its two ends. We also systematically investigated the localized surface plasmon resonance (LSPR) properties of the Ag nanorods. With the transverse mode kept below 400 nm, the longitudinal mode could be readily tuned from the visible to the near-infrared region by varying the aspect ratio. As an important demonstration, we obtained Ag nanorods with no LSPR peak in the visible spectrum (400-800 nm), which are attractive for applications related to the fabrication of touchscreen displays, solar films, and energy-saving smart windows. PMID:26372854

  5. Electrochemical promotion of propane oxidation on Pt deposited on a dense β"-Al2O3 ceramic Ag+ conductor

    NASA Astrophysics Data System (ADS)

    Tsampas, Michail; Kambolis, Anastasios; Obeid, Emil; Lizarraga, Leonardo; Sapountzi, Foteini; Vernoux, Philippe

    2013-08-01

    A new kind of electrochemical catalyst based on a Pt porous catalyst film deposited on a β"-Al2O3 ceramic Ag+ conductor was developed and evaluated during propane oxidation. It was observed that upon anodic polarization, the rate of propane combustion was significantly electropromoted up to 400%. Moreover, for the first time, exponential increase of the catalytic rate was evidenced during galvanostatic transient experiment in excellent agreement with EPOC equation.

  6. Factors affecting the optical properties of Pd-free Au-Pt-based dental alloys.

    PubMed

    Shiraishi, Takanobu; Takuma, Yasuko; Miura, Eri; Tanaka, Yasuhiro; Hisatsune, Kunihiro

    2003-12-01

    The optical properties of experimental Au-Pt-based alloys containing a small amount of In, Sn, and Zn were investigated by spectrophotometric colorimetry to extract factors affecting color of Au-Pt-based high-karat dental alloys. It was found that the optical properties of Au-Pt-based alloys are strongly affected by the number of valence electrons per atom in an alloy, namely, the electron:atom ratio, e/a. That is, by increasing the e/a-value, activities of reflection in the long-wavelength range and absorption in the short-wavelength range in the visible spectrum apparently increased. As a result, the maximum slope of the spectral reflectance curve at the absorption edge, which is located near 515 nm (approximately 2.4 eV), apparently increased with e/a-value. Due to this effect, the b*-coordinate (yellow-blue) in the CIELAB color space considerably increased and the a*-coordinate (red-green) slightly increased with e/a-value. The addition of a third element with a higher number of valence electrons to the binary Au-Pt alloy is, therefore, effective in giving a gold tinge to the parent Au-Pt alloy. This information may be useful in controlling the color of Au-Pt-based dental alloys. PMID:15348493

  7. Study of the interaction of DNA with cisplatin and other Pd(II) and Pt(II) complexes by atomic force microscopy.

    PubMed Central

    Onoa, G B; Cervantes, G; Moreno, V; Prieto, M J

    1998-01-01

    Modifications in the structure of a 260 bp DNA (hlyM) fragment from Escherichia coli caused by interaction with Pd(II) and Pt(II) complexes were studied. Cisplatin and transplatin [cis- and trans-PtCl2(NH3)2 respectively], Pt2Cl2(Spym)4 (Spym = 2-mercaptopyrimidine anion), Pd-famotidine and Pt-famotidine were incubated with DNA for 24 h at 37 degrees C and then observed with an atomic force microscope. Atomic force microscopy (AFM) provides the opportunity for nanometer resolution in research on the interaction between nucleic acids and metal complexes. The complexes induced noticeable changes in DNA topography according to their different characteristics and structure. In the case of cisplatin a shortening in DNA strands was observed. Transplatin and Pt2Cl2(Spym)4 caused shortening and compaction, whilst an aggregation of two strands was observed for the Pt-famotidine compound but not for the Pd-famotidine compound or the metal-free famotidine. PMID:9490794

  8. Low-temperature growth of carbon nanotubes by thermal chemical vapor deposition using Pd, Cr, and Pt as co-catalyst

    NASA Astrophysics Data System (ADS)

    Lee, Cheol Jin; Park, Jeunghee; Kim, Jae Myung; Huh, Yoon; Lee, Jeong Yong; No, Kwang Soo

    2000-09-01

    Palladium (Pd), chromium (Cr), and platinum (Pt) are used as co-catalysts to decrease the growth temperature of carbon nanotubes to 500-550°C. Pd is found to be the most efficient co-catalyst for the growth of carbon nanotubes on cobalt-nickel catalytic particles deposited on a silicon oxide substrate by thermal chemical vapor deposition using C 2H 2. High-resolution transmission electron microscopy reveals the bamboo-shaped carbon nanotubes grown at 500°C using Pd, while the curled carbon nanofibers are grown at 550°C using Cr.

  9. Detailed Evaluation of the Geometric and Electronic Structures of One-electron Oxidized Group 10 (Ni, Pd, and Pt) Metal(II)-(Disalicylidene)diamine Complexes

    PubMed Central

    Stack, T. Daniel P.

    2009-01-01

    The geometric and electronic structures of a series of one-electron oxidized group 10 metal salens (Ni, Pd, Pt) have been investigated in solution and in the solid state. Ni (1) and Pd (2) complexes of the tetradentate salen ligand N,N’-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine (H2Salcn) have been examined along with the Pt (3) complex of the salen ligand N,N’-bis(3,5-di-tert-butylsalicylidene)-1,2-ethylenediamine (H2Salen). All three oxidized compounds exist as ligand radical species in solution and in the solid state. The solid state structures of [1]+ and [3]+ exhibit a symmetric coordination sphere contraction relative to the neutral forms. By contrast, the coordination sphere of the Pd derivative [2]+ exhibits a pronounced asymmetry in the solid state. In solution, the oxidized derivatives display intense low-energy NIR transitions consistent with their classification as ligand radical compounds. Interestingly, the degree of communication between the phenolate moieties depends strongly on the central metal ion, within the Ni, Pd, and Pt series. Electrochemical measurements and UV-Vis-NIR spectroscopy, in conjunction with DFT calculations provide insights into the degree of delocalization of the one-electron hole in these systems. The Pd complex [2]+ is the least delocalized and is best described as a borderline Class II/III intervalence complex based on the Robin-Day classification system. The Ni [1]+ and Pt [3]+ analogues are Class III (fully delocalized) intervalence compounds. Delocalization is dependent on the electronic coupling between the redox-active phenolate ligands, mediated by overlap between the formally filled metal dxz orbital and the appropriate ligand molecular orbital. The degree of coupling increases in the order Pd < Ni < Pt for the one-electron oxidized group 10 metal salens. PMID:19639970

  10. A facile approach to prepare silicon-based Pt-Ag tubular dendritic nano-forests (tDNFs) for solar-light-enhanced methanol oxidation reaction.

    PubMed

    Lin, Chun-Ting; Shiao, Ming-Hua; Chang, Mao-Nan; Chu, Nancy; Chen, Yu-Wei; Peng, Yu-Hsuan; Liao, Bo-Huei; Huang, Hung Ji; Hsiao, Chien-Nan; Tseng, Fan-Gang

    2015-01-01

    In this paper, a facile two-step Galvanic replacement reaction (GRR) is proposed to prepare Pt-Ag tubular dendritic nano-forests (tDNFs) in ambient condition for enhancing methanol oxidation reaction (MOR) under solar illumination. In the first GRR, a homogeneous layer of silver dendritic nano-forests (DNFs) with 10 μm in thickness was grown on Si wafer in 5 min in silver nitride (AgNO3) and buffer oxide etchant (BOE) solution. In the second GRR, we utilized chloroplatinic acid (H2PtCl6) as the precursor for platinum (Pt) deposition to further transform the prepared Ag DNFs into Pt-Ag tDNFs. The catalytic performance and solar response of the Pt-Ag tDNFs toward methanol electro-oxidation are also studied by cyclic voltammetry (CV) and chronoamperometry (CA). The methanol oxidation current was boosted by 6.4% under solar illumination on the Pt-Ag tDNFs due to the induced localized surface plasmon resonance (LSPR) on the dendritic structure. Current results provide a cost-effective and facile approach to prepare solar-driven metallic electrodes potentially applicable to photo-electro-chemical fuel cells. PMID:25852370

  11. A facile approach to prepare silicon-based Pt-Ag tubular dendritic nano-forests (tDNFs) for solar-light-enhanced methanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Lin, Chun-Ting; Shiao, Ming-Hua; Chang, Mao-Nan; Chu, Nancy; Chen, Yu-Wei; Peng, Yu-Hsuan; Liao, Bo-Huei; Huang, Hung Ji; Hsiao, Chien-Nan; Tseng, Fan-Gang

    2015-02-01

    In this paper, a facile two-step Galvanic replacement reaction (GRR) is proposed to prepare Pt-Ag tubular dendritic nano-forests (tDNFs) in ambient condition for enhancing methanol oxidation reaction (MOR) under solar illumination. In the first GRR, a homogeneous layer of silver dendritic nano-forests (DNFs) with 10 μm in thickness was grown on Si wafer in 5 min in silver nitride (AgNO3) and buffer oxide etchant (BOE) solution. In the second GRR, we utilized chloroplatinic acid (H2PtCl6) as the precursor for platinum (Pt) deposition to further transform the prepared Ag DNFs into Pt-Ag tDNFs. The catalytic performance and solar response of the Pt-Ag tDNFs toward methanol electro-oxidation are also studied by cyclic voltammetry (CV) and chronoamperometry (CA). The methanol oxidation current was boosted by 6.4% under solar illumination on the Pt-Ag tDNFs due to the induced localized surface plasmon resonance (LSPR) on the dendritic structure. Current results provide a cost-effective and facile approach to prepare solar-driven metallic electrodes potentially applicable to photo-electro-chemical fuel cells.

  12. The Disposition of Pt, Pd, Ir, Os, and Ru in Marine Sediments and the K/T Boundary

    NASA Technical Reports Server (NTRS)

    Lee, Cin-Ty; Wasserburg, Gerald; Kyte, Frank

    2003-01-01

    The marine record of platinum group elements (PGEs) and Os isotopic compositions provides information on different inputs of PGEs into the oceans. Some studies based on a smaller subset of the PGEs suggest that the PGEs may suffer post-depositional mobility during diagenesis. In some K/T boundary clays, Kyte and others showed that the relative abundances of Pt, Pd, Ir, and Os can differ significantly from chondritic, which is the signature expected from fallout of the meteorite impact. In some K/T boundary sections, elevated Ir concentrations are observed as far as 1 meter from the cm-thick boundary clay containing the meteoritic ejecta. The purpose of this study was to characterize Pt, Pd, Ir, Os, and Ru abundances in zones including the K/T boundary. We determined PGE abundances of boundary clays at two hemipelagic sites (Stevns Klint, Denmark and Caravaca, Spain) in which previous studies by Kyte and others showed that the Ir anomaly is confined to within a few cm. We also analyzed two pelagic Pacific sites: a boundary clay from the north Pacific (Hole 465A) characterized by a 0.5 m thick Ir anomaly and a transect across the K/T boundary from the south Pacific (Hole 596) where the Ir anomaly spans 2 m. The Stevns Klint, Caravaca, and north Pacific sites are characterized by abundant marls and limestones in the section, whereas the south Pacific site is dominated by clays. Samples were spiked with isotopic tracers, mixed with a flux, S and Ni, and equilibrated by fusion. PGEs were extracted from the Ni and analyzed on a Finnigan Element ICP-MS. We find that the narrow Caravaca and Stevns Klint boundary clays have relative PGE abundance patterns indistinguishable from chondritic values. The two Pacific sites were found to have nearly identical PGE patterns but have ratios at the peak, which differ from chondritic values as found earlier by Evans et al. The Pacific sites were found to have nearly identical PGE patterns but are extremely depleted in OS (Os/Ir = 0

  13. Structural and magnetic phase transitions in CeCu6-xTx (T = Ag,Pd)

    DOE PAGESBeta

    Poudel, Lekhanath N.; De la cruz, Clarina; Payzant, E. Andrew; Koehler, Michael R.; May, Andrew F.; Garlea, Vasile O.; Taylor, Alice E.; Parker, David S.; Cao, Huibo B.; McGuire, Michael A.; et al

    2015-12-15

    The structural and the magnetic properties of CeCu6-xAgx (0 ≤ x ≤ 0.85) and CeCu6-xPdx (0 ≤ x ≤ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu6-xAgx and CeCu6-xPdx as a function of Ag/Pd composition are reported. The end member, CeCu6, undergoes a structural phase transition from an orthorhombic (Pnma) to a monoclinic (P21/c) phase at 240 K. In CeCu6-xAgx, the structural phase transition temperature (Ts) decreases linearly with Ag concentration and extrapolates to zero at xS ≈ 0.1. The structural transitionmore » in CeCu6-xPdx remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu6-xAgx and CeCu6-xPdx, exhibit a magnetic quantum critical point (QCP), at x ≈ 0.2 and x ≈ 0.05, respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ1 0 δ2), where δ1 ~ 0.62, δ2 ~ 0.25, x = 0.125 for CeCu6-xPdx and δ1 ~ 0.64, δ2 ~ 0.3, x = 0.3 for CeCu6-xAgx. As a result, the magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.« less

  14. Total Ionizing Dose (TID) Effects of γ Ray Radiation on Ag/AlOx/Pt Resistive Switching Memory

    NASA Astrophysics Data System (ADS)

    Yuan, Fang; Zhang, Zhigang; Shen, Shanshan; Pan, Liyang; Xu, Jun; Memory Research Team

    2014-03-01

    The TID effects of γ rays generated from a 60Co source on the Ag/AlOx/Pt resistive switching (RS) memory is studied. Memory performances, including initial resistance state (IRS), low/high resistance state (LRS/HRS), forming voltage (Vf) , switching voltage (Vset/Vreset) and retention reliability are examined on the memory devices before and after exposure to 1M rad (Si) radiation. The LRS is robust to the radiation whereas a little degeneration of uniformity is found in IRS and HRS, which is caused by the radiation induced defects (mainly holes), trapped in the oxide. For the same reason, Vf increases several multiples after radiation. However surprisingly, both Vset and Vreset decrease during the RS and the retention performance is greatly improved. Based on these TID effects, it is proposed that the RS mechanism in Ag/AlOx/Pt, Ag conducting filament based switching, may be reinforced through γ radiation, which assists in stabilizing the growth/rupture of Ag filaments. The high radiation tolerance of AlOx-based RS memory devices suggests a potential for aerospace and nuclear applications. Supported by the National Natural Science Foundation of China (20111300789).

  15. Self-rectifying performance in the sandwiched structure of Ag/In-Ga-Zn-O/Pt bipolar resistive switching memory

    PubMed Central

    2014-01-01

    We reported that the resistive switching of Ag/In-Ga-Zn-O/Pt cells exhibited self-rectifying performance at low-resistance state (LRS). The self-rectifying behavior with reliability was dynamic at elevated temperature from 303 to 393 K. The Schottky barrier originated from the interface between Ag electrode and In-Ga-Zn-O films, identified by replacing Ag electrode with Cu and Ti metals. The reverse current at 1.2 V of LRS is strongly suppressed and more than three orders of magnitude lower than the forward current. The Schottky barrier height was calculated as approximately 0.32 eV, and the electron injection process and resistive switching mechanism were discussed. PMID:25294977

  16. Chemical bonding and charge redistribution - Valence band and core level correlations for the Ni/Si, Pd/Si, and Pt/Si systems

    NASA Technical Reports Server (NTRS)

    Grunthaner, P. J.; Grunthaner, F. J.; Madhukar, A.

    1982-01-01

    Via a systematic study of the correlation between the core and valence level X-ray photoemission spectra, the nature of the chemical bonding and charge redistribution for bulk transition metal silicides has been examined. Particular emphasis is placed on Pt2Si and PtSi. It is observed that the strength of the metal (d)-silicon (p) interaction increases in the order Ni2Si, Pd2Si, Pt2Si. It is also observed that both the metal and silicon core lines shift to higher binding energy as the silicides are formed. The notion of charge redistribution for metallic bonds is invoked to explain these data.

  17. Electronic Properties of MoSi2-Type Hf2X Intermetallic Compounds (X=Pd, Ag, Cd)

    NASA Astrophysics Data System (ADS)

    Yaar, I.; Maytal-Beck, S.; Berant, Z.

    2001-11-01

    The Hf z coordinate and the value of the electric field gradient (efg) main component (V zz ), were calculated for three Hf2X compounds (X = Pd, Ag, Cd) on a first-principle basis, using the full potential linear augmented plane wave (LAPW) method. Exchange and correlation effects were treated either by the local spine density approximation (LSDA) or by the more advanced generalized gradient approximation (GGA). The calculated V zz values, in the Hf site, were in very good agreement with available 181Hf TDPAC experimental results.

  18. Investigation of nanostructured Pd-Ag/n-ZnO thin film based Schottky junction for methane sensing

    NASA Astrophysics Data System (ADS)

    Roy, S.; Das, S.; Sarkar, C. K.

    2016-07-01

    Undoped nanocrystalline n-type ZnO thin film was deposited by chemical deposition technique on a thermally oxidized p-Si (~5 Ω cm resistivity and <100> orientation) substrate. Formation of stable zinc oxide thin film was confirmed by two-dimensional X-Ray Diffraction (XRD) and EDX analysis. The average crystallite size of the ZnO sample was evaluated as ~50 nm. The surface was characterized by Field Emission Scanning Electron Microscopy (FESEM) and Atomic Force Microscopy (AFM) that confirm the formation of nanocrystalline (grain size ~50 nm) ZnO thin film with surface roughness of ~100 nm. Good conversion of precursor into ZnO thin film in the chemical deposition method was evident by Fourier Transform Infrared Spectroscopy (FTIR). A small peak at 479 cm-1was observed in the FTIR spectrum confirming the formation of quartzite structure of the ZnO. The band gap (~3.44 eV) of the material was calculated from the optical absorption spectroscopy. To prepare Pd-Ag/n-ZnO Schottky junction, Pd-Ag contacts were taken by electron beam evaporation method. I-V characteristics of the junction were studied at different temperatures in inert and reducing ambient (N2 and N2 + CH4) with turn on voltage of around 0.2 V. The parameters like ideality factor ( η), saturation current ( I 0), series resistance ( Rs), and barrier height ( Φ BO) of the junction were calculated in the temperature range 50-200 °C in N2 as well as in 1 % CH4 + N2 ambient. It was observed that the ideality factor decreases in the temperature range 50-200 °C ( η = 12.34 at 50 °C and η = 1.52 at 200 °C) in N2 ambient and η = 1.18 in N2 +CH4 ambient at 200 °C. Schottky Barrier Height ( Φ BO) of the Pd-Ag/n-ZnO junction was found to increase with temperature. A close observation of Pd-Ag/n-ZnO junction in the presence of methane was performed to appreciate its application as methane sensor. The sensing mechanism was illustrated by a simplified energy band diagram.

  19. Investigation of nanostructured Pd-Ag/n-ZnO thin film based Schottky junction for methane sensing

    NASA Astrophysics Data System (ADS)

    Roy, S.; Das, S.; Sarkar, C. K.

    2016-07-01

    Undoped nanocrystalline n-type ZnO thin film was deposited by chemical deposition technique on a thermally oxidized p-Si (~5 Ω cm resistivity and <100> orientation) substrate. Formation of stable zinc oxide thin film was confirmed by two-dimensional X-Ray Diffraction (XRD) and EDX analysis. The average crystallite size of the ZnO sample was evaluated as ~50 nm. The surface was characterized by Field Emission Scanning Electron Microscopy (FESEM) and Atomic Force Microscopy (AFM) that confirm the formation of nanocrystalline (grain size ~50 nm) ZnO thin film with surface roughness of ~100 nm. Good conversion of precursor into ZnO thin film in the chemical deposition method was evident by Fourier Transform Infrared Spectroscopy (FTIR). A small peak at 479 cm-1was observed in the FTIR spectrum confirming the formation of quartzite structure of the ZnO. The band gap (~3.44 eV) of the material was calculated from the optical absorption spectroscopy. To prepare Pd-Ag/n-ZnO Schottky junction, Pd-Ag contacts were taken by electron beam evaporation method. I-V characteristics of the junction were studied at different temperatures in inert and reducing ambient (N2 and N2 + CH4) with turn on voltage of around 0.2 V. The parameters like ideality factor (η), saturation current (I 0), series resistance (Rs), and barrier height (Φ BO) of the junction were calculated in the temperature range 50-200 °C in N2 as well as in 1 % CH4 + N2 ambient. It was observed that the ideality factor decreases in the temperature range 50-200 °C (η = 12.34 at 50 °C and η = 1.52 at 200 °C) in N2 ambient and η = 1.18 in N2 +CH4 ambient at 200 °C. Schottky Barrier Height (Φ BO) of the Pd-Ag/n-ZnO junction was found to increase with temperature. A close observation of Pd-Ag/n-ZnO junction in the presence of methane was performed to appreciate its application as methane sensor. The sensing mechanism was illustrated by a simplified energy band diagram.

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

  1. A further discussion of the factors controlling the distribution of Pt, Pd, Rh and Au in road dust, gullies, road sweeper and gully flusher sediment in the city of Sheffield, UK.

    PubMed

    Prichard, H M; Sampson, J; Jackson, M

    2009-02-15

    Forty paired road dust and gully sediments from the city of Sheffield in NE England show that high platinum, palladium and rhodium concentrations derived from catalytic converters depend on proximity to both roundabouts rather than traffic lights and to topographic lows. Road dust outside schools and control samples, further away on the same road, show that Pt, Pd and Rh concentrations are dependent on passing traffic flow rather than numbers of stopping vehicles. Highest values of Pt+Pd in road dust are 852 ppb and 694 ppb in gullies. Rh has maximum values of 113 ppb in road dust and 49 ppb in gullies. Pt and Pd values of a few ppb to just over 100 ppb occur in road dust where traffic does not stop, on roads away from junctions. Pt, Pd, Rh and Au are all picked up by road sweepers and gully flushers both with maximum values of just over 100 ppb Pt and Pd. High Au values (maximum 610 ppb in a road dust) were located on pavements, in suburbs, outside schools and in road sweepers collecting in residential areas rather than on high traffic flow roads. Stratification of Pt and Pd in gullies was not observed whereas a high Au value was recorded at the bottom of a gully suggesting gravity concentration for Au. Anomalous Pd grades of 1050 ppb in road dust from a school entrance and 2040 ppb in a street sweeper sample were recorded. These high Pd- and Au-bearing samples do not have anomalous Pt or Rh values and may be sourced from jewellery or dental fillings. However, most samples have consistent Pt/Pd ratios of about 1 and Pt/Rh values of 4 to 5 indicating a catalytic converter source. Pt and Pd are concentrated in road dust at levels well above background in all the samples, including on high and low traffic flow roads. PMID:19081605

  2. Temperature, pressure, and size dependence of Pd-H interaction in size selected Pd-Ag and Pd-Cu alloy nanoparticles: In-situ X-ray diffraction studies

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Kulriya, P. K.

    2014-03-21

    In this study, in-situ X-ray diffraction has been carried out to investigate the effect of temperature and pressure on hydrogen induced lattice parameter variation in size selected Pd-Ag and Pd-Cu alloy nanoparticles. The nanoparticles of three different mobility equivalent diameters (20, 40, and 60 nm) having a narrow size distribution were prepared by gas phase synthesis method. In the present range of temperature (350 K to 250 K) and pressure (10{sup −4} to 100 millibars), no α (H/Pd ≤ 0.03) ↔ β (H/Pd ≥ 0.54) phase transition is observed. At temperature higher than 300 °C or pressure lower than 25 millibars, there is a large difference in the rate at which lattice constant varies as a function of pressure and temperature. Further, the lattice variation with temperature and pressure is also observed to depend upon the nanoparticle size. At lower temperature or higher pressure, size of the nanoparticle seems to be relatively less important. These results are explained on the basis of the relative dominance of physical absorption and diffusion of H in Pd alloy nanoparticles at different temperature and pressure. In the present study, absence of α ↔ β phase transition points towards the advantage of using Pd-alloy nanoparticles in applications requiring long term and repeated hydrogen cycling.

  3. A Strategy for Fabricating Porous PdNi@Pt Core-shell Nanostructures and Their Enhanced Activity and Durability for the Methanol Electrooxidation

    NASA Astrophysics Data System (ADS)

    Liu, Xinyu; Xu, Guangrui; Chen, Yu; Lu, Tianhong; Tang, Yawen; Xing, Wei

    2015-01-01

    Three-dimensionally (3D) porous morphology of nanostructures can effectively improve their electrocatalytic activity and durability for various electrochemical reactions owing to big surface area and interconnected structure. Cyanogel, a jelly-like inorganic polymer, can be used to synthesize various three-dimensionally (3D) porous alloy nanomaterials owing to its double-metal property and particular 3D backbone. Here, 3D porous PdNi@Pt core-shell nanostructures (CSNSs) are facilely synthesized by first preparing the Pd-Ni alloy networks (Pd-Ni ANWs) core via cyanogel-reduction method followed by a galvanic displacement reaction to generate the Pt-rich shell. The as-synthesized PdNi@Pt CSNSs exhibit a much improved catalytic activity and durability for the methanol oxidation reaction (MOR) in the acidic media compared to the commercial used Pt black because of their specific structural characteristics. The facile and mild method described herein is highly attractive for the synthisis of 3D porous core-shell nanostructures.

  4. Ultrasensitive electrochemical immunosensor for SCCA detection based on ternary Pt/PdCu nanocube anchored on three-dimensional graphene framework for signal amplification.

    PubMed

    Liu, Yuanyuan; Ma, Hongmin; Gao, Jian; Wu, Dan; Ren, Xiang; Yan, Tao; Pang, Xuehui; Wei, Qin

    2016-05-15

    In this study, a novel and ultrasensitive sandwich-type electrochemical immunosensor was designed for the quantitative detection of squamous cell carcinoma antigen (SCCA) based on the β-cyclodextrin functionalized graphene nanosheet (CD-GN) and the ternary hollow Pt/PdCu nanocube anchored on three-dimensional graphene framework (Pt/PdCu-3DGF). CD-GN exhibited high specific surface area and good dispersibility and stability in water, which were beneficial to fix captured antibodies (Ab1) through the supramolecular host-guest interaction between CD and Ab1. The abundant oxygen-containing functional groups on 3DGF provided binding sites for anchoring noble metal nanoparticles. Pt/PdCu-3DGF could capture detected antibodies via the interaction of Pd-NH2 and Pt-NH2. Furthermore, the ternary metal nanoparticles exhibited high electrocatalytic activity toward the reduction of hydrogen peroxide. Under optimal conditions, the fabricated immunosensor showed a sensitive response to SCCA with two linear ranges. The linear ranges are 0.0001-1 ng/mL and 1-30 ng/mL with a detection limit of 25 fg/mL. Additionally, the proposed immunosensor showed good reproducibility and stability. PMID:26700578

  5. Fabrication and application of amperometric glucose biosensor based on a novel PtPd bimetallic nanoparticle decorated multi-walled carbon nanotube catalyst.

    PubMed

    Chen, Kuan-Jung; Lee, Chia-Feng; Rick, John; Wang, Shih-Han; Liu, Chung-Chiun; Hwang, Bing-Joe

    2012-03-15

    A sensitive, selective and stable amperometric glucose biosensor employing novel PtPd bimetallic nanoparticles decorated on multi-walled carbon nanotubes (PtPd-MWCNTs) was investigated. PtPd-MWCNTs were prepared by a modified Watanabe method, and characterized by XRD and TEM. The biosensor was constructed by immobilizing the PtPd-MWCNTs catalysts in a Nafion film on a glassy carbon electrode. An inner Nafion film coating was used to eliminate common interferents such as uric acid, ascorbic acid and fructose. Finally, a highly porous surface with an orderly three-dimensional network enzyme layer (CS-GA-GOx) was fabricated by electrodeposition. The resulting biosensor exhibited a good response to glucose with a wide linear range (0.062-14.07 mM) and a low detection limit 0.031 mM. The biosensor also showed a short response time (within 5 s), and a high sensitivity (112 μA mM(-1)cm(-2)). The Michaelis-Menten constant (K(m)) was determined as 3.3 mM. In addition, the biosensor exhibited high reproducibility, good storage stability and satisfactory anti-interference ability. The applicability of the biosensor to actual serum sample analysis was also evaluated. PMID:22277115

  6. Evaluation of carbon-supported Pt and Pd nanoparticles for the hydrogen evolution reaction in PEM water electrolysers

    NASA Astrophysics Data System (ADS)

    Grigoriev, S. A.; Millet, P.; Fateev, V. N.

    Carbon-supported Pt and Pd nanoparticles (CSNs) were synthesized and electrochemically characterized in view of potential application in proton exchange membrane (PEM) water electrolysers. Electroactive metallic nanoparticles were obtained by chemical reduction of precursor salts adsorbed to the surface of Vulcan XC-72 carbon carrier, using ethylene glycol as initial reductant and with final addition of formaldehyde. CSNs were then coated over the surface of electron-conducting working electrodes using an alcoholic solution of perfluorinated polymer. Their electrocatalytic activities with regard to the hydrogen evolution reaction (HER) were measured in sulfuric acid solution using cyclic voltammetry, and in a PEM cell during water electrolysis. Results obtained show that palladium can be advantageously used as an alternative electrocatalyst to platinum for the HER in PEM water electrolysers. Developed electrocatalysts could also be used in PEM fuel cells.

  7. H2 production by the photocatalytic reforming of cellulose and raw biomass using Ni, Pd, Pt and Au on titania

    PubMed Central

    Jones, W.; Hardacre, C.; Bowker, M.

    2016-01-01

    Here, we report a method for sustainable hydrogen production using sunlight and biomass. It is shown that cellulose can be photoreformed to produce hydrogen, even in solid form, by use of metal-loaded titania photocatalysts. The experiments performed verified that the process is enabled by initial hydrolysis via glucose, which itself is shown to be efficiently converted to produce hydrogen by photocatalysis. Importantly, it is shown that not only precious metals such as Pt, Pd and Au can be used as the metal component, but also much more economic and less environmentally damaging Ni is effective. Even more importantly, we show for the first time, to the best our knowledge, that fescue grass as raw biomass can be effective for hydrogen production without significant pre-treatment. This provides additional benefits for the efficiency of biomass hydrogen production, because fewer processing steps for the raw material are required than in the production of purer forms of cellulose, for example. PMID:27493561

  8. Oxygen chemisorption effects on the spatial atomic distribution of CuNi, CuPd and NiPt nanostructures

    NASA Astrophysics Data System (ADS)

    Montejano-Carrizales, J. M.; Morán-López, J. L.

    1993-05-01

    The spatial atomic distribution in cubo-octahedral CuNi, CuPd and NiPt clusters with a total number of atoms, N = 147, in the presence of chemisorbed oxygen, is studied. The equilibrium atomic configuration is obtained by calculating the free energy within the regular solution model and by assuming that the surface of the cluster is covered by oxygen atoms. Depending on the interaction between oxygen and the cluster components, the atomic distribution in the cluster can be completely modified as compared to the case of clusters with a clean surface. We present result for the temperature dependence of the concentration at the different shells around the central atom.

  9. Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters

    NASA Astrophysics Data System (ADS)

    Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y.; Nobusada, Katsuyuki; Jin, Rongchao

    2016-03-01

    Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared

  10. Study of the oxidation effects on isothermal solidification based high temperature stable Pt/In/Au and Pt/In/Ag thick film interconnections on LTCC substrate

    NASA Astrophysics Data System (ADS)

    Kumar, Duguta Suresh; Suri, Nikhil; Khanna, P. K.; Sharma, R. P.

    2016-03-01

    The objective of the presented paper is to determine the oxidized phase compositions of indium lead-free solders during solidification at 190 ° C under room environment with the help of X-ray diffraction (XRD) and Energy dispersive spectroscopy (EDX). Many lead-free solders alloys available oxidizes and have poor wetting properties. The oxidation of pure indium solder foil, Au, Pt, and Ag alloys were identified and investigated, in the process of isothermal solidification based solder joints construction at room environment and humidity. Both EDX and XRD characterization techniques were performed to trace out the amount of oxide levels and variety of oxide formations at solder interface respectively. The paper also aims to report the isothermal solidification technique to provide interconnections to pads on Low temperature co-fired ceramic (LTCC) substrate. It also elaborates advantages of isothermal solidification over the other methods of interconnection. Scanning electron microscope (SEM) used to identify the oxidized spots on the surface of Pt, Ag substrates and In solder. The identified oxides were reported.

  11. Sensitive determination of dopamine in the presence of uric acid and ascorbic acid using TiO2 nanotubes modified with Pd, Pt and Au nanoparticles.

    PubMed

    Mahshid, Sara; Li, Chengcheng; Mahshid, Sahar Sadat; Askari, Masoud; Dolati, Abolghasem; Yang, Lixia; Luo, Shenglian; Cai, Qingyun

    2011-06-01

    A simple modified TiO(2) nanotubes electrode was fabricated by electrodeposition of Pd, Pt and Au nanoparticles. The TiO(2) nanotubes electrode was prepared using the anodizing method, followed by modifying Pd nanoparticles onto the tubes surface, offering a uniform conductive surface for electrodeposition of Pt and Au. The performance of the modified electrode was characterized by cyclic voltammetry and differential pulse voltammetry methods. The Au/Pt/Pd/TiO(2) NTs modified electrode represented a high sensitivity towards individual detection of dopamine as well as simultaneous detection of dopamine and uric acid using 0.1 M phosphate buffer solution (pH 7.00) as the base solution. In both case, electro-oxidation peak currents of dopamine were linearly related to accumulated concentration over a wide concentration range of 5.0 × 10(-8) to 3.0 × 10(-5) M. However in the same range of dopamine concentration, the sensitivity had a significant loss at Pt/Pd/TiO(2) NTs electrode, suggesting the necessity for Au nanoparticles in modified electrode. The limit of the detection was determined as 3 × 10(-8) M for dopamine at signal-to-noise ratio equal to 3. Furthermore, the Au/Pt/Pd/TiO(2) NTs modified electrode was able to distinguish the oxidation response of dopamine, uric acid and ascorbic acid in mixture solution of different acidity. It was shown that the modified electrode possessed a very good reproducibility and long-term stability. The method was also successfully applied for determination of DA in human urine samples with satisfactory results. PMID:21494708

  12. Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters.

    PubMed

    Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y; Nobusada, Katsuyuki; Jin, Rongchao

    2016-03-24

    Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications. PMID:26967673

  13. Development of Pd-Ag Compostie Membrane for Separation of Hydrogen at Elevated Temperature

    SciTech Connect

    Shamsuddin Ilias

    2009-02-28

    Pd-based membrane reactor offers the possibility of combining reaction and separation in a single operation at high temperatures to overcome the equilibrium limitations experienced in conventional reactor configurations. In this project to develop a defect-free and hermally-stable Pd-film on microporous stainless steel (MPSS) support for H2-separation and membrane reactor applications, the electroless plating process was revisited with an aim to improve the membrane morphology. Specifically, this study includes; (a) an improvement f activation step using Pulse Laser Deposition (PLD), (b) development of a novel surfactant induced electroless plating (SIEP) for depositing robust Pd-film on microporous support, and (c) application of Pd-membrane as membrane reactor in steam methanol reforming (SMR) reactions.

  14. Structural and magnetic phase transitions in CeCu6-xTx (T = Ag,Pd)

    SciTech Connect

    Poudel, Lekhanath N.; De la cruz, Clarina; Payzant, E. Andrew; Koehler, Michael R.; May, Andrew F.; Garlea, Vasile O.; Taylor, Alice E.; Parker, David S.; Cao, Huibo B.; McGuire, Michael A.; Tian, Wei; Matsuda, Masaaki; Jeen, Hyoung Jeen; Lee, Ho Nyung; Hong, Tao; Calder, Stuart A.; Lumsden, Mark D.; Zhou, Haidong; Keppens, Veerle; Mandrus, D.; Christianson, Andrew D.

    2015-12-15

    The structural and the magnetic properties of CeCu6-xAgx (0 ≤ x ≤ 0.85) and CeCu6-xPdx (0 ≤ x ≤ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu6-xAgx and CeCu6-xPdx as a function of Ag/Pd composition are reported. The end member, CeCu6, undergoes a structural phase transition from an orthorhombic (Pnma) to a monoclinic (P21/c) phase at 240 K. In CeCu6-xAgx, the structural phase transition temperature (Ts) decreases linearly with Ag concentration and extrapolates to zero at xS ≈ 0.1. The structural transition in CeCu6-xPdx remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu6-xAgx and CeCu6-xPdx, exhibit a magnetic quantum critical point (QCP), at x ≈ 0.2 and x ≈ 0.05, respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ1 0 δ2), where δ1 ~ 0.62, δ2 ~ 0.25, x = 0.125 for CeCu6-xPdx and δ1 ~ 0.64, δ2 ~ 0.3, x = 0.3 for CeCu6-xAgx. As a result, the magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.

  15. Nucleation and growth mechanism of Pd/Pt bimetallic clusters in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles as studied by in situ X-ray absorption spectroscopy.

    PubMed

    Chen, Ching-Hsiang; Hwang, Bing-Joe; Wang, Guo-Rung; Sarma, Loka Subramanyam; Tang, Mau-Tsu; Liu, Din-Goa; Lee, Jyh-Fu

    2005-11-24

    We report in situ X-ray absorption spectroscopy (XAS) investigations on the formation of palladium-platinum (Pd/Pt) bimetallic clusters at the early stage within the water-in-oil microemulsion system of water/AOT/n-heptane. The reduction of palladium and platinum ions and the formation of corresponding clusters are monitored as a function of dosage of reducing agent, hydrazine (N(2)H(5)OH). Upon successive addition of the reducing agent, hydrazine (N(2)H(5)OH), five distinguishable steps are observed in the formation process of Pd/Pt clusters at the early stage. Both in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis for both the Pd K-edge and Pt L(III)-edge revealed the formation of Pd/Pt bimetallic clusters. A corresponding structural model is proposed for each step to provide a detailed insight into the nucleation and growth mechanism of Pd/Pt bimetallic clusters. We also discussed the atomic distribution of Pd and Pt atoms in Pd/Pt bimetallic clusters based on the calculated XAS structural parameters. PMID:16853800

  16. Modification of energy band alignment and electric properties of Pt/Ba{sub 0.6}Sr{sub 0.4}TiO{sub 3}/Pt thin-film ferroelectric varactors by Ag impurities at interfaces

    SciTech Connect

    Hirsch, S.; Komissinskiy, P. Flege, S.; Li, S.; Rachut, K.; Klein, A.; Alff, L.

    2014-06-28

    We report on the effects of Ag impurities at interfaces of parallel-plate Pt/Ba{sub 0.6}Sr{sub 0.4}TiO{sub 3}/Pt thin film ferroelectric varactors. Ag impurities occur at the interfaces due to diffusion of Ag from colloidal silver paint used to attach the varactor samples with their back side to the plate heated at 600–750 °C during deposition of Ba{sub 0.6}Sr{sub 0.4}TiO{sub 3}. X-ray photoelectron spectroscopy and secondary ion mass spectrometry suggest that amount and distribution of Ag adsorbed at the interfaces depend strongly on the adsorbent surface layer. In particular, Ag preferentially accumulates on top of the Pt bottom electrode. The presence of Ag significantly reduces the barrier height between Pt and Ba{sub 0.6}Sr{sub 0.4}TiO{sub 3} leading to an increased leakage current density and, thus, to a severe degradation of the varactor performance.

  17. Modification of energy band alignment and electric properties of Pt/Ba0.6Sr0.4TiO3/Pt thin-film ferroelectric varactors by Ag impurities at interfaces

    NASA Astrophysics Data System (ADS)

    Hirsch, S.; Komissinskiy, P.; Flege, S.; Li, S.; Rachut, K.; Klein, A.; Alff, L.

    2014-06-01

    We report on the effects of Ag impurities at interfaces of parallel-plate Pt/Ba0.6Sr0.4TiO3/Pt thin film ferroelectric varactors. Ag impurities occur at the interfaces due to diffusion of Ag from colloidal silver paint used to attach the varactor samples with their back side to the plate heated at 600-750 °C during deposition of Ba0.6Sr0.4TiO3. X-ray photoelectron spectroscopy and secondary ion mass spectrometry suggest that amount and distribution of Ag adsorbed at the interfaces depend strongly on the adsorbent surface layer. In particular, Ag preferentially accumulates on top of the Pt bottom electrode. The presence of Ag significantly reduces the barrier height between Pt and Ba0.6Sr0.4TiO3 leading to an increased leakage current density and, thus, to a severe degradation of the varactor performance.

  18. Ultrasonic-electrodeposition of PtPd alloy nanoparticles on ionic liquid-functionalized graphene paper: towards a flexible and versatile nanohybrid electrode

    NASA Astrophysics Data System (ADS)

    Sun, Yimin; Zheng, Huaming; Wang, Chenxu; Yang, Mengmeng; Zhou, Aijun; Duan, Hongwei

    2016-01-01

    Here we fabricate a new type of flexible and versatile nanohybrid paper electrode by ultrasonic-electrodeposition of PtPd alloy nanoparticles on freestanding ionic liquid (IL)-functionalized graphene paper, and explore its multifunctional applications in electrochemical catalysis and sensing systems. The graphene-based paper materials demonstrate intrinsic flexibility, exceptional mechanical strength and high electrical conductivity, and therefore can serve as an ideal freestanding flexible electrode for electrochemical devices. Furthermore, the functionalization of graphene with IL (i.e., 1-butyl-3-methylimidazolium tetrafluoroborate) not only increases the electroactive surface area of a graphene-based nanohybrid paper electrode, but also improves the adhesion and dispersion of metal nanoparticles on the paper surface. These unique attributes, combined with the merits of an ultrasonic-electrodeposition method, lead to the formation of PtPd alloy nanoparticles on IL-graphene paper with high loading, uniform distribution, controlled morphology and favourable size. Consequently, the resultant nanohybrid paper electrode exhibits remarkable catalytic activity as well as excellent cycle stability and improved anti-poisoning ability towards electrooxidation of fuel molecules such as methanol and ethanol. Furthermore, for nonenzymatic electrochemical sensing of some specific biomarkers such as glucose and reactive oxygen species, the nanohybrid paper electrode shows high selectivity, sensitivity and biocompatibility in these bio-catalytic processes, and can be used for real-time tracking hydrogen peroxide secretion by living human cells. All these features demonstrate its promising application as a versatile nanohybrid electrode material in flexible and lightweight electrochemical energy conversion and biosensing systems such as bendable on-chip power sources, wearable/implantable detectors and in vivo micro-biosensors.Here we fabricate a new type of flexible and

  19. Solid-solution precursor to melting in onion-ring Pd-Pt nanoclusters: a case of second-order-like phase change?

    PubMed

    Calvo, Florent

    2008-01-01

    The thermodynamical behaviour of icosahedral, multilayer Pd-Pt clusters is addressed using a combination of simulation tools, mainly parallel tempering Monte Carlo. A preferential swapping trial move is introduced to increase the chance of successfully exchanging Pd and Pt atoms in the cluster. The 2-, 3- and 4-shell, Pd-rich clusters have been studied. We generally find that the clusters melt at a temperature significantly below the bulk melting point at the same corresponding composition. More interestingly, for the smaller clusters melting is initiated by a solid-solution intermediate phase in which the overall icosahedral frame remains, but the Pd and Pt atoms can swap sites. The transition to this solid-solution phase is seen to have a continuous, second-order like character, which is interpreted from the similarity between the present system with the ferromagnetic Ising model on the 3D cubic lattice. As the cluster grows, the onion-ring structure becomes thermodynamically unstable. The 4-layer cluster already exhibits a solid-solution in its core at temperatures as low as 100 K. The bulk behaviour is thus recovered at very small scales. PMID:18447010

  20. New insights into the surface structure of Pt-Pd core-shell nanoparticles as revealed by Cs-corrected STEM

    NASA Astrophysics Data System (ADS)

    Khanal, Subarna; Casillas, Gilberto; Velazquez-Salazar, J. Jesus; Ponce, Arturo; Yacaman, Miguel Jose

    2012-10-01

    Bimetallic nanoparticles of Pt-Pd core-shell structures have been found to possess significant applications in fuel cells, hydrogen storage, catalysis, etc. However, the cost of Pt makes it unpractical to use in big quantities; therefore, one of the big challenges is to very small catalysts with only a few layers of the active metal in the shell in order to maximize the efficiency in their use. In this work the modified polyol method was used to synthesize Pt-Pd core-shell nanoparticles in the size range of 20 nm and characterized them by Cs-corrected scanning transmission electron microscopy. This technique allowed us to probe the structure at the atomic level of these nanoparticles revealing new structural information. We determined the structure of the three main polyhedral morphologies obtained in the synthesis: octahedral, decahedral and triangular plates. These final shapes of the core-shell structures were determined by the seed morphology. In addition the STEM energy dispersive X-ray spectroscopy (EDS) chemical analysis can be better identified the chemical composition of the nanocrystals. The overgrowth of the thin Pd shells on the Pt cores due to the epitaxial growth modes was observed. In this work, we have been able to observed Shockley partial dislocations, stacking faults, and adatoms at the surfaces of the nanoparticles.

  1. Growth of L10-ordered crystal in FePt and FePd thin films on MgO(001) substrate

    NASA Astrophysics Data System (ADS)

    Futamoto, Masaaki; Nakamura, Masahiro; Ohtake, Mitsuru; Inaba, Nobuyuki; Shimotsu, Teruho

    2016-08-01

    Formation of L10-oredered structure from disordered A1 phase has been investigated for FePt and FePd films on MgO(001) substrates employing a two-step method consisting of low temperature deposition at 200 °C followed by high-temperature annealing at 600 °C. L10-(001) variant crystal with the c-axis perpendicular to the substrate grows preferentially in FePd films whereas L10-(100), (010) variants tend to be mixed with the L10-(001) variant in FePt films. The structure analysis by X-ray diffraction indicates that a difference in A1 lattice strain is the influential factor that determines the resulting L10-variant structure in ordered thin films. Misfit dislocations and anti-phase boundaries are observed in high-resolution transmission electron micrographs of 10 nm-thick Fe(Pt, Pd) film consisting of L10-(001) variants which are formed through atomic diffusion at 600 °C in a laterally strained FePt/PeFd epitaxial thin film. Based on the experimental results, a nucleation and growth model for explaining L10-variant formation is proposed, which suggests a possibility in tailoring the L10 variant structure in ordered magnetic thin films by controlling the alloy composition, the layer structure, and the substrate material.

  2. Indole-7-carbaldehyde thiosemicarbazone as a flexidentate ligand toward ZnII, CdII, PdII and PtII ions: cytotoxic and apoptosis-inducing properties of the PtII complex.

    PubMed

    Ibrahim, Abeer A; Khaledi, Hamid; Hassandarvish, Pouya; Mohd Ali, Hapipah; Karimian, Hamed

    2014-03-14

    A new thiosemicarbazone (LH2) derived from indole-7-carbaldehyde was synthesized and reacted with Zn(II), Cd(II), Pd(II) and Pt(II) salts. The reactions with zinc and cadmium salts in 2 : 1 (ligand-metal) molar ratio afforded complexes of the type MX2(LH2)2, (X = Cl, Br or OAc), in which the thiosemicarbazone acts as a neutral S-monodentate ligand. In the presence of potassium hydroxide, the reaction of LH2 with ZnBr2 resulted in deprotonation of the thiosemicarbazone at the hydrazine and indole nitrogens to form Zn(L)(CH3OH). The reaction of LH2 with K2PdCl4 in the presence of triethylamine, afforded Pd(L)(LH2) which contains two thiosemicarbazone ligands: one being dianionic N,N,S-tridentate while the other one is neutral S-monodentate. When PdCl2(PPh3)2 was used as the Pd(II) ion source, Pd(L)(PPh3) was obtained. In a similar manner, the analogous platinum complex, Pt(L)(PPh3), was synthesized. The thiosemicarbazone in the latter two complexes behaves in a dianionic N,N,S-tridentate fashion. The platinum complex was found to have significant cytotoxicity toward four cancer cells lines, namely MDA-MB-231, MCF-7, HT-29, and HCT-116 but not toward the normal liver WRL-68 cell line. The apoptosis-inducing properties of the Pt complex was explored through fluorescence microscopy visualization, DNA fragmentation analysis and propidium iodide flow cytometry. PMID:24442181

  3. Associations of Pd, U and Ag in the SiC layer of neutron-irradiated TRISO fuel

    SciTech Connect

    Lillo, Thomas; Rooyen, Isabella Van

    2015-05-01

    Knowledge of the associations and composition of fission products in the neutron irradiated SiC layer of high-temperature gas reactor TRISO fuel is important to the understanding of various aspects of fuel performance that presently are not well understood. Recently, advanced characterization techniques have been used to examine fuel particles from the Idaho National Laboratory’s AGR-1 experiment. Nano-sized Ag and Pd precipitates were previously identified in grain boundaries and triple points in the SiC layer of irradiated TRISO nuclear fuel. Continuation of this initial research is reported in this paper and consists of the characterization of a relatively large number of nano-sized precipitates in three areas of the SiC layer of a single irradiated TRISO nuclear fuel particle using standardless EDS analysis on focused ion beam-prepared transmission electron microscopy samples. Composition and distribution analyses of these precipitates, which were located on grain boundaries, triple junctions and intragranular precipitates, revealed low levels, generally <10 atomic %, of palladium, silver and/or uranium with palladium being the most common element found. Palladium by itself, or associated with either silver or uranium, was found throughout the SiC layer. A small number of precipitates on grain boundaries and triple junctions were found to contain only silver or silver in association with palladium while uranium was always associated with palladium but never found by itself or in association with silver. Intergranular precipitates containing uranium were found to have migrated ~23 μm along a radial direction through the 35 μm thick SiC coating during the AGR-1 experiment while silver-containing intergranular precipitates were found at depths up to ~24 μm in the SiC layer. Also, Pd-rich, nano-precipitates (~10 nm in diameter), without evidence for the presence of either Ag or U, were revealed in intragranular regions throughout the SiC layer. Because not all

  4. Associations of Pd, U and Ag in the SiC layer of neutron-irradiated TRISO fuel

    NASA Astrophysics Data System (ADS)

    Lillo, T. M.; van Rooyen, I. J.

    2015-05-01

    Knowledge of the associations and composition of fission products in the neutron irradiated SiC layer of high-temperature gas reactor TRISO fuel is important to the understanding of various aspects of fuel performance that presently are not well understood. Recently, advanced characterization techniques have been used to examine fuel particles from the Idaho National Laboratory's AGR-1 experiment. Nano-sized Ag and Pd precipitates were previously identified in grain boundaries and triple points in the SiC layer of irradiated TRISO nuclear fuel. Continuation of this initial research is reported in this paper and consists of the characterization of a relatively large number of nano-sized precipitates in three areas of the SiC layer of a single irradiated TRISO nuclear fuel particle using standardless EDS analysis on focused ion beam-prepared transmission electron microscopy samples. Composition and distribution analyses of these precipitates, which were located on grain boundaries, triple junctions and intragranular precipitates, revealed low levels, generally <10 atomic %, of palladium, silver and/or uranium with palladium being the most common element found. Palladium by itself, or associated with either silver or uranium, was found throughout the SiC layer. A small number of precipitates on grain boundaries and triple junctions were found to contain only silver or silver in association with palladium while uranium was always associated with palladium but never found by itself or in association with silver. Intergranular precipitates containing uranium were found to have migrated ∼23 μm along a radial direction through the 35 μm thick SiC coating during the AGR-1 experiment while silver-containing intergranular precipitates were found at depths up to ∼24 μm in the SiC layer. Also, Pd-rich, nano-precipitates (∼10 nm in diameter), without evidence for the presence of either Ag or U, were revealed in intragranular regions throughout the SiC layer. Because not

  5. Particle swarm optimization of the stable structure of tetrahexahedral Pt-based bimetallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Tun-Dong; Fan, Tian-E.; Shao, Gui-Fang; Zheng, Ji-Wen; Wen, Yu-Hua

    2014-08-01

    Bimetallic nanoparticles, enclosed by high-index facets, have great catalytic activity and selectivity owing to the synergy effects of high-index facets and the electronic structures of alloy. In this paper, a discrete particle swarm optimization algorithm was employed to systematically investigate the structural stability and features of tetrahexahedral Pt-based bimetallic nanoparticles with high-index facets. Different Pt/Ag, Pt/Cu, Pt/Pd atom ratios and particle sizes were considered in this work. The simulation results reveal that these alloy nanoparticles exhibit considerably different structural characteristics. Pt-Ag nanoparticles tend to form Pt-Ag core-shell structure. Pt-Cu nanoparticles are preferred to take multi-shell structure with Cu on the outer surface while Pt-Pd nanoparticles present a mixing structure in the interior and Pd-dominated surface. Atomic distribution and bonding characteristics were applied to further characterize the structural features of Pt-based nanoparticles. This study provides an important insight into the structural stability and features of Pt-based nanoparticles with different alloys.

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

    DOE PAGESBeta

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

    2016-02-16

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-03-01

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

  10. Semiempirical calculation of radiative constants in the spectra of nickel-like ions Kr IX, Sr XI, Y XII, Ru XVII, Pd XIX, and Ag XX

    NASA Astrophysics Data System (ADS)

    Loginov, A. V.

    2015-03-01

    The probabilities of the electric-dipole transitions 3 d 94 p, 3 d 94 f-3 d 10, 3 d 94 s, and 3 d 94 d in the spectra of nickel-like ions Kr IX, Sr XI, Y XII, Ru XVII, Pd XIX, and Ag XX are calculated semiempirically with the use of published energy levels.

  11. Hydrogen FBG sensor using Pd/Ag film with application in propulsion system fuel tank model of aerospace vehicle

    NASA Astrophysics Data System (ADS)

    Saad, Said; Hassine, Lotfi; Elfahem, Wassim

    2014-09-01

    The high efficiency hydrogen fiber Bragg grating (FBG) sensor is presented. The sensitive film was a new alliance of palladium-silver (Pd-Ag). In addition, the titanium (Ti) layer was used as the adhesive layer. The presented sensor showed the resolution of more than 60 pm/1% H2, and a fast response time of 4 s-5 s was guaranteed in the 0.1% H2-4% H2 range. Moreover, the life time of the sensor was investigated. The obtained results showed that the sensor had an enhanced life time. Furthermore, the sensor was applied in the propulsion system fuel tank model of the aerospace vehicle. The obtained results indicated that it is a prevention system against the disaster aerospace due to hydrogen leakage.

  12. Synthesis of Ag or Pt nanoparticle-deposited TiO2 nanorods for the highly efficient photoreduction of CO2 to CH4

    NASA Astrophysics Data System (ADS)

    Wang, Qingli; Dong, Peimei; Huang, Zhengfeng; Zhang, Xiwen

    2015-10-01

    Ag or Pt-deposited TiO2 nanocomposites were prepared by a simple method, in which oriented TiO2 nanorods were synthesized by a hydrothermal method and a noble metal (Ag or Pt) was deposited on TiO2 by photocatalytic reduction under UV irradiation. The oriented TiO2 nanorods with Ag or Pt nanoparticles (<20 nm) exhibited high CO2 photoreduction efficiency, with CH4 yield rates up to 16.0 ppm/g h and 10.8 ppm/g h, respectively, considerably higher than that of the pure TiO2 nanorods (4.2 ppm/g h). The improvement in the CH4 yield was attributed to the formation of a Schottky barrier and surface plasmon resonance.

  13. Quadratic scaling of intrinsic Gilbert damping with spin-orbital coupling in L10 FePdPt films: experiments and Ab initio calculations.

    PubMed

    He, P; Ma, X; Zhang, J W; Zhao, H B; Lüpke, G; Shi, Z; Zhou, S M

    2013-02-15

    The dependence of the intrinsic Gilbert damping parameter α(0) on the spin-orbital coupling strength ξ is investigated in L1(0) ordered FePd(1-x) Pt(x) films by time-resolved magneto-optical Kerr effect measurements and spin-dependent ab initio calculations. Continuous tuning of α(0) over more than one order of magnitude is realized by changing the Pt/Pd concentration ratio showing that α(0) is proportional to ξ(2) as changes of other leading parameters are found to be negligible. The perpendicular magnetic anisotropy is shown to have a similar variation trend with x. The present results may facilitate the design and fabrication of new magnetic alloys with large perpendicular magnetic anisotropy and tailored damping properties. PMID:25166400

  14. New sterically-hindered o-quinones annelated with metal-dithiolates: regiospecificity in oxidative addition reactions of a bifacial ligand to the Pd and Pt complexes.

    PubMed

    Martyanov, K A; Cherkasov, V K; Abakumov, G A; Samsonov, M A; Khrizanforova, V V; Budnikova, Y H; Kuropatov, V A

    2016-04-25

    An unusual reactivity of sterically hindered o-quinones with an annelated dithiete ring towards coordination at a dithiolene site has been discovered. New Pd and Pt dithiolate complexes have been synthesized. The reaction proceeds regioselectively, and the quinone site of the parent ligand is not affected even while using an excess of the metal complex. Both Pt and Pd complexes display a square planar surrounding for the metal ion and have very similar NMR, IR and UV/Vis spectra. Surprisingly, being coordinated at the dithiolene site to the metal, the ligand exhibits activity like an o-quinone, it could be reduced with different metals resulting in the corresponding o-semiquinonates which were confirmed by EPR spectroscopy. It was shown that an unpaired electron exhibits HFC with the phosphorus nuclei of phosphine ligands coordinated to the metal ions at the dithiolene site of the molecule. PMID:27040038

  15. Synthesis of superparamagnetic carbon nanotubes immobilized Pt and Pd pincer complexes: highly active and selective catalysts towards cyclohexane oxidation with dioxygen.

    PubMed

    Machado, Kelly; Mishra, Jaya; Suzuki, Shinzo; Mishra, Gopal S

    2014-12-14

    Single-walled carbon nanotubes (SWNTs) with Ni/Co have been prepared using an arc discharge technique and Ni/Co-carbon composite rods in an inert atmosphere and were surface modified using 3-aminophenyl trimethoxysilane. These NH2-functionalized magnetic carbon nanotubes have been used as a novel support for Pd((II)) and Pt((II)) pincer complexes immobilized as magnetic nano-catalysts. The morphology of the support and the catalysts have been characterized by IR, EPR, SEM, TGA, TEM, XRD, AAS and EDS analysis. These magnetic nano-catalysts have been tested on the industrially important cyclohexane (Cy-hx) oxidation with O2 and significantly high TONs of 1678 to 1946 were achieved under solvent free and relatively mild conditions. The SWNTs/Pd catalyst provided the best conversion, 22.7%, but the SWNTs/Pt system also provided a good conversion of 20.7%. PMID:25340475

  16. Magneto-optical Kerr effect in L1{sub 0} FePdPt ternary alloys: Experiments and first-principles calculations

    SciTech Connect

    Ma, L.; Shi, Z.; Zhou, S. M. E-mail: shiming@tongji.edu.cn; Hu, J.; Costa, M.; Wu, R. Q. E-mail: shiming@tongji.edu.cn; Li, J.; Xu, X. G.; Jiang, Y.; Guo, G. Y.

    2014-05-14

    We have studied the magneto-optical Kerr effect (MOKE) of L1{sub 0} Fe{sub 0.5}(Pd{sub 1−x}Pt{sub x}){sub 0.5} alloy films with both experiments and first-principles calculations. In the visible region, negative Kerr rotation and ellipticity peaks are, respectively, observed in the regions of 1.5–2.0 eV and 1.7–2.6 eV. These peaks are shifted towards higher energies, and their magnitudes are enhanced for larger x. The MOKE evolution is mainly ascribed to the anomalous Hall conductivity contributed by the spin-down d{sub ↓,x{sup 2}−y{sup 2}} bands from Pd and Pt. We established a close correlation among the MOKE spectra, the spin orbit coupling strength, and the band feature for this prototypical system.

  17. Synthesis and electrocatalytic effect of Ag@Pt core-shell nanoparticles supported on reduced graphene oxide for sensitive and simple label-free electrochemical aptasensor.

    PubMed

    Mazloum-Ardakani, Mohammad; Hosseinzadeh, Laleh; Taleat, Zahra

    2015-12-15

    Bimetallic Ag@Pt core-shell nanoparticles supported on reduced graphene oxide nanosheets (Ag@Pt-GRs) was synthesized and used as novel desirable sensor platform and electrocatalyst for catechol as probe in aptasensor. Gold screen-printed electrodes modified with Ag@Pt-GRs and applied to advance enzyme-free and label-free electrochemical aptasensor for detection of protein biomarker tumor necrosis factor-alpha (TNF-α). The morphology of the Ag@Pt-GRs could be characterized by transmission electron microscopy, X-ray diffraction and UV-vis spectra. The results showed that these nanocomposite exhibited attractive electrocatalytic activity and also yielded large surface area, which improve the amount of immobilized TNF-α aptamer. Due to the excellent electrocatalytic activity of Ag@Pt-GRs towards the oxidation of catechol, determination of TNF-α antigen was based on its obstruction to the electrocatalytic oxidation of catechol by Ag@Pt-GRs after binding to the surface of electrode through interaction with the aptamer. The calibration curve was obtained by differential pulse voltammetry and square wave voltammetry. Under optimum conditions, the results demonstrated that this electrochemical aptasensor possessed a dynamic range from 0.0 pg/mL to 60 pg/mL with a low detection limit of 2.07 pg/mL for TNF-α. The analytical usefulness of the aptasensor was finally demonstrated analyzing serum samples. The simple fabrication method, high sensitivity, specificity, good reproducibility and stability as well as acceptable accuracy for TNF-α detection in human serum samples are the main advantages of this aptasensor, which might have broad applications in protein diagnostics and bioassay. PMID:26094037

  18. EuTZn (T=Pd, Pt, Au) with TiNiSi-type structure-Magnetic properties and {sup 151}Eu Moessbauer spectroscopy

    SciTech Connect

    Mishra, Trinath; Hermes, Wilfried; Harmening, Thomas; Eul, Matthias; Poettgen, Rainer

    2009-09-15

    The europium compounds EuTZn (T=Pd, Pt, Au) were synthesized from the elements in sealed tantalum tubes in an induction furnace. These intermetallics crystallize with the orthorhombic TiNiSi-type structure, space group Pnma. The structures were investigated by X-ray diffraction on powders and single crystals: a=732.3(2), b=448.5(2), c=787.7(2) pm, R{sub 1}/wR{sub 2}=0.0400/0.0594, 565 F{sup 2} values for EuPdZn, a=727.8(3), b=443.7(1), c=781.7(3) pm, R{sub 1}/wR{sub 2}=0.0605/0.0866, 573 F{sup 2} values for EuPtZn, and a=747.4(2), b=465.8(2), c=789.1(4) pm, R{sub 1}/wR{sub 2}=0.0351/0.0590, 658 F{sup 2} values for EuAuZn, with 20 variables per refinement. Together the T and zinc atoms build up three-dimensional [TZn] networks with short T-Zn distances. The EuTZn compounds show Curie-Weiss behavior in the temperature range from 75 to 300 K with mu{sub eff}=7.97(1), 7.70(1), and 7.94(1) mu{sub B}/Eu atom and theta{sub P}=18.6(1), 34.9(1), and 55.5(1) K for T=Pd, Pt, and Au, respectively, indicating divalent europium. Antiferromagntic ordering was detected at 15.1(3) K for EuPdZn and canted ferromagnetic ordering at 21.2(3) and 51.1(3) K for EuPtZn and EuAuZn. {sup 151}Eu Moessbauer spectroscopic measurements confirm the divalent nature of the europium atoms by isomer shift values ranging from -8.22(8) (EuPtZn) to -9.23(2) mm/s (EuAuZn). At 4.2 K full magnetic hyperfine field splitting is observed in all three compounds due to magnetic ordering of the europium magnetic moments. - Graphical abstract: Europium coordination in EuPdZn, EuPtZn, and EuAuZn.

  19. An integrated sensing system for detection of cholesterol based on TiO₂-graphene-Pt-Pd hybrid nanocomposites.

    PubMed

    Cao, Shurui; Zhang, Lei; Chai, Yaqin; Yuan, Ruo

    2013-04-15

    In this article, we used the TiO₂-graphene-Pt-Pd hybrid nanocomposites (TGPHs) as an enhanced element of the integrated sensing platform for increasing the surface area as well as improving the electronic transmission rate. Subsequently, Au nanoparticles (AuNPS) and cholesterol oxidase (ChOx) were successively self-assembled to TGPHs with high load amount and superior biological activity. The morphology of TGPHs and stepwise fabrication processes were characterized with cyclic voltammetry (CV), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Based on the efficiently catalytic ability of TGPHs and AuNPS, the fabricated biosensor exhibited wide linear ranges of responses to cholesterol in the concentration ranges of 5.0×10⁻⁸-5.9×10⁻⁴ M, the limit of detection was 0.017 μM (S/N=3). The response time was less than 7 s and the Michaelis-Menten constant (K(m)(app)) was found as 0.21 mM. The fabricated biosensor was further tested using real food samples egg, meat, margarine and fish oil, showing that the biosensor has the potential to be used as a facile cholesterol detection tool in food and supplement quality control. PMID:23247336

  20. Adsorption of thiophene on Pt, Pd, Au, and Rh(100) surfaces with the role of the van der Waals' interaction

    NASA Astrophysics Data System (ADS)

    Malone, Walter; Matos, Jeronimo; Kara, Abdelkader

    We explore the adsorption of thiophene (C4H4S) on Pt(100), Au(100), Pd(100), and Rh(100) surfaces using density functional theory with and without self-consistent van der Waals interactions (vdWs). The six functionals we use are PBE, optB86b-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, and rPW86-vdW2. We examine a variety of adsorption sites with the molecule's plane both parallel and perpendicular to the surface. In the case of parallel adsorption the highest binding energy occurs when the molecule is centered over a hollow site with the sulfur atom near an atop site. The highest adsorption energy for perpendicular configurations is achieved when the sulfur atom lies over a bridge site and the carbon atoms near hollow sites. We find that for thiophene on the coinage metals the vdW functionals predict higher adsorption energies than those predicted by the PBE functional. On the other hand, for thiophene on the reactive transition metal substrates only optB86b-vdW, optB88-vdW, and optPBE-vdW result in an enhancement in the adsorption energy over the PBE value. We also explore some of the electronic properties of the system including charge transfer and change in the work function. Our results indicate that adsorption characteristics depends heavily on the functional used and geometry.

  1. Schottky or Ohmic metal-semiconductor contact: influence on photocatalytic efficiency of Ag/ZnO and Pt/ZnO model systems.

    PubMed

    Yan, Fengpo; Wang, Yonghao; Zhang, Jiye; Lin, Zhang; Zheng, Jinsheng; Huang, Feng

    2014-01-01

    The relationship between the contact type in metal-semiconductor junctions and their photocatalytic efficiencies is investigated. Two metal-semiconductor junctions, silver on zinc oxide (Ag/ZnO) and platinum on zinc oxide (Pt/ZnO) serve as model system for Ohmic and Schottky metal-semiconductor contact, respectively. Ag/ZnO, with Ohmic contact, exhibits a higher photocatalytic efficiency than Pt/ZnO, with Schottky contact. The direction of electric fields within the semiconductor is found to play a crucial role in the separation of photogenerated charges, and thus strongly influences the photocatalytic efficiency. PMID:24458735

  2. Preparation of well-defined surfaces at atmospheric pressure: Studies of structural transformations of I, Ag-Adlattices on Pt(111) by leed and electrochemistry

    NASA Astrophysics Data System (ADS)

    Wieckowski, Andrzej; Schardt, Bruce C.; Rosasco, Stephen D.; Stickney, John L.; Hubbard, Arthur T.

    1984-10-01

    Pt(111) surfaces disordered by ion-bombardment or electrochemical oxidation were converted to well-defined, ordered states by annealing in iodine vapor at atmospheric pressure. A structure not obtainable in vacuum was formed, Pt(111)(3 3 × 9 3)R30°-I , containing 0.62 I atoms per surfa ce Pt atom in a slightly distorted hexagonal array. The I-I interatomic distances in this structure, 0.33 and 0.36 nm, were less than the Van der Waals distance, 0.43 nm. Gentle heating of this structure under pure Ar yielded I 2 molecules, I atoms and a series of structures: Pt(111)(3 3 × 9 3)R30°-I ?( 3 × 3)R30°-I ?Pt(111) (clean surface). The Pt(111)( 7 × 7 )R19.1°-I adlattice proved to be identifiable from its distinctive electrochemical behavior in electrodeposition of Ag from aqueous solutions of AgClO 4, which consists of three prominent structural transitions. Kinematic calculations of the directions and qualitative intensities of the LEED beams at selected kinetic energies has led to proposed structures consisting of Ag atoms close-packed in registry with the three-fold sites of Pt but with I atoms substituted for Ag atoms at the ( 3 × 3)R30° positions. Phase boundaries caused by reversals of the two packing sites of the 3 unit mesh at intervals 17 Pt unit vectors divide the surface into hexagonal antiphase domains.

  3. Exohedral M-C60 and M2-C60 (M = Pt, Pd) systems as tunable-gap building blocks for nanoarchitecture and nanocatalysis

    NASA Astrophysics Data System (ADS)

    Özdamar, Burak; Boero, Mauro; Massobrio, Carlo; Felder-Flesch, Delphine; Le Roux, Sébastien

    2015-09-01

    Transition metal-fullerenes complexes with metal atoms bound on the external surface of C60 are promising building blocks for next-generation fuel cells and catalysts. Yet, at variance with endohedral M@C60, they have received a limited attention. By resorting to first principles simulations, we elucidate structural and electronic properties for the Pd-C60, Pt-C60, PtPd-C60, Pd2-C60, and Pt2-C60 complexes. The most stable structures feature the metal atom located above a high electron density site, namely, the π bond between two adjacent hexagons (π-66 bond). When two metal atoms are added, the most stable configuration is those in which metal atoms still stand on π-66 bonds but tends to clusterize. The electronic structure, rationalized in terms of localized Wannier functions, provides a clear picture of the underlying interactions responsible for the stability or instability of the complexes, showing a strict relationship between structure and electronic gap.

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

    PubMed

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

    2005-06-01

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

  5. Synthesis, crystal structure, and electronic properties of high-pressure PdF2-type oxides MO2 (M = Ru, Rh, Os, Ir, Pt).

    PubMed

    Shirako, Yuichi; Wang, Xia; Tsujimoto, Yoshihiro; Tanaka, Kie; Guo, Yanfeng; Matsushita, Yoshitaka; Nemoto, Yoshihiro; Katsuya, Yoshio; Shi, Youguo; Mori, Daisuke; Kojitani, Hiroshi; Yamaura, Kazunari; Inaguma, Yoshiyuki; Akaogi, Masaki

    2014-11-01

    The polycrystalline MO2's (HP-PdF2-type MO2, M = Rh, Os, Pt) with high-pressure PdF2 compounds were successfully synthesized under high-pressure conditions for the first time, to the best of our knowledge. The crystal structures and electromagnetic properties were studied. Previously unreported electronic properties of the polycrystalline HP-PdF2-type RuO2 and IrO2 were also studied. The refined structures clearly indicated that all compounds crystallized into the HP-PdF2-type structure, M(4+)O(2-)2, rather than the pyrite-type structure, M(n+)(O2)(n-) (n < 4). The MO2 compounds (M = Ru, Rh, Os, Ir) exhibited metallic conduction, while PtO2 was highly insulating, probably because of the fully occupied t2g band. Neither superconductivity nor a magnetic transition was detected down to a temperature of 2 K, unlike the case of 3d transition metal chalcogenide pyrites. PMID:25337807

  6. Effects of electron correlation, electron-phonon coupling, and spin-orbit coupling on the isovalent Pd-substituted superconductor SrPt3P

    NASA Astrophysics Data System (ADS)

    Hu, Kangkang; Gao, Bo; Ji, Qiucheng; Ma, Yonghui; Li, Wei; Xu, Xuguang; Zhang, Hui; Mu, Gang; Huang, Fuqiang; Cai, Chuanbing; Xie, Xiaoming; Jiang, Mianheng

    2016-06-01

    We present a systematical study on the roles of interactions among electron correlation, electron-phonon coupling, and spin-orbit coupling in the isovalent Pd-substituted superconductor SrPt3P . By using the solid state reaction method, the Pd element with the 4 d orbital was successfully substituted in the strong spin-orbit coupling superconductors Sr (Pt1-xPdx) 3P . As increasing the isovalent Pd concentrations without introducing any extra electron/hole carriers, the superconducting transition temperature Tc decreases monotonously. In addition, combining the data of resistivity and specific heat, as well as electronic band structure calculations, we found that the electron correlation is enhanced while the electron-phonon coupling and the spin-orbit coupling are suppressed by Pd substitution. Our results may provide significant insights in the natures of the interplay among the electron correlation, electron-phonon coupling, and spin-orbit coupling in superconductivity, and may also pave a route for understanding the mechanism of superconductivity in heavily 5 d -based superconductors.

  7. Spectroscopic, thermal characterization and cytotoxic activity of bi-, tri- and tetra-nuclear Pd(II) and Pt(II) complexes with diSchiff base ligands

    NASA Astrophysics Data System (ADS)

    Hegazy, Wael Hussein

    2014-10-01

    In this paper; new di-, tri-, and tetra-nuclear Pd(II) and Pt(II) complexes of N,N‧-bis(3,4-dihydroxybenzylidene)ethan-1,2-diamine (EDH4), N,N‧-bis(3,4-dihydroxy-benzylidene)-benzene-1,2-diamine (PDH4) and N,N‧-bis-(3,4-dihydroxybenzylidene)-4,5-dimethyl-1,2-diamine (MPDH4) ligands were synthesized by two different methods. The first method involve the synthesis of the three ligands from condensation reaction of 3,4-dihydroxybenzaldehyde (L‧H2) with ethylenediamine (en), o-phenylenediamine (o-PD), or 4,5-dimethyl-1,2-phenylendiamine (DMPD) in a mole ratio of 2:1 followed by the reaction of the resulting Schiff bases ligands with Pd(II) or Pt(II) ions in the presence of 2,2‧-dipyridyl (L) to form the di- and tri-nuclear metal complexes. The second method involve the condensation of the Pd complex LPd(II)L‧, (L = 2,2‧-dipyridyl, L‧ = 4-formylbenzene-1,2-bis(olate)) with en, o-PD, or DMPD in a mole ratio of 2:1, respectively, followed by reaction with PdCl2 to form di-, tri-, and tetra-nuclear palladium(II) complexes, respectively. Structures of ligands and metal complexes are characterized by physical properties, FT-IR spectra and nuclear magnetic resonance. The geometries of metal complexes are suggested according to elemental analysis, electronic absorption spectra, thermal analysis, atomic absorption, magnetic susceptibility and molar conductance. Cytotoxic activity against lung large cell carcinoma (H460), prostate carcinoma (DU145), breast adenocarcinoma (MCF-7), amelanotic melanoma (M-14), colon adenocarcinoma (HT-29), and chronic myelogenous leukemia (K562) is also reported.

  8. Ultrasonic-electrodeposition of PtPd alloy nanoparticles on ionic liquid-functionalized graphene paper: towards a flexible and versatile nanohybrid electrode

    NASA Astrophysics Data System (ADS)

    Sun, Yimin; Zheng, Huaming; Wang, Chenxu; Yang, Mengmeng; Zhou, Aijun; Duan, Hongwei

    2016-01-01

    Here we fabricate a new type of flexible and versatile nanohybrid paper electrode by ultrasonic-electrodeposition of PtPd alloy nanoparticles on freestanding ionic liquid (IL)-functionalized graphene paper, and explore its multifunctional applications in electrochemical catalysis and sensing systems. The graphene-based paper materials demonstrate intrinsic flexibility, exceptional mechanical strength and high electrical conductivity, and therefore can serve as an ideal freestanding flexible electrode for electrochemical devices. Furthermore, the functionalization of graphene with IL (i.e., 1-butyl-3-methylimidazolium tetrafluoroborate) not only increases the electroactive surface area of a graphene-based nanohybrid paper electrode, but also improves the adhesion and dispersion of metal nanoparticles on the paper surface. These unique attributes, combined with the merits of an ultrasonic-electrodeposition method, lead to the formation of PtPd alloy nanoparticles on IL-graphene paper with high loading, uniform distribution, controlled morphology and favourable size. Consequently, the resultant nanohybrid paper electrode exhibits remarkable catalytic activity as well as excellent cycle stability and improved anti-poisoning ability towards electrooxidation of fuel molecules such as methanol and ethanol. Furthermore, for nonenzymatic electrochemical sensing of some specific biomarkers such as glucose and reactive oxygen species, the nanohybrid paper electrode shows high selectivity, sensitivity and biocompatibility in these bio-catalytic processes, and can be used for real-time tracking hydrogen peroxide secretion by living human cells. All these features demonstrate its promising application as a versatile nanohybrid electrode material in flexible and lightweight electrochemical energy conversion and biosensing systems such as bendable on-chip power sources, wearable/implantable detectors and in vivo micro-biosensors.Here we fabricate a new type of flexible and

  9. Facile fabrication of Pt-Ag bimetallic nanoparticles decorated reduced graphene oxide for highly sensitive non-enzymatic hydrogen peroxide sensing.

    PubMed

    Zhang, Cong; Zhang, Yanyan; Du, Xin; Chen, Yuan; Dong, Wenhao; Han, Bingkai; Chen, Qiang

    2016-10-01

    A new electrocatalyst, Pt-Ag bimetallic nanoparticles decorated reduced graphene oxide nanocomposite, was successfully synthesized by a facile, eco-friendly and controllable route. The morphological characterization of RGO/Pt-Ag NPs nanocomposite was examined by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX) analyzer, X-ray diffraction (XRD) spectrum, and Fourier transform infrared spectrum (FT-IR), respectively. And then, the RGO/Pt-Ag NPs nanocomposite was immobilized on the surface of glassy carbon (GC) electrode to fabricate a novel and highly sensitive non-enzymatic hydrogen peroxide sensor. The electrochemical behaviors of the prepared sensor were investigated by cyclic voltammetry and chronoamperometry. The sensor showed excellent performance toward H2O2 with sensitivity as high as 699.6 μA mM(-1)cm(-2) and 402.7 μA mM(-1)cm(-2), wide linear range of 0.005-1.5mM and 1.5-7mM, and low detection limit of 0.04μM (S/N=3). Moreover, the prepared hydrogen peroxide sensor was applied to in real samples with satisfactory results. These excellent results indicate that the prepared RGO/Pt-Ag NPs nanocomposite has broad application prospect in the field of sensors. PMID:27474309

  10. Ag/GeSx/Pt-based complementary resistive switches for hybrid CMOS/Nanoelectronic logic and memory architectures

    PubMed Central

    van den Hurk, Jan; Havel, Viktor; Linn, Eike; Waser, Rainer; Valov, Ilia

    2013-01-01

    Complementary resistive switches based on two anti-serially connected Ag/GeSx/Pt devices were studied. The main focus was placed on the pulse mode properties as typically required in memory and logic applications. A self-designed measurement setup was applied to access each CRS part-cell individually. Our findings reveal the existence of two distinct read voltage regimes enabling both spike read as well as level read approaches. Furthermore, we experimentally verified the theoretically predicted kinetic properties in terms of pulse height vs. switching time relationship. The results obtained by this alternative approach allow a significant improvement of the basic understanding of the interplay between the two part-cells in a complementary resistive switch configuration. Furthermore, from these observations we can deduce a simplified write voltage scheme which is applicable for the considered type of memory cell. PMID:24091355

  11. Energy loss of slow Ne ions in Pt and Ag from TOF-MEIS and Monte-Carlo simulations

    NASA Astrophysics Data System (ADS)

    Naqvi, S. R.; Possnert, G.; Primetzhofer, D.

    2016-03-01

    Time-Of-Flight Medium Energy Ion Scattering (TOF-MEIS) experiments were performed to investigate the different energy loss mechanisms for slow Ne ions (a few keV/nucleon) in polycrystalline thin films of Ag and Pt deposited on Si. To disentangle electronic (Se) and nuclear (Sn) contributions to the stopping power, Monte-Carlo (MC) simulations using the TRBS (TRim for BackScattering) code were conducted. The plateau-width of the experimental signal recorded in backscattering geometry was analyzed in order to extract additional information on the effective nuclear stopping. Electronic stopping powers were found to show the expected velocity dependence while the contribution from nuclear stopping was found low. The implications for experiments performed to study energy loss or related parameters are discussed.

  12. Generation of intense and cold beam of Pt-Ag bi-element cluster ions having single-composition

    NASA Astrophysics Data System (ADS)

    Yasumatsu, H.

    2011-07-01

    An intense beam of bi-element Pt-Ag cluster ions with a single atomic-composition has been gained toward development of new-functional materials of the clusters fixed on a solid surface. Mass production of the bi-element cluster ions has been achieved by operating dual magnetron-sputtering devices independently in a gas aggregation cell, and the ions having a single composition are filtered out by passing through a quadrupole mass filter. The kinetic energies of the cluster ions have been reduced by collision with cold helium in order for low-energy cluster-impact deposition of the clusters on the surface. The cooling process was examined further by means of molecular-dynamics simulation.

  13. 15N NMR coordination shifts in Pd(II), Pt(II), Au(III), Co(III), Rh(III), Ir(III), Pd(IV), and Pt(IV) complexes with pyridine, 2,2'-bipyridine, 1,10-phenanthroline, quinoline, isoquinoline, 2,2'-biquinoline, 2,2':6', 2'-terpyridine and their alkyl or aryl derivatives.

    PubMed

    Pazderski, Leszek

    2008-01-01

    The 15N NMR data for 105 complexes of Pd(II), Pt(II), Au(III), Co(III), Rh(III), Ir(III), Pd(IV), and Pt(IV) complexes with simple azines such as pyridine, 2,2'-bipyridine, 1,10-phenanthroline, quinoline, isoquinoline, 2,2'-biquinoline, 2,2':6', 2''-terpyridine and their alkyl or aryl derivatives have been reviewed. The 15N NMR coordination shifts, i.e. the differences between the 15N chemical shifts of the same nitrogen in the molecules of the complex and the ligand (Delta(15N) (coord) = delta(15N) (compl)--delta(15N) (lig)), have been related to some structural features of the reviewed coordination compounds, like the type of the central ion and the character of auxiliary ligands (mainly in trans position). These Delta(15N) (coord) parameters are negative, their absolute magnitudes (ca 30-150 ppm) generally increasing in the metal order Au(III) < Pd(II) < Pt(II) and Rh(III) < Co(III) < Pt(IV) < Ir(III), as well as with the enhanced trans influence of the other donor atoms (H, C < Cl < N). PMID:18855335

  14. Spin polarization and additional magneto-optical activity of nonmagnetic layers in Fe/Ag CMF

    NASA Astrophysics Data System (ADS)

    Xu, Y. B.; Zhai, H. R.; Lu, M.; Jin, Q. Y.; Miao, Y. Z.

    1992-08-01

    The experimental magneto-optical Kerr rotation spectra of Fe/Ag compositionally modulated films reported by Katayama et al. are studied theoretically. It is found that the free electrons of Ag are spin polarized. The magnitude of the polarization is about 1% with a direction opposite to that of Fe. The polarized Ag also gives rise to an additional magneto-optical activity as in Pt and Pd.

  15. 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.

    PubMed

    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. PMID:26790717

  16. Total ionizing dose (TID) effects of γ ray radiation on switching behaviors of Ag/AlO x /Pt RRAM device

    PubMed Central

    2014-01-01

    The total ionizing dose (TID) effects of 60Co γ ray radiation on the resistive random access memory (RRAM) devices with the structure of Ag/AlO x /Pt were studied. The resistance in low resistance state (LRS), set voltage, and reset voltage are almost immune to radiation, whereas the initial resistance, resistance at high resistance state (HRS), and forming voltage were significantly impacted after radiation due to the radiation-induced holes. A novel hybrid filament model is proposed to explain the radiation effects, presuming that holes are co-operated with Ag ions to build filaments. In addition, the thermal coefficients of the resistivity in LRS can support this hybrid filament model. The Ag/AlO x /Pt RRAM devices exhibit radiation immunity to a TID up to 1 Mrad(Si) and are highly suitable for radiation-hard electronics applications. PMID:25246866

  17. Nanostructured, Gd-doped ceria promoted by Pt or Pd: investigation of the electronic and surface structures and relations to chemical properties.

    PubMed

    Borchert, Holger; Borchert, Yulia; Kaichev, Vasiliy V; Prosvirin, Igor P; Alikina, Galina M; Lukashevich, Anton I; Zaikovskii, Vladimir I; Moroz, Ella M; Paukshtis, Eugenii A; Bukhtiyarov, Valerii I; Sadykov, Vladislav A

    2005-11-01

    Nanostructured ceria doped with other rare earth elements is a good oxygen ion conductor, which gives rise to various catalytic applications such as the construction of membranes for syngas production by partial oxidation of methane. This article focuses on the Gd-doped cerium dioxides, which can be modified with Pt or Pd to enhance the reactivity of the lattice oxygen in interaction with methane. The aim of the work is the elucidation of correlations between the structural, electronic, and chemical properties of these nanomaterials. Detailed studies were performed for a series of samples with and without surface modification by noble metals using a complex combination of physicochemical methods: XRD, TEM, CH(4) TPR, XPS, SIMS, and FTIR spectroscopy of adsorbed CO. XPS and TPR data revealed that surface modification with noble metals enhances the reducibility of the doped ceria support, where the effect is more pronounced for Pd than for Pt. The formation of highly cationic Pd species due to strong metal support interactions provides a possible explanation for this behavior. Furthermore, the results obtained in the present work for the Gd-doped ceria system are compared to those obtained previously for the Pr-doped ceria system. PMID:16853596

  18. Clathrates with Me = Mg, Pd, Ni, Au, Ag, Cu, Zn, Al, Sn

    NASA Astrophysics Data System (ADS)

    Wunderlich, Wilfried; Amano, Mao; Matsumura, Yoshihito

    2014-06-01

    Clathrate materials of AlSi, CuSi or NiSi type consisting of abundant elements have a realistic chance of becoming useful thermoelectrics in the near future, because the rattling effect due to their crystal cage structure provides a large figure of merit ZT even in experiments measured under large temperature gradients. In the search for better thermoelectrics, new element combinations in the clathrate type I structure with cubic space group Pm3n were calculated using VASP ab initio software. Predictions of the Seebeck coefficient were made by checking the electronic band structure and density of states for a large variety of input data. For x values around 4 to 6 in the structural formula Ba8Me x Si46- x the substituents Cu, Au, and Ag are best for good thermoelectric behavior, which is discussed in this paper as a result of the low electron-phonon interaction parameter.

  19. [Study on the age-hardenable silver alloy (3 rd report). III. On the ageing process of dental Ag-Pd-Cu-Au alloy (author's transl)].

    PubMed

    Ota, M; Hisatsune, K; Yamane, M

    1975-05-01

    The precipitation hardening process of a dental silver base alloy, Ag-28 Pd-10 Cu-12 wt % Au, was studied by means of X-ray diffraction, hardness measurement and metallographic observations. After solution treatment at 900 degrees C for 30 min, specimens were subjected to anisothermal annealing at the rate of 1 degrees C/min. PdCu ordered phase and alpha2 solid solution (Ag rich phase) precipitated hetelogeneously at the grain boundaries and then grew up into each grain. Drastic increase in hardness was recognized with the spread of nodular region. Electron microscopic observation of these precipitates showed very fine lamellar structure. It is concluded that the age hardening of this alloy could be attributed to this grain boundary precipitation and the softening at the overaged stage to the second grain boundary reaction which produced very coarse lamellar structure. PMID:1058263

  20. Perpendicular magnetic tunnel junctions with a synthetic storage or reference layer: A new route towards Pt- and Pd-free junctions

    PubMed Central

    Cuchet, Léa; Rodmacq, Bernard; Auffret, Stéphane; Sousa, Ricardo C.; Prejbeanu, Ioan L.; Dieny, Bernard

    2016-01-01

    We report here the development of Pt and Pd-free perpendicular magnetic tunnel junctions (p-MTJ) for STT-MRAM applications. We start by studying a p-MTJ consisting of a bottom synthetic Co/Pt reference layer and a synthetic FeCoB/Ru/FeCoB storage layer covered with an MgO layer. We first investigate the evolution of RKKY coupling with Ru spacer thickness in such a storage layer. The coupling becomes antiferromagnetic above 0.5 nm and its strength decreases monotonously with increasing Ru thickness. This contrasts with the behavior of Co-based systems for which a maximum in interlayer coupling is generally observed around 0.8 nm. A thin Ta insertion below the Ru spacer considerably decreases the coupling energy, without basically changing its variation with Ru thickness. After optimization of the non-magnetic and magnetic layer thicknesses, it appears that such a FeCoB/Ru/FeCoB synthetic storage layer sandwiched between MgO barriers can be made stable enough to actually be used as hard reference layer in single or double magnetic tunnel junctions, the storage layer being now a single soft FeCoB layer. Finally, we realize Pt- or Pd-free robust perpendicular magnetic tunnel junctions, still keeping the advantage of a synthetic reference layer in terms of reduction of stray fields at small pillar sizes. PMID:26883933

  1. Perpendicular magnetic tunnel junctions with a synthetic storage or reference layer: A new route towards Pt- and Pd-free junctions.

    PubMed

    Cuchet, Léa; Rodmacq, Bernard; Auffret, Stéphane; Sousa, Ricardo C; Prejbeanu, Ioan L; Dieny, Bernard

    2016-01-01

    We report here the development of Pt and Pd-free perpendicular magnetic tunnel junctions (p-MTJ) for STT-MRAM applications. We start by studying a p-MTJ consisting of a bottom synthetic Co/Pt reference layer and a synthetic FeCoB/Ru/FeCoB storage layer covered with an MgO layer. We first investigate the evolution of RKKY coupling with Ru spacer thickness in such a storage layer. The coupling becomes antiferromagnetic above 0.5 nm and its strength decreases monotonously with increasing Ru thickness. This contrasts with the behavior of Co-based systems for which a maximum in interlayer coupling is generally observed around 0.8 nm. A thin Ta insertion below the Ru spacer considerably decreases the coupling energy, without basically changing its variation with Ru thickness. After optimization of the non-magnetic and magnetic layer thicknesses, it appears that such a FeCoB/Ru/FeCoB synthetic storage layer sandwiched between MgO barriers can be made stable enough to actually be used as hard reference layer in single or double magnetic tunnel junctions, the storage layer being now a single soft FeCoB layer. Finally, we realize Pt- or Pd-free robust perpendicular magnetic tunnel junctions, still keeping the advantage of a synthetic reference layer in terms of reduction of stray fields at small pillar sizes. PMID:26883933

  2. Perpendicular magnetic tunnel junctions with a synthetic storage or reference layer: A new route towards Pt- and Pd-free junctions

    NASA Astrophysics Data System (ADS)

    Cuchet, Léa; Rodmacq, Bernard; Auffret, Stéphane; Sousa, Ricardo C.; Prejbeanu, Ioan L.; Dieny, Bernard

    2016-02-01

    We report here the development of Pt and Pd-free perpendicular magnetic tunnel junctions (p-MTJ) for STT-MRAM applications. We start by studying a p-MTJ consisting of a bottom synthetic Co/Pt reference layer and a synthetic FeCoB/Ru/FeCoB storage layer covered with an MgO layer. We first investigate the evolution of RKKY coupling with Ru spacer thickness in such a storage layer. The coupling becomes antiferromagnetic above 0.5 nm and its strength decreases monotonously with increasing Ru thickness. This contrasts with the behavior of Co-based systems for which a maximum in interlayer coupling is generally observed around 0.8 nm. A thin Ta insertion below the Ru spacer considerably decreases the coupling energy, without basically changing its variation with Ru thickness. After optimization of the non-magnetic and magnetic layer thicknesses, it appears that such a FeCoB/Ru/FeCoB synthetic storage layer sandwiched between MgO barriers can be made stable enough to actually be used as hard reference layer in single or double magnetic tunnel junctions, the storage layer being now a single soft FeCoB layer. Finally, we realize Pt- or Pd-free robust perpendicular magnetic tunnel junctions, still keeping the advantage of a synthetic reference layer in terms of reduction of stray fields at small pillar sizes.

  3. Pd-Pt alloys nanowires as support-less electrocatalyst with high synergistic enhancement in efficiency for methanol oxidation in acidic medium.

    PubMed

    Rana, Moumita; Patil, Pramod K; Chhetri, Manjeet; Dileep, K; Datta, Ranjan; Gautam, Ujjal K

    2016-02-01

    In a facile approach, Pd73Pt27 alloy nanowires (NWs) with large aspect ratios were synthesized in high yield by using sacrificial templates. Unlike majority of processes, our synthesis was carried out in aqueous solution with no intermittent separating stages for the products, while maintaining the NW morphology up to ∼30% of Pt. Upon evaporation of their dispersion, the NWs transform into a stable porous membrane due to self-entanglement and can be directly lifted and employed for electrocatalytic applications without external catalyst supports. We show that the NW membranes exhibit efficient electrocatalytic performance for methanol oxidation reaction (MOR) with 10 times higher mass activity and 4.4 times higher specific activity in acidic media as compared to commercial Pt catalysts. The membrane electrocatalysts is robust and exhibited very good stability with retention of ∼70% mass-activity after 4000 potential cycles. Since Pd was found to be inert towards MOR in acidic medium, our investigation provides a direct estimate of synergistic enhancement of efficiency. Over 10 times increment of mass activity appears to be significantly higher than previous investigations in various other reaction media. PMID:26520816

  4. Quantitative description of short-range order and its influence on the electronic structure in Ag-Pd alloys.

    PubMed

    Hoffmann, M; Marmodoro, A; Ernst, A; Hergert, W; Dahl, J; Lång, J; Laukkanen, P; Punkkinen, M P J; Kokko, K

    2016-08-01

    We investigate the effect of short-range order (SRO) on the electronic structure in alloys from the theoretical point of view using density of states (DOS) data. In particular, the interaction between the atoms at different lattice sites is affected by chemical disorder, which in turn is reflected in the fine structure of the DOS and, hence, in the outcome of spectroscopic measurements. We aim at quantifying the degree of potential SRO with a proper parameter. The theoretical modeling is done with the Korringa-Kohn-Rostoker Green's function method. Therein, the extended multi-sublattice non-local coherent potential approximation is used to include SRO. As a model system, we use the binary solid solution Ag c Pd1-c at three representative concentrations c  =  0.25, 0.5 and 0.75. The degree of SRO is varied from local ordering to local segregation through an intermediate completely uncorrelated state. We observe some pronounced features, which change over the whole energy range of the valence bands as a function of SRO in the alloy. These spectral variations should be traceable in modern photoemission experiments. PMID:27269809

  5. Quantitative description of short-range order and its influence on the electronic structure in Ag-Pd alloys

    NASA Astrophysics Data System (ADS)

    Hoffmann, M.; Marmodoro, A.; Ernst, A.; Hergert, W.; Dahl, J.; Lång, J.; Laukkanen, P.; Punkkinen, M. P. J.; Kokko, K.

    2016-08-01

    We investigate the effect of short-range order (SRO) on the electronic structure in alloys from the theoretical point of view using density of states (DOS) data. In particular, the interaction between the atoms at different lattice sites is affected by chemical disorder, which in turn is reflected in the fine structure of the DOS and, hence, in the outcome of spectroscopic measurements. We aim at quantifying the degree of potential SRO with a proper parameter. The theoretical modeling is done with the Korringa–Kohn–Rostoker Green’s function method. Therein, the extended multi-sublattice non-local coherent potential approximation is used to include SRO. As a model system, we use the binary solid solution Ag c Pd1‑c at three representative concentrations c  =  0.25, 0.5 and 0.75. The degree of SRO is varied from local ordering to local segregation through an intermediate completely uncorrelated state. We observe some pronounced features, which change over the whole energy range of the valence bands as a function of SRO in the alloy. These spectral variations should be traceable in modern photoemission experiments.

  6. Novel Galvanic Nanostructures of Ag and Pd for Efficient Laser Desorption/Ionization of Low Molecular Weight Compounds

    NASA Astrophysics Data System (ADS)

    Silina, Yuliya E.; Meier, Florian; Nebolsin, Valeriy A.; Koch, Marcus; Volmer, Dietrich A.

    2014-05-01

    A simple approach for synthesis of palladium and silver nanostructures with readily adjustable morphologies was developed using galvanic electrochemical deposition, for application to surface-assisted laser desorption/ionization (SALDI) of small biological molecules. A range of fatty acids, triglycerides, carbohydrates, and antibiotics were investigated to assess the performance of the new materials. Intense analyte cations were generated from the galvanic surfaces upon UV laser irradiation such as potassium adducts for a film thickness <100 nm (originating from impurities of the electrolyte solution) and Pd and Ag cluster ions for films with a thickness >120 nm. Possible laser desorption/ionization mechanisms of these galvanic structures are discussed. The films exhibited self-organizing abilities and adjustable morphologies by changing electrochemical parameters. They did not require any stabilizing agents and were inexpensive and very easy to produce. SALDI analysis showed that the materials were stable under ambient conditions and analytical results with excellent measurement reproducibility and detection sensitivity similar to MALDI were obtained. Finally, we applied the galvanic surfaces to fast screening of natural oils with minimum sample preparation.

  7. Hardening by cooling rate control and post-firing heat treatment in Pd-Ag-Sn alloy for bonding porcelain.

    PubMed

    Yu, Young-Jun; Seol, Hyo-Joung; Cho, Mi-Hyang; Kim, Hyung-Il; Kwon, Yong Hoon

    2016-01-01

    The aim of this study was to determine the hardening effect by controlling the cooling rate during the porcelain firing process and performing an additional post-firing heat treatment in a Pd-Ag-Sn alloy. The most effective cooling rate for alloy hardening was determined by cooling the specimens at various cooling rates after oxidation treatment. A subsequent porcelain firing simulation followed by cooling at the selected cooling rate was performed. A post-firing heat treatment was then done at 600°C in a porcelain furnace. The hardening mechanism was characterized by a hardness test, X-ray diffraction, field emission scanning electron microscopy and energy dispersive X-ray spectroscopy. Alloy softening occurred during the porcelain firing process followed by cooling at a controlled cooling rate. A post-firing heat treatment allowed apparent precipitation hardening. It is advisable to perform a postfiring heat treatment at 600°C in a porcelain furnace by annealing metal substructure after porcelain fusing. PMID:27041022

  8. The Electronic and Optical Properties of X-Doped SrTiO3 (x = Rh, Pd, Ag): a First-Principles Calculations

    NASA Astrophysics Data System (ADS)

    Qiu, Bo; Yan, Xin-Guo; Huang, Wei-Qing; Huang, Gui-Fang; Jiao, Chao; Zhan, Si-Qi; Long, Jin-Ping; Yang, Zheng-Mei; Wan, Zhuo; Peng, P.

    2014-12-01

    The electronic and optical properties of X-doped (X = Rh, Pd, Ag) cubic SrTiO3 in perovskite structure are investigated using first-principles calculations. The strength of the Ti-O bonds near the substitutional X impurity is found to be weakened by the shorter X-O bonds. Three types of electronic characteristics due to X-doping are demonstrated. X-doping decreases the band gap of SrTiO3, extending the optical absorption edge to visible light. Although Pd-doped SrTiO3 has the greatest absorption in the visible light region, its photocatalytic activity is lower than that of Rh-doped SrTiO3, because the intermediate bands from the 4d orbitals of the Pd dopant act as recombination centers. The theoretical results coincide with the available experimental results.

  9. Granular L10 FePt:X (X = Ag, B, C, SiOx, TaOx) thin films for heat assisted magnetic recording

    NASA Astrophysics Data System (ADS)

    Granz, Steven D.; Barmak, Katayun; Kryder, Mark H.

    2013-03-01

    Ordered L10 FePt thin films are of interest as potential Heat Assisted Magnetic Recording media. In order to achieve the microstructure and magnetic properties to support recording at densities beyond 1 Tbit/in2, it is necessary to add segregants into the FePt films. In this work, the effects of a number of segregants, X, on the microstructure and magnetic properties of FePt:X (X = Ag, B, C, SiO x , TaO x ) thin films, deposited by RF sputtering with various volume content (0-50%), various in-situ heating temperatures (450-600 °C), various Ar pressures (10-40 mtorr) and various sputtering powers (25-200 W) onto 1'' Si substrates with a MgO texture (002) underlayer (20 nm), were investigated. It was observed that introducing segregants (B, C, SiO x , and TaO x ) into the FePt reduced ordering and grain size of the FePt:X thin films. Ag was found to offset the reduction of ordering in the FePt:X films. The B, SiO x and TaO x promoted columnar growth whereas C promoted a secondary nucleation layer but produced the least reduction of ordering. By varying the volume content of the segregants, the grain size of the FePt:X can be controllably reduced throughout the 2.5-10 nm range. It was found that TaO x produced the best exchange decoupling, thermal durability, grain isolation and hindered grain coalescence as compared with the films deposited with B, C or SiO x . With the FePt:C:Ag films sputtered at 450 °C, a perpendicular coercivity measured at room temperature as high as 25 kOe was achieved; whereas with B, SiO x , and TaO x , perpendicular coercivities as high as 11 kOe were obtained. These FePt:X thin films with small grain size, columnar microstructure and high coercivity are believed to be favorable for application in Heat Assisted Magnetic Recording. The role of surface energies of FePt and the segregant in columnar growth of FePt grains is discussed.

  10. Spatial variation of contaminant elements of roadside dust samples from Budapest (Hungary) and Seoul (Republic of Korea), including Pt, Pd and Ir.

    PubMed

    Sager, Manfred; Chon, Hyo-Taek; Marton, Laszlo

    2015-02-01

    Roadside dusts were studied to explain the spatial variation and present levels of contaminant elements including Pt, Pd and Ir in urban environment and around Budapest (Hungary) and Seoul (Republic of Korea). The samples were collected from six sites of high traffic volumes in Seoul metropolitan city and from two control sites within the suburbs of Seoul, for comparison. Similarly, road dust samples were obtained two times from traffic focal points in Budapest, from the large bridges across the River Danube, from Margitsziget (an island in the Danube in the northern part of Budapest, used for recreation) as well as from main roads (no highways) outside Budapest. The samples were analysed for contaminant elements by ICP-AES and for Pt, Pd and Ir by ICP-MS. The highest Pt, Pd and Ir levels in road dusts were found from major roads with high traffic volume, but correlations with other contaminant elements were low, however. This reflects automobile catalytic converter to be an important source. To interpret the obtained multi-element results in short, pollution index, contamination index and geo-accumulation index were calculated. Finally, the obtained data were compared with total concentrations encountered in dust samples from Madrid, Oslo, Tokyo and Muscat (Oman). Dust samples from Seoul reached top level concentrations for Cd-Zn-As-Co-Cr-Cu-Mo-Ni-Sn. Just Pb was rather low because unleaded gasoline was introduced as compulsory in 1993. Concentrations in Budapest dust samples were lower than from Seoul, except for Pb and Mg. Compared with Madrid as another continental site, Budapest was higher in Co-V-Zn. Dust from Oslo, which is not so large, contained more Mn-Na-Sr than dust from other towns, but less other metals. PMID:25108588

  11. Final report of APMP.T-S7: APMP regional comparison of Co-C eutectic melting point using Pt/Pd thermocouples

    NASA Astrophysics Data System (ADS)

    Kim, Y.-G.; Wei, Z.; Ogura, H.; Jahan, F.; Singh, Y. P.

    2016-01-01

    A regional supplementary comparison on the Co-C eutectic point (1324 °C in ITS-90) was carried out in APMP involving five NMIs: KRISS (Korea), NIM (China), NMIJ (Japan), NMIA (Australia) and NPLI (India). The comparison was done through a round robin style with two Pt/Pd thermocouples having greatly different thermoelectric inhomogeneity (± 0.0196 % and ± 0.132 % at 1324 °C), which were made by the pilot laboratory (KRISS). Both were calibrated twice, before and after the circulation by the pilot laboratory. As a reference value, the weighted mean was adopted since the Birge ration criterion was safely satisfied. The participants were asked to supply the temperature profile of the furnace used to realize the Co-C point in order to estimate the uncertainty due to thermoelectric inhomogeneity. Results from all laboratories were consistent with the reference value within the calculated uncertainties. Birge number of 0.2 to 0.3 and En number less than 0.5 were obtained, meaning that the comparison successfully demonstrated the use of Pt/Pd thermocouple to compare the calibration capabilities of participating laboratories at the melting temperature of Co-C eutectic point regardless of the amount of thermoelectric inhomogeneity. It was verified that the calibration uncertainty level of {(0.2 °C ~ 0.3 °C) + ucell} (k = 2) can be obtained at the Co-C eutectic melting point by means of Pt/Pd thermocouple having a small inhomogeneity of about 0.02 %. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCT, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

  12. Pt and Pd catalyzed oxidation of Li2O2 and DMSO during Li–O2 battery charging

    SciTech Connect

    Gittleson, Forrest S.; Ryu, Won-Hee; Schwab, Mark; Tong, Xiao; Taylor, André D.

    2016-01-01

    Rechargeable Li-O2 and Li-air batteries require electrode and electrolyte materials that synergistcally promote long-term cell operation. We investigate the role of noble metals Pt and Pd as catalysts for the Li-O2 oxidation process and their compatibility with a dimethyl sulfoxide (DMSO) based electrolyte. Lastly, we identify a basis for low potential Li2O2 evolution followed by oxidative decomposition of the electrolyte to form carbonate side products.

  13. Unusual Transport and Strongly Anisotropic Thermopower in PtCoO2 and PdCoO2

    SciTech Connect

    Ong, Khuong P.; Singh, David J.; Wu, Ping

    2010-04-28

    We show, using Boltzmann transport calculations and analysis of experimental data, that hexagonal PdCoO2 and PtCoO2 have a highly unusual metallic transport. The in-plane transport is typical of a very good metal, with high conductivity and low positive thermopower. The c-axis transport is completely different, with 2 orders of magnitude lower, but still coherent, conductivity and remarkably a very large negative thermopower. This large anisotropy of the thermopower provides an opportunity for investigating transport in a highly unusual regime using bulk materials.

  14. Scaling of submonolayer island sizes in Ag growth on stepped Pt surfaces

    NASA Astrophysics Data System (ADS)

    Ramadan, A.; Picaud, F.; Ramseyer, C.

    2010-09-01

    Simulations based on an atomic description of the growth mechanisms are used to interpret physical behavior of silver adatoms growth on stepped platinum surface. We study in details the influence of atom confinement during the growth process on vicinal Pt surfaces with different terrace widths. The behavior of the mean island density on terraces and steps and their size is analyzed in a general way as a function of the flux F, the diffusion coefficient D and the terrace width using Kinetic Monte-Carlo simulations. Specific scaling factors are found to describe the growth near the defects or on the terraces depending on the confinement.

  15. Effect of Cumulative Nanosecond Laser Pulses on the Plasma Emission Intensity and Surface Morphology of Pt- and Ag-Ion Deposited Silicon

    NASA Astrophysics Data System (ADS)

    Khurram, Siraj; Muhammad Zakria, Butt; Muhammad, Khaleeq-Urrahman; Muhammad Shahid, Rafique; Saima, Rafique; Fakhar-Un-Nisa

    2012-04-01

    In this work, the laser induced plasma plume characteristics and surface morphology of Pt- and Ag-ion deposited silicon were studied. The deposited silicon was exposed to cumulative laser pulses. The plasma plume images produced by each laser shot were captured through a computer controlled image capturing system and analyzed with image-J software. The integrated optical emission intensity of both samples showed an increasing trend with increasing pulses. Ag-ion deposited silicon showed higher optical emission intensity as compared to Pt-ion deposited silicon, suggesting that more damage occurred to the silicon by Ag ions, which was confirmed by SRIM/TRIM simulations. The surface morphologies of both samples were examined by optical microscope showing thermal, exfoliational and hydrodynamical sputtering processes along with the re-deposition of the material, debris and heat affected zones' formation. The crater of Pt-ion deposited silicon was deeper but had less lateral damage than Ag- ion deposited silicon. The novel results clearly indicated that the ion deposited silicon surface produced incubation centers, which led to more absorption of incident light resulting into a higher emission intensity from the plasma plume and deeper crater formation as compared to pure silicon. The approach can be effectively utilized in the laser induced breakdown spectroscopy technique, which endures poor limits of detection.

  16. Enhancement of order degree and perpendicular magnetic anisotropy of L10 ordered Fe(Pt,Pd) alloy film by introducing a thin MgO cap-layer

    NASA Astrophysics Data System (ADS)

    Noguchi, Youhei; Ohtake, Mitsuru; Futamoto, Masaaki; Kirino, Fumiyoshi; Inaba, Nobuyuki

    2016-07-01

    Fe50PtxPd50-x (at%, x=0-50) alloy films of 10 nm thickness with and without 2-nm-thick MgO cap-layers are prepared on MgO(001) single-crystal substrates by employing a two-step method consisting of low-temperature deposition at 200 °C followed by high-temperature annealing at 600 °C. The influences of MgO cap-layer on the structure and the magnetic properties are investigated. Fe50PtxPd50-x films epitaxially grow on the substrates at 200 °C. The Fe50Pd50 and the Fe50Pt12.5Pd37.5 films are respectively composed of (001) single-crystals with disordered fcc-based (A1) and bcc-based (A2) structures. The films with x>25 consist of mixtures of A1 and A2 crystals. The volume ratio of A2 to A1 crystal decreases with increasing the x value from 25 to 50. The in-plane and out-of-plane lattices are respectively expanded and shrunk due to accommodation of lattice mismatch between film and substrate. When the films are annealed at 600 °C, phase transformation to L10 ordered phase takes place. L10 phase transformation of Fe50PtxPd50-x film is promoted for a sample with MgO cap-layer and the order degree is higher than that without cap-layer. Furthermore, L10 ordering with the c-axis perpendicular to the substrate surface is enhanced for the film with cap-layer. The cap-layer is considered to be giving a tension stress to the magnetic film in lateral direction which promotes L10 ordering with the c-axis perpendicular to the substrate. Deposition of cap-layer is shown effective in achieving higher order degree and in enhancing perpendicular magnetic anisotropy with Fe(Pt,Pd) films.

  17. Direct functionalization of M-C (M = Pt(II), Pd(II)) bonds using environmentally benign oxidants, O2 and H2O2.

    PubMed

    Vedernikov, Andrei N

    2012-06-19

    Atom economy and the use of "green" reagents in organic oxidation, including oxidation of hydrocarbons, remain challenges for organic synthesis. Solutions to this problem would lead to a more sustainable economy because of improved access to energy resources such as natural gas. Although natural gas is still abundant, about a third of methane extracted in distant oil fields currently cannot be used as a chemical feedstock because of a dearth of economically and ecologically viable methodologies for partial methane oxidation. Two readily available "atom-economical" "green" oxidants are dioxygen and hydrogen peroxide, but few methodologies have utilized these oxidants effectively in selective organic transformations. Hydrocarbon oxidation and C-H functionalization reactions rely on Pd(II) and Pt(II) complexes. These reagents have practical advantages because they can tolerate moisture and atmospheric oxygen. But this tolerance for atmospheric oxygen also makes it challenging to develop novel organometallic palladium and platinum-catalyzed C-H oxidation reactions utilizing O(2) or H(2)O(2). This Account focuses on these challenges: the development of M-C bond (M = Pt(II), Pd(II)) functionalization and related selective hydrocarbon C-H oxidations with O(2) or H(2)O(2). Reactions discussed in this Account do not involve mediators, since the latter can impart low reaction selectivity and catalyst instability. As an efficient solution to the problem of direct M-C oxidation and functionalization with O(2) and H(2)O(2), this Account introduces the use of facially chelating semilabile ligands such as di(2-pyridyl)methanesulfonate and the hydrated form of di(2-pyridyl)ketone that enable selective and facile M(II)-C(sp(n)) bond functionalization with O(2) (M = Pt, n = 3; M = Pd, n = 3 (benzylic)) or H(2)O(2) (M = Pd, n = 2). The reactions proceed efficiently in protic solvents such as water, methanol, or acetic acid. With the exception of benzylic Pd(II) complexes, the

  18. Ce{sub 2}PdIn{sub 8}, Ce{sub 3}PdIn{sub 11} and Ce{sub 5}Pd{sub 2}In{sub 19}—members of homological series based on AuCu{sub 3}- and PtHg{sub 2}-type structural units

    SciTech Connect

    Tursina, A.; Nesterenko, S.; Seropegin, Y.; Noël, H.; Kaczorowski, D.

    2013-04-15

    Crystal structures of three members of a unique homological series with the general formula Ce{sub m}Pd{sub n}In{sub 3m+2n} based on the AuCu{sub 3} and PtHg{sub 2} structure types were studied by single-crystal X-ray diffraction. The compounds crystallize with space group P4/mmm (Z=1) and the lattice parameters: a=4.6900(9) Å, c=12.185(6) Å for Ce{sub 2}PdIn{sub 8}, a=4.6846(8) Å, c=16.846(8) Å for Ce{sub 3}PdIn{sub 11}, and a=4.70120(10) Å, c=29.1359(4) Å for Ce{sub 5}Pd{sub 2}In{sub 19}. The crystal structures of Ce{sub 3}PdIn{sub 11} and Ce{sub 5}Pd{sub 2}In{sub 19} represent new types. The three structures constitute of [CeIn{sub 3}] cuboctahedra layers and [PdIn{sub 2}] rectangular polyhedra layers, alternating along the tetragonal c-axis in accordance with the m:n proportion. The magnetic and electrical transport properties of the novel compounds Ce{sub 3}PdIn{sub 11} and Ce{sub 5}Pd{sub 2}In{sub 19} were investigated down to 1.72 K. Both indides are Curie–Weiss paramagnets due to the presence of fairly well localized 4f electrons of trivalent cerium ions. The electrical resistivity of both materials is dominated over an extended temperature range by strong spin–flip Kondo interactions with the characteristic temperature scale of 20–30 K. - Graphical abstract: TOC Figure Crystal structures of Ce{sub 3}PdIn{sub 11}, Ce{sub 2}PdIn{sub 8}, and Ce{sub 5}Pd{sub 2}In{sub 19}. Highlights: ► Large section of Ce–Pd–In phase diagram was examined. ► Three distinct ternary phases were identified, two of them for the first time. ► Crystal structures of two novel compounds constitute new structure types. ► The determined crystal structures show close mutual relationship. ► Ce{sub 3}PdIn{sub 11} and Ce{sub 5}Pd{sub 2}In{sub 19} are paramagnetic Kondo lattices.

  19. Structure and properties of YbZnSn, YbAgSn, and Yb{sub 2}Pt{sub 2}Pb

    SciTech Connect

    Poettgen, R.; Arpe, P.E.; Kussmann, D.; Kuennen, B.; Kotzyba, G.; Muellmann, R.; Mosel, B.D.; Felser, C.

    1999-07-01

    YbZnSn, YbAgSn, and Yb{sub 2}Pt{sub 2}Pb were synthesized by reacting the elements in sealed tantalum tubes in a high-frequency furnace. The structures of YbAgSn and Yb{sub 2}Pt{sub 2}Pb were refined from single crystal X-ray data: YbAgPb type, P{bar 6}m2, a = 479.2(2) pm, c = 1087.3(3) pm, wR2 = 0.050, BASF = 0.34(8), 509 F{sup 2} values, 18 variables for Yb{sub 2}Pt{sub 2}Pb. The lattice constants of YbZnSn are confirmed: NdPtSb type, P6{sub 3}mc, a = 464.7(1) pm, c = 747.7(2) pm. The stannides YbZnSn and YbAgSn crystallize with superstructures of the AlB{sub 2} type. The zinc (silver) and tin atoms form ordered Zn{sub 3}Sn{sub 3} and Ag{sub 3}Sn{sub 3} hexagons, respectively. Magnetic susceptibility measurements on YbZnSn and YbAgSn show Pauli paramagnetism with room temperature susceptibilities of 2.5(1) {times} 10{sup {minus}9} and 4.6(1) {times} 10{sup {minus}9} m{sup 3}/mol. Electrical resistivity measurements indicate metallic conductivity with specific resistivities of 440 {+-} 40 {mu}{Omega}cm (YbZnSn) and 490 {+-} 40 {mu}{Omega}cm (YbAgSn) at 300 K. {sup 119}Sn Moessbauer spectra of YbZnSn show a single signal at room temperature with an isomer shift of {delta} = 1.85(1) mm/s. YbAgSn shows two superimposed signals at 78 K: a singlet at {delta} = 1.94(1) mm/s and a second signal at {delta} = 1.99(1) mm/s subjected to quadrupole splitting of {Delta}E{sub Q} = 1.35(1) mm/s, in agreement with the two crystallographically different tin sites.

  20. Charge effect in S enhanced CO adsorption: A theoretical study of CO on Au, Ag, Cu, and Pd (111) surfaces coadsorbed with S, O, Cl, and Na

    NASA Astrophysics Data System (ADS)

    Gan, Li-Yong; Zhao, Yu-Jun

    2010-09-01

    The extraordinary sulfur enhanced CO adsorption on Au surface creates curiosity to many scientists in the field, and is expected to have potential applications in catalyst design. In this work, we have investigated the interactions of the coadsorption of CO and various adatoms X (X=Na, S, O, and Cl) on Au and Pd(111) surfaces and made further comparison with CO adsorption on charged Au and Pd surfaces by a first-principles study. We find out that the enhancement of CO adsorption by S on Au originates from S-induced positive polarization of Au surface. The d band of metal atoms in the positively polarized Au surface shifts up toward the Fermi level (EF) without remarkable changes of its shape and occupation. In contrast, in the negatively polarized Au(111) surface, achieved by electropositive adatom such as Na adsorption or artificially adding additional electrons to the substrate, d bands shift down relative to EF, and thus CO adsorption is weakened. Further study of CO coadsorption with X on two other noble metal (Ag and Cu) surfaces manifests that Ag shows the same behavior as Au does, while the situation of Cu is just between that on Au and Pd. It suggests that the extraordinary S-induced enhancement of CO adsorption on Au/Ag, different from other transition metals (TMs), ultimately results from the inertness of d bands buried below EF. The S-induced charge can introduce a significant d band shift on Au/Ag with respect to EF due to their narrow density of states at EF and thus strengthens CO adsorption subsequently.

  1. Site-specific growth of AgPd nanodendrites on highly purified Au bipyramids with remarkable catalytic performance

    NASA Astrophysics Data System (ADS)

    Zhou, Lin; Liu, Zeke; Zhang, Han; Cheng, Si; Fan, Li-Juan; Ma, Wanli

    2014-10-01

    Au nanorods have been extensively explored in various applications as the template for heterogeneous metallic nanostructures. However, Au bipyramids (AuBPs) have been paid much less attention although they possess an intriguing crystalline structure and extremely superior plasmonic properties which are absent in AuNRs. The state-of-the-art synthesis cannot produce pure AuBPs, which has become a major barrier to their various applications like catalysis since purity is often critical for achieving the desired performance. Herein, we have shown a facile approach to obtain large-scale high-purity AuBPs. The purity of AuBPs can be improved from 30 to 50% for the as-synthesized AuBP solution to over 95% for the purified solution. Site-specific growth of AgPd nanodendrites on multiply twinned AuBPs from core-shell to tipped nanostructures was achieved for the first time by coupling a galvanic replacement with a co-reduction process, which show remarkable catalytic activity in the reduction reaction of 4-nitrophenol (4-NP) by NaBH4. The use of ascorbic acid (AA) as a reductant in the co-reduction process and the intriguing crystalline structure of AuBPs play a critical role in forming these unique structures. We believe that this work would provide a general strategy to prepare high-purity AuBP based trimetallic nanostructures, which offers the opportunity for AuBPs to be widely used in catalysis or other plasmonic-effect related applications in the near future.Au nanorods have been extensively explored in various applications as the template for heterogeneous metallic nanostructures. However, Au bipyramids (AuBPs) have been paid much less attention although they possess an intriguing crystalline structure and extremely superior plasmonic properties which are absent in AuNRs. The state-of-the-art synthesis cannot produce pure AuBPs, which has become a major barrier to their various applications like catalysis since purity is often critical for achieving the desired

  2. Fabrication of nanoporous Cu-Pt(Pd) core/shell structure by galvanic replacement and its application in electrocatalysis.

    PubMed

    Xu, Caixia; Liu, Yunqing; Wang, Jinping; Geng, Haoran; Qiu, Huajun

    2011-12-01

    We describe a general strategy to fabricate a new type of nanoporous core/shell structured bimetallic nanocomposites with controllable metal components. Nanoporous copper (NPC) obtained by dealloying Cu/Al alloy is used as both reducing agent and three-dimensional substrate. Electron microscope and X-ray diffraction characterizations demonstrated that a simply galvanic-replacement reaction with H(2)PtCl(6) aqueous solution can easily generate nanoporous core/shell structure with a thin Pt/Cu alloy shell and Cu (or Pt/Cu alloy) core. The morphology and crystal structure evolution of the nanocomposites are studied and discussed in detail. The as-prepared bimetallic PtCu nanocomposites show greatly enhanced catalytic activity and stability toward methanol electro-oxidation as compared with commercial Pt/C catalyst. This facile in situ preparation strategy is also suitable for large-scale production of this novel and inexpensive catalyst. PMID:22034948

  3. Bimetallic Pd-Pt supported graphene promoted enzymatic redox cycling for ultrasensitive electrochemical quantification of microRNA from cell lysates.

    PubMed

    Cheng, Fang-Fang; Zhang, Jing-Jing; He, Ting-Ting; Shi, Jian-Jun; Abdel-Halim, E S; Zhu, Jun-Jie

    2014-08-21

    The expression of microRNAs (miRNAs) is related to some cancer diseases. Recently, miRNAs have emerged as new candidate diagnostic and prognostic biomarkers for detecting a wide variety of cancers. Due to low levels, short sequences and high sequence homology among family members, the quantitative miRNA analysis is still a challenge. A novel electrochemical biosensor with triple signal amplification for the ultrasensitive detection of miRNA was developed based on phosphatase, redox-cycling amplification, a bimetallic Pd-Pt supported graphene functionalized screen-printed gold electrode, and two stem-loop structured DNAs as target capturers. The proposed biosensor is highly sensitive due to the enhanced electrochemical signal of Pd-Pt supported graphene and sufficiently selective to discriminate the target miRNA from homologous miRNAs in the presence of loop-stem structure probes with T4 DNA ligase. Therefore, this strategy provided a new and ultrasensitive platform for amplified detection and subsequent analysis of miRNA in biomedical research and clinical diagnosis. PMID:24976373

  4. 1H, 13C and 15N nuclear magnetic resonance coordination shifts in Au(III), Pd(II) and Pt(II) chloride complexes with phenylpyridines.

    PubMed

    Pazderski, Leszek; Tousek, Jaromír; Sitkowski, Jerzy; Kozerski, Lech; Szłyk, Edward

    2009-08-01

    1H, 13C and 15N nuclear magnetic resonance studies of gold(III), palladium(II) and platinum(II) chloride complexes with phenylpyridines (PPY: 4-phenylpyridine, 4ppy; 3-phenylpyridine, 3ppy; and 2-phenylpyridine, 2ppy) having the general formulae [Au(PPY)Cl3], trans-/cis-[Pd(PPY)2Cl2] and trans-/cis-[Pt(PPY)2Cl2] were performed and the respective chemical shifts (delta1H, delta13C and delta15N) reported. 1H, 13C and 15N coordination shifts (i.e. differences between chemical shifts of the same atom in the complex and ligand molecules: Delta(coord)(1H) = delta(complex)(1H)-delta(ligand)(1H), Delta(coord)(13C) = delta(complex)(13C)-delta(ligand)(13C), Delta(coord)(15N) = delta(complex)(15N)-delta(ligand)(15N)) were discussed in relation to the type of the central atom (Au(III), Pd(II) and Pt(II)), geometry (trans-/cis-) and the position of a phenyl group in the pyridine ring system. PMID:19472306

  5. Study of Nd3+, Pd2+, Pt4+, and Fe3+ dopant effect on photoreactivity of TiO2 nanoparticles

    PubMed Central

    Shah, S. I.; Li, W.; Huang, C.-P.; Jung, O.; Ni, C.

    2002-01-01

    The metallorganic chemical vapor deposition method was successfully used to synthesize pure TiO2 and Nd3+-, Pd2+-, Pt4+-, and Fe3+-doped TiO2 nanoparticles. Polycrystalline TiO2 structure was verified with x-ray diffraction, which showed typical characteristic anatase reflections without any separate dopant-related peaks. Transmission electron microscopy observations confirmed the existence of homogeneously distributed 22 ± 3 nm TiO2 nanoparticles. The particle size remained the same for the doped samples. The doping level of transition metals was kept at ≈1 atomic percent, which was determined by x-ray photoelectron spectra and energy dispersive x-ray spectroscopy. The effects of different types of dopants on the photocatalytic activity were revealed by the degradation of 2-chlorophenols with an UV light source. The photocatalytic efficiency was remarkably enhanced by the introduction of Pd2+ and Nd3+. Nd3+-doped TiO2 showed the largest enhancement. However, Pt4+ changed the 2-chlorophenol degradation rate only slightly, and Fe3+ was detrimental to this process. These effects were related to the position of the dopants in the nanoparticles and the difference in their ionic radii with respect to that of Ti4+. PMID:11880607

  6. Single Atom (Pd/Pt) Supported on Graphitic Carbon Nitride as an Efficient Photocatalyst for Visible-Light Reduction of Carbon Dioxide.

    PubMed

    Gao, Guoping; Jiao, Yan; Waclawik, Eric R; Du, Aijun

    2016-05-18

    Reducing carbon dioxide to hydrocarbon fuel with solar energy is significant for high-density solar energy storage and carbon balance. In this work, single atoms of palladium and platinum supported on graphitic carbon nitride (g-C3N4), i.e., Pd/g-C3N4 and Pt/g-C3N4, respectively, acting as photocatalysts for CO2 reduction were investigated by density functional theory calculations for the first time. During CO2 reduction, the individual metal atoms function as the active sites, while g-C3N4 provides the source of hydrogen (H*) from the hydrogen evolution reaction. The complete, as-designed photocatalysts exhibit excellent activity in CO2 reduction. HCOOH is the preferred product of CO2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4 catalyst prefers to reduce CO2 to CH4 with a rate-determining barrier of 1.16 eV. In addition, deposition of atom catalysts on g-C3N4 significantly enhances the visible-light absorption, rendering them ideal for visible-light reduction of CO2. Our findings open a new avenue of CO2 reduction for renewable energy supply. PMID:27116595

  7. Graphite/InP and graphite/GaN Schottky barriers with electrophoretically deposited Pd or Pt nanoparticles for hydrogen detection

    PubMed Central

    2012-01-01

    Large attention has been devoted worldwide to the investigation of hydrogen sensors based on various Schottky diodes. We prepared graphite semimetal Schottky contacts on polished n-InP and n-GaN wafers partly covered with nanoparticles of catalytic metals Pd or Pt by applying colloidal graphite. Metal nanoparticles were deposited electrophoretically from colloids prepared beforehand. Deposited nanoparticles were imaged by scanning electron microscopy, atomic force microscopy, and scanning tunneling microscopy on the as-made and annealed-in-vacuum samples. Current–voltage characteristics of prepared Schottky diodes had very high rectification ratios, better than 107 at 1 V. It was shown that the barrier heights of these diodes were equal to the difference between the electron affinity of InP or GaN and the electron work function of the metal Pd or Pt (Schottky-Mott limit). That was a good precondition for the high sensitivity of the diodes to hydrogen, and indeed, high sensitivity to hydrogen, with the detection limit better than 1 ppm, was proved. PMID:22824169

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  9. Electrochemical promotion of propane oxidation on Pt deposited on a dense β″-Al2O3 ceramic Ag+ conductor

    PubMed Central

    Tsampas, Mihalis N.; Kambolis, Anastasios; Obeid, Emil; Lizarraga, Leonardo; Sapountzi, Foteini M.; Vernoux, Philippe

    2013-01-01

    A new kind of electrochemical catalyst based on a Pt porous catalyst film deposited on a β″-Al2O3 ceramic Ag+ conductor was developed and evaluated during propane oxidation. It was observed that, upon anodic polarization, the rate of propane combustion was significantly electropromoted up to 400%. Moreover, for the first time, exponential increase of the catalytic rate was evidenced during galvanostatic transient experiment in excellent agreement with EPOC equation. PMID:24790942

  10. Current-induced spin polarization in transition metals and Bi/Ag bilayers observed by spin-polarized positron beam

    NASA Astrophysics Data System (ADS)

    Zhang, Hongjun; Yamamoto, Shunya; Fukaya, Yuki; Maekawa, Masaki; Li, Hui; Kawasuso, Atsuo; Seki, Takeshi; Saitoh, Eiji; Takanashi, Koki; JAEA Team; Tohoku Team

    2015-03-01

    Current-induced spin polarization (CISP) on the outermost surfaces of Au, Cu, Pt, Pd, Ta, and W films were studied by spin-polarized positron beam (SPPB). The Au and Cu surfaces showed no significant CISP. In contrast, the Pt, Pd, Ta, and W films exhibited large CISP (3 ~ 15% per charge current of 105 A/cm2) and the CISP of Ta and W were opposite to those of Pt and Pd. The sign of the CISP obeys the same rule in spin Hall effect suggesting that the spin-orbit coupling is mainly responsible for the CISP. The outermost spin poalrization of Bi/Ag/Al2O3andAg/Bi/Al2O3 (charge currents directly connected to Ag layers) were probed by SPPB. The opposite outermost spin polarization of Bi/Ag/Al2O3andAg/Bi/Al2O3 clarified the charge-to-spin conversion in Bi/Ag bilayers. Nevertheless, the magnitudes of the outermost spin polarization of Bi(0.3 ~5)/Ag(25)/Al2O3 (numbers in parentheses denote thickness in nm) and Ag(25 ~500)/Bi(8)/Al2O3 decrease exponentially with increasing Bi thickness and Ag thickness, respectively. This provides probably the first direct evidence for spin diffusion mechanism. Financial support from JSPS Kakenhi Grant 24310072.

  11. Photocatalytic Properties of TiO2 Thin Films Modified with Ag and Pt Nanoparticles Deposited by Gas Flow Sputtering.

    PubMed

    Maicu, M; Glöss, D; Frach, Peter; Hecker, D; Gerlach, G; Córdoba, José M

    2015-09-01

    In this work, a gas flow sputtering (GFS) process which allows the production and deposition of metal nanoparticles (NPs) in a vacuum environment is described. Aim of the study is to prove the potential of this technology for the fabrication of new TiO2 films with enhanced photocatalytic properties. For this purpose, Ag and Pt NPs have been produced and deposited on photocatalytic float glass coated with TiO2 thin films by magnetron sputtering. The influence of the process parameters and of the metal amount on the final properties of the particles (quantity, size, size distribution, oxidation state etc.,) was widely investigated. Moreover, the effect of the NPs on the photocatalytic activity of the resulting materials was evaluated for the case of the decomposition of stearic acid (SA) during UV-A irradiation. The reduction of the water contact angle (WCA) during the irradiation period was measured in order to test the photo-induced super-hydrophilicity (PSH). PMID:26716202

  12. Interfacial Engineering of Bimetallic Ag/Pt Nanoparticles on Reduced Graphene Oxide Matrix for Enhanced Antimicrobial Activity.

    PubMed

    Zhang, Mei; Zhao, Yanhua; Yan, Li; Peltier, Raoul; Hui, Wenli; Yao, Xi; Cui, Yali; Chen, Xianfeng; Sun, Hongyan; Wang, Zuankai

    2016-04-01

    Environmental biofouling caused by the formation of biofilm has been one of the most urgent global concerns. Silver nanoparticles (NPs), owing to their wide-spectrum antimicrobial property, have been widely explored to combat biofilm, but their extensive use has raised growing concern because they persist in the environment. Here we report a novel hybrid nanocomposite that imparts enhanced antimicrobial activity and low cytotoxicity yet with the advantage of reduced silver loading. The nanocomposite consists of Pt/Ag bimetallic NPs (BNPs) decorated on the porous reduced graphene oxide (rGO) nanosheets. We demonstrate that the enhanced antimicrobial property against Escherichia coli is ascribed to the intricate control of the interfaces between metal compositions, rGO matrix, and bacteria, where the BNPs lead to a rapid release of silver ions, and the trapping of bacteria by the porous rGO matrix further provides high concentration silver ion sites for efficient bacteria-bactericide interaction. We envision that our facile approach significantly expands the design space for the creation of silver-based antimicrobial materials to achieve a wide spectrum of functionalities. PMID:27007980

  13. 1H, 13C, 195Pt and 15N NMR structural correlations in Pd(II) and Pt(II) chloride complexes with various alkyl and aryl derivatives of 2,2'-bipyridine and 1,10-phenanthroline.

    PubMed

    Pawlak, Tomasz; Pazderski, Leszek; Sitkowski, Jerzy; Kozerski, Lech; Szłyk, Edward

    2011-02-01

    (1)H, (13)C, (195)Pt and (15)N NMR studies of platinide(II) (M = Pd, Pt) chloride complexes with such alkyl and aryl derivatives of 2,2'-bipyridine and 1,10-phenanthroline as LL = 6,6'-dimethyl-bpy, 5,5'-dimethyl-bpy, 4,4'-di-tert-butyl-bpy, 2,9-dimethyl-phen, 2,9-dimethyl-4,7-diphenyl-phen, 3,4,7,8-tetramethyl-phen, having the general [M(LL)Cl(2)] formula were performed and the respective chemical shifts (δ(1H), δ(13C), δ(195Pt), δ(15N)) reported. (1)H high-frequency coordination shifts (Δ(coord)(1H) = δ(complex)(1H)-δ(ligand)(1H)) mostly pronounced for nitrogen-adjacent protons and methyl groups in the nearest adjacency of nitrogen, as well as (15)N low-frequency coordination shifts (Δ(coord)(15H) = δ(complex)(15H)-δ(ligand)(15H)) were discussed in relation to the molecular structures. PMID:21254225

  14. New N^C^N-coordinated Pd(ii) and Pt(ii) complexes of a tridentate N-heterocyclic carbene ligand featuring a 6-membered central ring: synthesis, structures and luminescence.

    PubMed

    Moussa, Jamal; Haddouche, Kamel; Chamoreau, Lise-Marie; Amouri, Hani; Gareth Williams, J A

    2016-08-01

    We describe Pd(ii) and Pt(ii) complexes of an N^C^N-coordinating pincer-like ligand featuring two lateral pyridine rings and a 6-membered carbene core. Their crystal structures display 1-dimensional chains with short π-π and M(ii)M(ii) interactions. Such interactions also impact on the photophysical properties, with the Pt(ii) complex being luminescent in the solid state at room temperature. PMID:27465432

  15. Experimental partitioning studies near the Fe-FeS eutectic, with an emphasis on elements important to iron meteorite chronologies (Pb, Ag, Pd, and Tl)

    NASA Technical Reports Server (NTRS)

    Jones, J. H.; Hart, S. R.; Benjamin, T. M.

    1993-01-01

    Partitioning coefficients for metal/sulfide liquid, troilite/sulfide liquid, and schreibersite/sulfide liquid were determined for Ag, Au, Mo, Ni, Pd, and Tl (using EMPA and proton-induced X-ray microprobe and ion microprobe analyses) in order to understand the chronometer systems of iron meteorites. In general, the obtained schreibersite/metal and troilite/metal partition coefficients for 'compatible' elements were quite similar to those inferred from natural assemblages, reinforcing an earlier made conclusion that there is a class of elements for which experimental troilite/metal and schreibersite/metal partition coefficients approximate those inferred from natural samples. The consistency between experimental and natural assemblages, however, was not observed for Ag, Pb, and Tl, indicating that the abundances of these elements determined in 'metal' and 'troilite' separates from iron meteorites are influenced by trace minerals that concentrate incompatible elements.

  16. The Development of a PdCr Integral Weldable Strain Measurement System Based on NASA Lewis PdCr/Pt Strain Sensor for User-Friendly Elevated Temperature Strain Measurements

    NASA Technical Reports Server (NTRS)

    Wnuk, S. P., Jr.; Wnuk, V. P.

    1997-01-01

    This report describes the development of a user friendly weldable strain gage employing the NASA Lewis PdCr/Pt wire strain sensor. The NASA sensors are pre-attached to Hastelloy X or Titanium alloy shims using name spray techniques developed under previous NASA programs. The weldable sensors are then pre-stabilized for 50 hours at 780 C in air. A weldable terminal and high temperature cable is then connected to the sensor and the assembly is pre-calibrated over the full test temperature range. Calibrated resistors are inserted into a bridge completion module at the cool end of the cable to condition the sensor in half or full bridge configuration. The sensor is attached to the structure using a common capacitive discharge spot welder. No additional high temperature stabilization or calibration is required. The resultant device is a pre-calibrated strain transducer which can be plugged into any common variety strain instrumentation.

  17. Tuning Effects of Spin-Orbit Coupling in L10 Ordered and Disordered FePdPt Films

    NASA Astrophysics Data System (ADS)

    Fan, W. J.; Shi, Z.; Chen, F. L.; Zhou, S. M.

    2015-09-01

    Effects of spin-orbit coupling (SOC) on magnetocrystalline anisotropy, magneto-optical Kerr effect (MOKE), magnetic damping parameter and anomalous Hall effect (AHE) have been studied in theory extensively. In contrast, few experimental reports have appeared on these issues. In this review paper, we introduce our recent experimental investigation on the SOC tuning effects on the perpendicular magnetic anisotropy, polar MOKE, intrinsic magnetic damping parameter and AHE in L10 ordered Fe0.5(Pd1-xPtx)0.5 ternary alloys. We also outline the SOC effects in polycrystalline disordered Fe0.5(Pd1-xPtx)0.5 films for comparison.

  18. A theoretical investigation on hydrolysis mechanism of biologically relevant Pt(II)/Pd(II) complexes with σ-donor and π-acceptor carrier ligand

    NASA Astrophysics Data System (ADS)

    Reddy B., Venkata P.; Mitra, Ishani; Mukherjee, Subhajit; Sengupta, P. S.; Dodda, Subba Reddy; Moi, Sankar Ch.

    2016-07-01

    The hydrolysis mechanism of cytotoxic agents complex 1 cis-[Pt(pic)Cl2] and complex 2 cis-[Pd(pic)Cl2] (where pic = 2-aminomethylpyridine) have been studied in solvent phase using DFT. The stationary states on potential energy surfaces were fully optimized and characterized. The rate constants and activation parameters of both the substitution processes has been calculated in CPCM model and the values were found to be k1 = 3.29 × 10-4 s-1, k2 = 8.88 × 10-9 s-1 for complex 1 and k1 = 0.13 × 10-1 s-1, k2 = 2.0 × 10-10 s-1 for complex 2 respectively. The second step is the rate-limiting process having higher activation energy compared to that of the first step for both the complexes.

  19. Large exchange bias enhancement in (Pt(or Pd)/Co)/IrMn/Co trilayers with ultrathin IrMn thanks to interfacial Cu dusting

    SciTech Connect

    Vinai, G.; Moritz, J.; Bandiera, S.; Prejbeanu, I. L.; Dieny, B.

    2014-04-21

    The magnitude of exchange bias (H{sub ex}) at room temperature can be significantly enhanced in IrMn/Co and (Pt(or Pd)/Co)/IrMn/Co structures thanks to the insertion of an ultrathin Cu dusting layer at the IrMn/Co interface. The combination of trilayer structure and interfacial Cu dusting leads to a three-fold increase in H{sub ex} as compared to the conventional IrMn/Co bilayer structure, with an increased blocking temperature (T{sub B}) and a concave curvature of the temperature dependence H{sub ex}(T), ideal for improved Thermally Assisted-Magnetic Random Access Memory storage layer. This exchange bias enhancement is ascribed to a reduction of the spin frustration at the IrMn/Co interface thanks to interfacial Cu addition.

  20. First principles study on the interfacial properties of NM/graphdiyne (NM = Pd, Pt, Rh and Ir): The implications for NM growing

    NASA Astrophysics Data System (ADS)

    Lu, Zhansheng; Li, Shuo; Lv, Peng; He, Chaozheng; Ma, Dongwei; Yang, Zongxian

    2016-01-01

    Based on the dispersion-corrected density functional calculations (DFT-D), we systematically studied the adsorption of noble metals (NM), Pd, Pt, Rh and Ir, on graphdiyne (GDY). We present a systematic study on the geometry, embedded adsorption energy and electronic structure of four different adatoms adsorbed on the GDY. The strong interaction between the NM adatoms and the GDY substrate is found with the NM embedded in the 18C-hexagon of the GDY. We investigated the mobility of the NM adatoms on the GDY, and found that the mobility barrier energy increases along with the increasing of the embedded adsorption energy. We present the NM adatoms growth of high concentrations on the GDY. Upon the analysis of the electronic structure and the frontier molecular orbitals, Rh and Ir adatoms of low concentrations (about 1.37 at%) on the GDY have the potential to be applied as single metal catalysts or gas molecule sensors.

  1. Conjugatable water-soluble Pt(II) and Pd(II) porphyrin complexes: novel nano- and molecular probes for optical oxygen tension measurement in tissue engineering.

    PubMed

    Giuntini, F; Chauhan, V M; Aylott, J W; Rosser, G A; Athanasiadis, A; Beeby, A; MacRobert, A J; Brown, R A; Boyle, R W

    2014-07-01

    Measurement of oxygen tension in compressed collagen sheets was performed using matrix-embedded optical oxygen sensors based on platinum(II) and palladium(II) porphyrins supported on polyacrylamide nanoparticles. Bespoke, fully water-soluble, mono-functionalised Pt(II) and Pd(II) porphyrin complexes designed for conjugation under mild conditions were obtained using microwave-assisted metallation. The new sensors display a linear response (1/τ vs. O2) to varying oxygen tension over a biologically relevant range (7.0 × 10(-4) to 2.7 × 10(-1) mM) in aqueous solutions; a behaviour that is maintained following conjugation to polyacrylamide nanoparticles, and following embedding of the nanosensors in compressed collagen sheets, paving the way to innovative approaches for real-time resolution of oxygen gradients throughout 3D matrices useful for tissue regeneration. PMID:24818569

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

    PubMed Central

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

    2012-01-01

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

  3. 5f delocalization-induced suppression of quadrupolar order in U(Pd1-xPtx)₃

    SciTech Connect

    Walker, H. C.; Le, M. D.; McEwen, K. A.; Bleckmann, M.; Süllow, S.; Mazzoli, C.; Wilkins, S. B.; Fort, D.

    2011-12-27

    We present bulk magnetic and transport measurements and x-ray resonant scattering measurements on U(Pd1-xPtx)₃ for x=0.005 and 0.01, which demonstrate the high sensitivity of the quadrupolar order in the canonical antiferroquadrupolar ordered system UPd₃ to doping with platinum. Bulk measurements for x=0.005 reveal behavior similar to that seen in UPd₃, albeit at a lower temperature, and x-ray resonant scattering provides evidence of quadrupolar order described by the Qxy order parameter. In contrast, bulk measurements reveal only an indistinct transition in x=0.01, consistent with the observation of short-range quadrupolar order in our x-ray resonant scattering results.

  4. Pt74Ag26 nanoparticle-decorated ultrathin MoS2 nanosheets as novel peroxidase mimics for highly selective colorimetric detection of H2O2 and glucose

    NASA Astrophysics Data System (ADS)

    Cai, Shuangfei; Han, Qiusen; Qi, Cui; Lian, Zheng; Jia, Xinghang; Yang, Rong; Wang, Chen

    2016-02-01

    To extend the functionalities of two-dimensional graphene-like layered compounds as versatile materials, the modification of transition metal dichalcogenide nanosheets such as MoS2 with metal nanoparticles is of great and widespread interest. However, few studies are available on the preparation of bimetallic nanoparticles supported on MoS2. Herein, a facile and efficient method to synthesize MoS2-PtAg nanohybrids by decorating ultrathin MoS2 nanosheets with octahedral Pt74Ag26 alloy nanoparticles has been reported. The as-prepared MoS2-Pt74Ag26 nanohybrids were investigated as novel peroxidase mimics to catalyze the oxidation of classical peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2, producing a blue colored reaction and exhibiting typical Michaelis-Menten kinetics. MoS2-Pt74Ag26 has a higher affinity for H2O2 than horseradish peroxidase (HRP) and a higher vmax value with TMB as the substrate than MoS2. The improved catalytic activity of hybrids for colorimetric reactions could be attributed to the synergistic effects of octahedral Pt74Ag26 nanoparticles and ultrathin MoS2 nanosheets as supports. Meanwhile, the generation of active oxygen species (&z.rad;OH) by H2O2 decomposition with MoS2-Pt74Ag26 was responsible for the oxidation of TMB. On the basis of these findings, a colorimetric method based on MoS2-Pt74Ag26 nanohybrids that is highly sensitive and selective was developed for glucose detection. Lower values of the limit of detection (LOD) were obtained, which is more sensitive than MoS2 nanosheets.To extend the functionalities of two-dimensional graphene-like layered compounds as versatile materials, the modification of transition metal dichalcogenide nanosheets such as MoS2 with metal nanoparticles is of great and widespread interest. However, few studies are available on the preparation of bimetallic nanoparticles supported on MoS2. Herein, a facile and efficient method to synthesize MoS2-PtAg nanohybrids by decorating

  5. Characterization of Ni19.5Ti50.5Pd25Pt5 High-Temperature Shape Memory Alloy Springs and their Potential Application in Aeronautics

    NASA Technical Reports Server (NTRS)

    Stebner, Aaron; Padula, Santo A.; Noebe, Ronald D.

    2008-01-01

    Shape memory alloys (SMAs) have been used as actuators in many different industries since the discovery of the shape memory effect, but the use of SMAs as actuation devices in aeronautics has been limited due to the temperature constraints of commercially available materials. Consequently, work is being done at NASA's Glenn Research Center to develop new SMAs capable of being used in high temperature environments. One of the more promising high-temperature shape memory alloys (HTSMAs) is Ni19.5Ti50.5Pd25Pt5. Recent work has shown that this material is capable of being used in operating environments of up to 250 C. This material has been shown to have very useful actuation capabilities, demonstrating repeatable strain recoveries up to 2.5% in the presence of an externally applied load. Based on these findings, further work has been initiated to explore potential applications and alternative forms of this alloy, such as springs. Thus, characterization of Ni19.5Ti50.5Pd25Pt5 springs, including their mechanical response and how variations in this response correlate to changes in geometric parameters, are discussed. The effects of loading history, or training, on spring behavior were also investigated. A comparison of the springs with wire actuators is made and the benefits of using one actuator form as opposed to the other discussed. These findings are used to discuss design considerations for a surge-control mechanism that could be used in the centrifugal compressor of a T-700 helicopter engine.

  6. A {sup 151}Eu Moessbauer spectroscopic and magnetic susceptibility investigation of the intermetallic compounds EuTIn (T = Zn, Pd, Pt, Au)

    SciTech Connect

    Muellmann, R.; Mosel, B.D.; Eckert, H.; Kotzyba, G.; Poettgen, R.

    1998-04-01

    The title compounds were investigated by magnetic susceptibility measurements and {sup 151}Eu Moessbauer spectroscopy. EuZnIn and EuPtIn show Curie-Weiss behavior above 60 K with experimental magnetic moments of 7.80(5) and 8.0(1) {mu}{sub B}/Eu, respectively, indicating divalent europium. The zinc compound orders antiferromagnetically at T{sub N} = 8.0(5) k and two metamagnetic transitions are detected at the critical field strengths B{sub C1} = 1.1(1) T and B{sub C2} = 2.6(2) T. At 5 K the saturation magnetic moment amounts to 7.0(1) {mu}{sub B}/Eu, suggesting a full parallel spin alignment. EuPdIn and EuAuIn order antiferromagnetically at 13.0(5) and 21.0(5) K in low external magnetic fields, respectively. The four compounds are metallic conductors. The Moessbauer measurements of the EuTIn compounds show {sup 151}Eu isomer shifts typical of divalent europium. The isomer shifts are found to linearly correlated with the closest Eu-Eu distance in the structure. Based on the Moessbauer data the onset of magnetic order is observed at T{sub N}(EuZnIn) = 9.5(5) K, T{sub N}(EuPdIn) = 15.5(5) K, T{sub N}(EuAuIn) = 20.0(5) K, and T{sub N}(EuPtIn) = 20.0(5) K, respectively. The magnetically split spectrum of EuZnIn reveals evidence of Eu site inequivalence.

  7. Ultrasonic-electrodeposition of PtPd alloy nanoparticles on ionic liquid-functionalized graphene paper: towards a flexible and versatile nanohybrid electrode.

    PubMed

    Sun, Yimin; Zheng, Huaming; Wang, Chenxu; Yang, Mengmeng; Zhou, Aijun; Duan, Hongwei

    2016-01-21

    Here we fabricate a new type of flexible and versatile nanohybrid paper electrode by ultrasonic-electrodeposition of PtPd alloy nanoparticles on freestanding ionic liquid (IL)-functionalized graphene paper, and explore its multifunctional applications in electrochemical catalysis and sensing systems. The graphene-based paper materials demonstrate intrinsic flexibility, exceptional mechanical strength and high electrical conductivity, and therefore can serve as an ideal freestanding flexible electrode for electrochemical devices. Furthermore, the functionalization of graphene with IL (i.e., 1-butyl-3-methylimidazolium tetrafluoroborate) not only increases the electroactive surface area of a graphene-based nanohybrid paper electrode, but also improves the adhesion and dispersion of metal nanoparticles on the paper surface. These unique attributes, combined with the merits of an ultrasonic-electrodeposition method, lead to the formation of PtPd alloy nanoparticles on IL-graphene paper with high loading, uniform distribution, controlled morphology and favourable size. Consequently, the resultant nanohybrid paper electrode exhibits remarkable catalytic activity as well as excellent cycle stability and improved anti-poisoning ability towards electrooxidation of fuel molecules such as methanol and ethanol. Furthermore, for nonenzymatic electrochemical sensing of some specific biomarkers such as glucose and reactive oxygen species, the nanohybrid paper electrode shows high selectivity, sensitivity and biocompatibility in these bio-catalytic processes, and can be used for real-time tracking hydrogen peroxide secretion by living human cells. All these features demonstrate its promising application as a versatile nanohybrid electrode material in flexible and lightweight electrochemical energy conversion and biosensing systems such as bendable on-chip power sources, wearable/implantable detectors and in vivo micro-biosensors. PMID:26681401

  8. Experimental and quantum-chemical studies of 1H, 13C and 15N NMR coordination shifts in Au(III), Pd(II) and Pt(II) chloride complexes with picolines.

    PubMed

    Pazderski, Leszek; Tousek, Jaromír; Sitkowski, Jerzy; Malináková, Katerina; Kozerski, Lech; Szłyk, Edward

    2009-03-01

    (1)H, (13)C and (15)N NMR studies of gold(III), palladium(II) and platinum(II) chloride complexes with picolines, [Au(PIC)Cl(3)], trans-[Pd(PIC)(2)Cl(2)], trans/cis-[Pt(PIC)(2)Cl(2)] and [Pt(PIC)(4)]Cl(2), were performed. After complexation, the (1)H and (13)C signals were shifted to higher frequency, whereas the (15)N ones to lower (by ca 80-110 ppm), with respect to the free ligands. The (15)N shielding phenomenon was enhanced in the series [Au(PIC)Cl(3)] < trans-[Pd(PIC)(2)Cl(2)] < cis-[Pt(PIC)(2)Cl(2)] < trans-[Pt(PIC)(2)Cl(2)]; it increased following the Pd(II) --> Pt(II) replacement, but decreased upon the trans --> cis-transition. Experimental (1)H, (13)C and (15)N NMR chemical shifts were compared to those quantum-chemically calculated by B3LYP/LanL2DZ + 6-31G**//B3LYP/LanL2DZ + 6-31G*. PMID:19097135

  9. A GREENER SYNTHESIS OF CORE (FE, CU)-SHELL (AU, PT, PD AND AG) NANOCRYSTALS USING AQUEOUS VITAMIN C

    EPA Science Inventory

    A greener method to fabricate the novel core (Fe and Cu)-shell (noble metals) metal nanocrystals using aqueous ascorbic acid (vitamin C) is described. Transition metal salts such as Cu and Fe were reduced using ascorbic acid, a benign naturally available antioxidant, and then add...

  10. Simplified method for the determination of Ru, Pd, Re, Os, Ir and Pt in chromitites and other geological materials by isotope dilution ICP-MS and acid digestion.

    PubMed

    Meisel, T; Moser, J; Fellner, N; Wegscheider, W; Schoenberg, R

    2001-03-01

    A method for the determination of low Ru, Pd, Re, Os, Ir and Pt abundances in geological reference materials by isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion in a high pressure asher (HPA-S) is presented. The digestion technique is similar to that using Carius tubes but easier to handle and reaches higher temperatures. Osmium can be determined as OsO4 with ICP-MS directly after digestion through a sparging technique. The remaining elements are preconcentrated by means of anion column chromatography. The resin is digested directly without elution leading to high yields but this causes problems if Zr is present at higher levels in the silicate rich materials. The analytical results for international platinum group element (PGE) reference materials, chromitite CHR-Bkg, basalt TDB-1 and gabbro WGB-1, are presented and compared with literature data, demonstrating the validity of the described method. Although higher in concentration, PGEs determined for reference material WGB-1 were worse than for TDB-1 indicating a more inhomogeneous distribution of the platinum group mineral phases. The low PGE abundance chromitite standard, CHR-Bkg, is likely to be homogeneous for Ru, Re, Os and Ir and is recommended as a reference material for the study of chromitites. Detection limits (3s x total procedure blank) range from 0.012 ng (Re and Os) to 0.77 ng (Pt), which could be further improved by applying higher quality acids. PMID:11284333

  11. Promotion effect of Pd on TiO2 for visible light photocatalytic degradation of gaseous formaldehyde.

    PubMed

    Wu, Ren-Jang; Liu, Yung-Shiuan; Lai, Hsiao-Fang; Wang, Jhe-Hao; Chavali, Murthy

    2014-09-01

    TiO2 and Pd doped TiO2 (Pd/TiO2) nanoparticles were prepared by sol gel method. Pd/TiO2 material was characterized by XRD, TEM, TPR, XPS and BET. From XRD data, the crystalline type of TiO2 is known to as Anatase type. TiO2 and Pd/TiO2 were in the order of 9-10 nm and 10-13 nm respectively. The photocatalytic activities of the TiO2 and Pd/TiO2 nanomaterials were evaluated and compared for the photodegradation of formaldehyde (HCHO). HCHO degradation on Pd/TiO2 catalyst, at 60 min, the degradation rate of gaseous HCHO is 95%. Using Pd/TiO2, the rate was faster than TiO2 or doped with other metals (Au/TiO2; Ag/TiO2; Pt/TiO2). PMID:25924333

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  13. Synthesis, structure, and optical properties of Pt(II) and Pd(II) complexes with oxazolyl- and pyridyl-functionalized DPPM-type ligands: a combined experimental and theoretical study.

    PubMed

    Zhang, Shuanming; Pattacini, Roberto; Braunstein, Pierre; De Cola, Luisa; Plummer, Edward; Mauro, Matteo; Gourlaouen, Christophe; Daniel, Chantal

    2014-12-15

    New square-planar complexes [Pt(1(-H))2] (2a) [1(-H) = (oxazolin-2-yl)bis(diphenylphosphino)methanide] and [Pd(1(-H))2] (2b), of general formula [M{(Ph2P)2C---C---NCH2CH2O}2] (M = Pt, 2a; M = Pd, 2b), result from deprotonation of 2-{bis(diphenylphosphino)methyl}oxazoline (1) at the PCHP site. The new, functionalized dppm-type ligand 4-{bis(diphenylphosphino)methyl}pyridine, (Ph2P)2CH(4-C5H4N) (4), was prepared by double lithiation and phosphorylation of 4-picoline. In the presence of NEt3, the reactions of 2 equiv of 4 with [PtCl2(NCPh)2] and [Pd(acac)2] (acac = acetylacetonate) afforded [Pt(4(-H))2] (5a) [4(-H) = bis(diphenylphosphino)(pyridin-4-yl)methanide] and [Pd(4(-H))2] (5b), of general formula [M{(Ph2P)2C(4-C5H4N)}2] (M = Pt, 5a; M = Pd, 5b), respectively. In the absence of base, the reactions of 2 equiv of 4 with [PtCl2(NCPh)2] and [PdCl2(NCPh)2] afforded (5a·2HCl) (6a) and (5b·2HCl) (6b), respectively, in which the PCHP proton of 4 has migrated from carbon to nitrogen to give a pyridinium derivative of general formula [M{(Ph2P)2C(4-C5H4NH)}2]Cl2 (M = Pt, 6a; M = Pd, 6b). The complexes 3a, 5a·2MeOH, and 6b·4CH2Cl2 have been structurally characterized by X-ray diffraction. The absorption/emission properties of the Pt(II) complexes 2a and 5a and the Pd(II) complexes 2b and 5b have been investigated by UV-vis spectroscopy and theoretical analysis based on density functional theory. The UV-vis absorption spectra of the neutral complexes recorded in dilute N,N'-dimethylformamide solutions are dominated by intense spin-allowed intraligand transitions in the region below 350 nm. The complexes exhibit charge-transfer bands between 350 and 500 nm. The experimental and theoretical absorption spectra agree qualitatively and point to two low-lying ligand-to-metal charge transfer states that contribute to the bands observed between 350 and 500 nm. The complexes are emissive in frozen solutions at 77 K, in the pure solid state, and when doped into films of poly

  14. Investigation of the interactions between Pt(II) and Pd(II) derivatives of 5,10,15,20-tetrakis (N-methyl-4-pyridyl) porphyrin and G-quadruplex DNA.

    PubMed

    Sabharwal, Navin C; Mendoza, Oscar; Nicoludis, John M; Ruan, Thomas; Mergny, Jean-Louis; Yatsunyk, Liliya A

    2016-04-01

    G-quadruplexes are non-canonical DNA structures formed by guanine-rich DNA sequences that are implicated in cancer and aging. Understanding how small molecule ligands interact with quadruplexes is essential both to the development of novel anticancer therapeutics and to the design of new quadruplex-selective probes needed for elucidation of quadruplex biological functions. In this work, UV-visible, fluorescence, and circular dichroism spectroscopies, fluorescence resonance energy transfer (FRET) melting assays, and resonance light scattering were used to investigate how the Pt(II) and Pd(II) derivatives of the well-studied 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin (TMPyP4) interact with quadruplexes formed by the human telomeric DNA, Tel22, and by the G-rich sequences from oncogene promoters. Our results suggest that Pt- and PdTMPyP4 interact with Tel22 via efficient π-π stacking with a binding affinity of 10(6)-10(7) M(-1). Under porphyrin excess, PtTMPyP4 aggregates using Tel22 as a template; the aggregates reach maximum size at [PtTMPyP4]/[Tel22] ~8 and dissolve at [PtTMPyP4]/[Tel22] ≤ 2. FRET assays reveal that both porphyrins are excellent stabilizers of human telomeric DNA, with stabilization temperature of 30.7 ± 0.6 °C for PtTMPyP4 and 30.9 ± 0.4 °C for PdTMPyP4 at [PtTMPyP4]/[Tel22] = 2 in K(+) buffer, values significantly higher as compared to those for TMPyP4. The porphyrins display modest selectivity for quadruplex vs. duplex DNA, with selectivity ratios of 150 and 330 for Pt- and PdTMPyP4, respectively. This selectivity was confirmed by observed 'light switch' effect: fluorescence of PtTMPyP4 increases significantly in the presence of a variety of DNA secondary structures, yet the strongest effect is produced by quadruplex DNA. PMID:26748794

  15. Structural and in vitro cytotoxicity studies on 1H-benzimidazol-2-ylmethyl-N-phenyl amine and its Pd(II) and Pt(II) complexes

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

    [MLCl 2]· zH 2O (L = (1H-benzimidazol-2-ylmethyl)-N-phenyl amine; M = Pd, z = 0; M = Pt, z = 1) and [PdL(OH 2) 2]·2X·zH 2O (X = Br, I, NO 3, z = 0; X = SCN, z = 1) complexes were synthesized as potential anticancer compounds and characterized by elemental analysis, spectral and thermal methods. FT-IR and 1H NMR studies revealed that the benzimidazole L is coordinated to the metal ions via the pyridine-type nitrogen (N py) of the benzimidazole ring and secondary amino group (NH sec). Quantum mechanical calculations of energies, geometries, vibrational wavenumbers, and 1H NMR of the benzimidazole L and its complexes were carried out by density functional theory using B3LYP functional combined with 6-31G(d) and LANL2DZ basis sets. Natural bond orbitals (NBOs) and frontier molecular orbitals were performed at B3LYP/LANL2DZ level of theory. The synthesized ligand, in comparison to its metal complexes was screened for its antibacterial activity. The benzimidazole L is more toxic against the bacterium Staphylococcus aureus (MIC = 58 μg/mL) than the standard tetracycline (MIC = 82 μg/mL). The complexes showed cytotoxicity against breast cancer, Colon Carcinoma, and human heptacellular Carcinoma cells. The platinum complex ( 6) displays cytotoxicity (IC 50 = 12.4 μM) against breast cancer compared with that reported for cis-platin 9.91 μM.

  16. Spin crossover behaviour in one-dimensional Fe(II) compounds based on the [M(CN)4](2-) (M = Pd, Pt) units.

    PubMed

    Zhang, Shao-Liang; Zhao, Xin-Hua; Wang, Yuan-Min; Shao, Dong; Wang, Xin-Yi

    2015-05-28

    Four one-dimensional heterobimetallic coordination polymers {Fe(pic)2[M(CN)4]}n (M = Pd(II) () and Pt(II) (), pic = 2-picolylamine), and {Fe(pypz)2[M(CN)4]}n (M = Pd(II) () and Pt(II) (), pypz = 2-(1H-pyrazol-3-yl)pyridine) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction, magnetic measurements and differential scanning calorimetry (DSC). Single-crystal X-ray analyses show that all the compounds are 1D neutral zigzag chain structures in which the planar [M(CN)4](2-) anion acts as a μ2-bridging ligand, and the two pic/pypz molecules as chelating coligands. Examination of the intermolecular contacts in compounds reveals the existence of the hydrogen bonding interactions involving the hydrogen donor groups of the pic and pypz ligands and the nitrogen atoms of the non-bridging cyanide groups of the [M(CN)4](2-) anions. Weak π-π interactions were also found to be important for the formation of the 3D structures of compounds and . The SCO properties of all compounds were confirmed by the detailed structural analyses of the coordination environments of the Fe(II) centres, DSC analyses, and magnetic susceptibility measurements. Compounds and exhibit complete SCO behaviour with very narrow thermal hysteresis loops centred near the room temperature (T1/2↓ = 270 K and T1/2↑ = 272 K for and T1/2↓ = 272 K and T1/2↑ = 274 K for ), whereas and exhibit abrupt SCO at 186 and 180 K, respectively. Compared to the mononuclear species of the pic and pypz ligands, the SCO temperatures are adjusted by the different ligand field strength of the [M(CN)4)](2-) units. The cooperativity from both the coordination bonds and supramolecular interaction leads to the observation of the hysteresis loops in the Fe-pic systems and the abrupt SCO transition in the Fe-pypz systems. Furthermore, the light-induced excited-spin-state trapping (LIESST) effect was observed for . PMID:25924017

  17. Cross-sections for populating excited states in 150-153Sm via the (p,d) and (p,t) reactions

    NASA Astrophysics Data System (ADS)

    Humby, P.; Simon, A.; Beausang, C. W.; Gell, K.; Tarlow, T.; Vyas, G.; Ross, T. J.; Hughes, R. O.; Burke, J. T.; Casperson, R. J.; Koglin, J.; Ota, S.; Allmond, J. M.; McCleskey, M.; McCleskey, E.; Saastamoinen, A.; Chyzh, R.; Dag, M.

    2014-09-01

    Light ion transfer reactions were used to populate low/medium spin states in 150-154Sm via the (p,p' γ), (p,d γ) and (p,t γ) reactions. The 25 MeV proton beam, with an average current of 1 nA, was provided by the K-150 Cyclotron at the Cyclotron Institute of Texas A&M University. The outgoing charged particles and coincident gamma-rays were detected using the STARLiTeR arrays. STARs (Silicon Telescope Array for Reaction studies), a highly segmented ΔE-E silicon telescope, provides particle identification as well as the energies, times and angular distributions of the protons, deuterons and tritons in the exit channels. LiTeR (Livermore Texas Richmond array), an array of six BGO shielded HPGe clover detectors, records the energy, time and angular distribution of the coincident gamma rays, providing excellent selectivity of the states of interest. Preliminary results for the cross-sections for direct population of states in 150-153Sm will be presented. Light ion transfer reactions were used to populate low/medium spin states in 150-154Sm via the (p,p' γ), (p,d γ) and (p,t γ) reactions. The 25 MeV proton beam, with an average current of 1 nA, was provided by the K-150 Cyclotron at the Cyclotron Institute of Texas A&M University. The outgoing charged particles and coincident gamma-rays were detected using the STARLiTeR arrays. STARs (Silicon Telescope Array for Reaction studies), a highly segmented ΔE-E silicon telescope, provides particle identification as well as the energies, times and angular distributions of the protons, deuterons and tritons in the exit channels. LiTeR (Livermore Texas Richmond array), an array of six BGO shielded HPGe clover detectors, records the energy, time and angular distribution of the coincident gamma rays, providing excellent selectivity of the states of interest. Preliminary results for the cross-sections for direct population of states in 150-153Sm will be presented. This work was partly supported by the US Department of Energy

  18. Levels of {sup 105}Pd populated in the decay of {sup 105}Ag{sup {ital m},{ital g}} and comparison with interacting boson-fermion model calculations

    SciTech Connect

    Meyer, R.A.; Jackson, S.V.; Brant, S.; Paar, V.

    1996-12-01

    Deexcitation properties of low-spin levels in {sup 105}Pd populated in the decay of {sup 105}Ag{sup {ital m}} and {sup 105}Ag{sup {ital g}} are investigated. The calculation for {sup 105}Pd is performed in the interacting boson-fermion model (IBFM), using a nearly spherical boson core corresponding to {sup 104}Pd. As a result, we obtain an approximate quasiweak-coupling pattern, which is in contrast to previously assumed symmetric rotor model calculations. Rather good agreement between theory and experiment was obtained. The extension of the IBFM calculations to lighter {ital N}=59 isotones is consistent with the recent discovery of coexisting structures and dual double-subshell closure in respective even-even core nuclei. {copyright} {ital 1996 The American Physical Society.}

  19. Phase stabilities of pyrite-related MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te): A systematic DFT study

    SciTech Connect

    Bachhuber, Frederik; Krach, Alexander; Furtner, Andrea; Söhnel, Tilo; Peter, Philipp; Rothballer, Jan; Weihrich, Richard

    2015-03-15

    Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine their stabilities, competing binary MT{sub 2} and MCh{sub 2} boundary phases are taken into account as well as ternary M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs{sub 2} type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units tha