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Sample records for ag pt au

  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. 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

  3. Thermomodulation spectra of high-energy interband transitions in Cu, Pd, Ag, Pt, and Au

    SciTech Connect

    Olson, C.G.; Lynch, D.W.; Rosei, R.

    1980-07-15

    Thermotransmission and thermoreflectance spectra were obtained for Cu, Pd, Ag, Pt, and Au in the 10 --30 eV spectral region. Structures due to transitions from the Fermi level to high-density bands 15 eV above the Fermi level were identified in Pt. All metals showed structures arising from interband transitions between the d bands and the same flat bands, 15--20 eV above the Fermi energy. Attempts to fit to interband critical points in Au revealed over 40 possible critical points in the region of these structures, most of them near the Brillouin-zone centers. Systematic trends in the series of metals make the qualitative identification of the structures more secure, and no energy shifts of calculated energy bands are required. The observed widths of structures are sometimes much narrower than the widths of free-electron-like bands at comparable energies.

  4. 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...

  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. 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

  7. Thermomodulation spectra of high-energy interband transitions in Cu, Pd, Ag, Pt, and Au

    SciTech Connect

    Olson, C.G.; Lynch, D.W.; Rosei, R.

    1980-05-01

    Many f.c.c. metals exhibit a rise in the reflectance at about 18 eV, leading to a broad peak. Thermomodulation spectra in this region reveal a richly-structured spectra. We have made thermotransmission measurements on unsupported thin films of Cu, Pd, Ag, and Au, and thermoreflectance measurements on Pt in the 15 to 30 eV spectral region. The temperature-modulated transmittance spectrum can be shown to be simply -d..delta mu.., the sample thickness multiplied by the negative of the temperature-induced change in the absorption coefficient. No data treatment is necessary. For Pt the thermoreflectance spectra were Kramers-Kronig analyzed to get ..delta mu... The data obtained for these metals are given. The spectra do not change appreciably when the ambient temperature is changed.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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.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

  9. A general approach to fabricate diverse noble-metal (Au, Pt, Ag, Pt/Au)/Fe2O3 hybrid nanomaterials.

    PubMed

    Zhang, Jun; Liu, Xianghong; Guo, Xianzhi; Wu, Shihua; Wang, Shurong

    2010-07-19

    A novel, facile, and general one-pot strategy is explored for the synthesis of diverse noble-metal (Au, Pt, Ag, or Pt/Au)/Fe(2)O(3) hybrid nanoparticles with the assistance of lysine (which is a nontoxic, user friendly amino acid that is compatible with organisms) and without using any other functionalization reagents. Control experiments show that lysine, which contains both amino and carboxylic groups, plays dual and crucial roles as both linker and capping agents in attaching noble metals with a small size and uniform distribution onto an Fe(2)O(3) support. Considering the perfect compatibility of lysine with organism, this approach may find potentials in biochemistry and biological applications. Furthermore, this novel route is also an attractive alternative and supplement to the current methods using a silane coupling agent or polyelectrolyte for preparing hybrid nanomaterials. To demonstrate the usage of such hybrid nanomaterials, a chemical gas sensor has been fabricated from the as-synthesized Au/Fe(2)O(3) nanoparticles and investigated for ethanol detection. Results show that the hybrid sensor exhibits significantly improved sensor performances in terms of high sensitivity, low detection limit, better selectivity, and good reproducibility in comparison with pristine Fe(2)O(3). Most importantly, this general approach can be further employed to fabricate other hybrid nanomaterials based on different support materials.

  10. A close look of Au/Pt/Ag nanocomposites using SERS assisted with optical, electrochemical, spectral and theoretical methods

    NASA Astrophysics Data System (ADS)

    Karthikeyan, B.; Loganathan, B.

    2013-03-01

    In the hope of gaining a close look or better characterization of trimetallic nanoparticles that are expected to possess higher surface-enhanced Raman scattering (SERS) activity, we have analysed Au/Pt/Ag trimetallic nanocomposites prepared by the microwave irradiation method. The plasmon absorption of the trimetallic nanocomposites shows a linear shift with the addition of 7-azaindole. The addition of 7-azaindole on trimetallic nanocomposites and the obtained spectral, optical and electrochemical studies give a close look of trimetallic nanocomposite's structure and its properties. In addition to that, core-shell preferences and Pt adsorbed surface complex of 7-azaindole are theoretically explained.

  11. Different structural preference of Ag(I) and Au(I) in neutral and cationic luminescent heteropolynuclear platinum(II) complexes: Z (U)-shaped Pt2M2 type vs. trinuclear PtM2 type.

    PubMed

    Nishihara, Kazuki; Ueda, Misa; Higashitani, Ami; Nakao, Yoshihide; Arikawa, Yasuhiro; Horiuchi, Shinnosuke; Sakuda, Eri; Umakoshi, Keisuke

    2016-03-28

    The reactions of monocationic Pt(II) complexes bearing N^C chelate ligands and Me2pzH, [Pt(N^C)(Me2pzH)2]PF6 (N^C = 2-phenylpyridinate (ppy(-)), 2-(2,4-difluorophenyl)pyridinate (dfppy(-)), benzo[h]quinolinate (bzq(-)); Me2pzH = 3,5-dimethylpyrazole), with Ag(I) ions gave Z (or U)-shaped neutral tetranuclear Pt2Ag2 complexes [Pt2Ag2(N^C)2(Me2pz)4], while those with Au(I) ions gave neutral trinuclear PtAu2 complexes [PtAu2(N^C)(Me2pz)3]. On the contrary, the reactions of the dicationic Pt(II) complex bearing a N^N chelate ligand and Me2pzH, [Pt(bpy)(Me2pzH)2](PF6)2 (bpy = 2,2'-bipyridine), with Ag(I) and Au(I) ions both gave Z (or U)-shaped dicationic tetranuclear Pt2M2 complexes, [Pt2M2(bpy)2(Me2pz)4](PF6)2 (M = Ag, Au). The structures of heteropolynuclear Pt(II) complexes were dominated by the nature of incorporated group 11 metal ions and the charge of complexes.

  12. Global optimization of bimetallic cluster structures. II. Size-matched Ag-Pd, Ag-Au, and Pd-Pt systems.

    PubMed

    Rossi, Giulia; Ferrando, Riccardo; Rapallo, Arnaldo; Fortunelli, Alessandro; Curley, Benjamin C; Lloyd, Lesley D; Johnston, Roy L

    2005-05-15

    Genetic algorithm global optimization of Ag-Pd, Ag-Au, and Pd-Pt clusters is performed. The 34- and 38-atom clusters are optimized for all compositions. The atom-atom interactions are modeled by a semiempirical potential. All three systems are characterized by a small size mismatch and a weak tendency of the larger atoms to segregate at the surface of the smaller ones. As a result, the global minimum structures exhibit a larger mixing than in Ag-Cu and Ag-Ni clusters. Polyicosahedral structures present generally favorable energetic configurations, even though they are less favorable than in the case of the size-mismatched systems. A comparison between all the systems studied here and in the previous paper (on size-mismatched systems) is presented.

  13. Proposed power-function N-body potential for the fcc structured metals Ag, Au, Cu, Ni, Pd, and Pt

    SciTech Connect

    Li, J. H.; Kong, Y.; Guo, H. B.; Liang, S. H.; Liu, B. X.

    2007-09-01

    We propose, for the fcc structured Ag, Au, Cu, Ni, Pd, and Pt metals, an N-body potential with a simple power-function form, which significantly simplifies the fitting procedure and computation. The proposed potentials are able to correctly reproduce the lattice constants, cohesion energies, elastic constants, relative stabilities of different structures, formation energies of vacancy, and surface energies. In addition, the thermal properties, such as melting points and heat capacities, etc., are also satisfactorily determined from the proposed potentials. Moreover, the proposed potential is applied to calculate the trigonal and tetragonal paths between the fcc and bcc structures, and the calculated paths match well with those obtained from the first principles calculations.

  14. Absorption and scattering of light by Pt, Pd, Ag, and Au nanodisks: absolute cross sections and branching ratios.

    PubMed

    Langhammer, Christoph; Kasemo, Bengt; Zorić, Igor

    2007-05-21

    Localized surface plasmons (LSPs) of metallic nanoparticles decay either radiatively or via an electron-hole pair cascade. In this work, the authors have experimentally and theoretically explored the branching ratio of the radiative and nonradiative LSP decay channels for nanodisks of Ag, Au, Pt, and Pd, with diameters D ranging from 38 to 530 nm and height h=20 nm, supported on a fused silica substrate. The branching ratio for the two plasmon decay channels was obtained by measuring the absorption and scattering cross sections as a function of photon energy. The former was obtained from measured extinction and scattering coefficients, using an integrating sphere detector combined with particle density measurements obtained from scanning electron microscopy images of the nanoparticles. Partly angle-resolved measurements of the scattered light allowed the authors to clearly identify contributions from dipolar and higher plasmonic modes to the extinction, scattering, and absorption cross sections. Based on these experiments they find that absorption dominates the total scattering cross section in all the examined cases for small metallic nanodisks (D<100 nm). For D>100 nm absorption still dominates for Pt and Pd nanodisks, while scattering dominates for Au and Ag. A theoretical approach, where the metal disks are approximated as oblate spheroids, is used to account for the trends in the measured cross sections. The field problem is solved in the electrostatic limit. The spheroid is treated as an induced dipole for which the dipolar polarizability is calculated based on spheroid geometry and the (bulk) dielectric response function of the metal the spheroid consists of and the dielectric medium surrounding it. One might expect this model to be inappropriate for disks with D>100 nm since effects due to the retardation of the incoming field across the metallic nanodisk and contributions from higher plasmonic modes are neglected. However, this model describes quite well

  15. 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.

  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. 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.

  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. 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

  20. Electronic structures of an epitaxial graphene monolayer on SiC(0001) after metal intercalation (metal = Al, Ag, Au, Pt, and Pd): A first-principles study

    NASA Astrophysics Data System (ADS)

    Hsu, Chia-Hsiu; Lin, Wen-Huan; Ozolins, Vidvuds; Chuang, Feng-Chuan

    2012-02-01

    The atomic structures and electronic properties of metal-intercalated (metal = Al, Ag, Au, Pt, and Pd) graphene monolayers on SiC(0001) were investigated using first-principles calculations. The unique Dirac cone of graphene near the K point reappeared as the graphite layer was intercalated by these metals at a coverage of 3/8 ML. Furthermore, our results show that metal intercalation leads to n-type doping of graphene. The bands contributed from graphene exhibit small splitting after intercalation, whereas the bands contributed from the intercalated metal layer have significant Rashba spin-orbit splittings in all cases except Al.

  1. 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.

  2. Search for strangelets and other rare objects in Au + Pt collisions at the AGS using a fixed-angle focusing spectrometer

    SciTech Connect

    Rusek, A.; Bassalleck, B.; Fischer, H.; Berdoz, A.; Franklin, G.B.; Buerger, T.; Burger, M.; Chrien, R.E.; Diebold, G.E.; En`yo, H.

    1995-12-31

    During the 1993 AGS heavy ion run, experiment E886 conducted a strangelet search in Au + Pt reactions, with beam momentum of 10.8 GeV/c per nucleon. Presented here are the upper limit for strangelet production, invariant cross sections for p, t, d, {sup 3}He, {sup 4}He, {sup 6}He, {sup 8}He, {sup 6}Li, {sup 7}Li, {sup 8}Li and {sup 7}Be, along with a demonstration of their agreement with a coalescence model fit to data collected by E886 during the 1992 engineering run, and upper limits for production cross sections for other rare objects, such as (H dibaryon)-nucleus systems. All results reported are preliminary.

  3. Phonon spectra and temperature variation of bulk properties of Cu, Ag, Au and Pt using Sutton-Chen and modified Sutton-Chen potentials

    NASA Astrophysics Data System (ADS)

    Januszko, A.; Bose, S. K.

    2015-07-01

    Three potentials of the Finnis-Sinclair type are studied with regard to their suitability for predicting bulk thermal and elastic properties of fcc metals Cu, Ag, Au and Pt over a wide temperature range. We start with a particular parametrization of the Finnis-Sinclair model known as the Sutton-Chen potential and a later version of the same, known as the quantum Sutton-Chen potential. The quasiharmonic lattice dynamics method is used to study the temperature variation of the thermodynamic properties. Both models are found to yield poor results for thermal expansion, which can be traced to rapid softening of transverse phonon frequencies with increasing lattice parameter. The form of the Sutton-Chen potential is modified here to seek improvement in the agreement between quasiharmonic calculations and experimental data. It is found that the modified potential better predicts bulk properties in nearly all cases studied. Significant improvement is seen over the Sutton-Chen potential, while lesser but still substantial improvement is observed over the Quantum-Sutton Chen potential.

  4. Synthesis and optical property characterization of elongated AuPt and Pt@Au metal nanoframes

    NASA Astrophysics Data System (ADS)

    Lee, Sangji; Jang, Hee-Jeong; Jang, Ho Young; Hong, Soonchang; Moh, Sang Hyun; Park, Sungho

    2016-02-01

    We report a facile method to synthesize elongated nanoframes consisting of Pt and Au in solution. Pentagonal Au nanorods served as templates and successfully led to an elongated AuPt nanoframe after etching the core Au. Subsequently, the coating of Au around Pt ridges resulted in Pt@Au metal nanoframes. The resulting elongated nanostructure exhibited 5 well-defined ridges continuously connected along the long axis. During the shape evolution from pure Au nanorods to elongated Pt@Au metal nanoframes, their corresponding localized surface plasmon resonance bands were monitored. Especially, unique surface plasmon features were observed for elongated Pt@Au nanoframes where the short-axis oscillation of surface free electrons is strongly coupled but the long-axis oscillation is not coupled among the ridges.We report a facile method to synthesize elongated nanoframes consisting of Pt and Au in solution. Pentagonal Au nanorods served as templates and successfully led to an elongated AuPt nanoframe after etching the core Au. Subsequently, the coating of Au around Pt ridges resulted in Pt@Au metal nanoframes. The resulting elongated nanostructure exhibited 5 well-defined ridges continuously connected along the long axis. During the shape evolution from pure Au nanorods to elongated Pt@Au metal nanoframes, their corresponding localized surface plasmon resonance bands were monitored. Especially, unique surface plasmon features were observed for elongated Pt@Au nanoframes where the short-axis oscillation of surface free electrons is strongly coupled but the long-axis oscillation is not coupled among the ridges. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08200e

  5. 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.

  6. Poly (vinyl alcohol)/gum karaya electrospun plasma treated membrane for the removal of nanoparticles (Au, Ag, Pt, CuO and Fe3O4) from aqueous solutions.

    PubMed

    Padil, Vinod Vellora Thekkae; Černík, Miroslav

    2015-04-28

    In the present work, nanofibre membranes composed of polyvinyl alcohol (PVA) and a natural gum karaya (GK) hydrocolloid were prepared using electrospinning. The electrospun membranes of PVA/GK were cross-linked with heat treatment and later methane plasma was used to obtain a hydrophobic membrane. The morphology, characterization and adsorption ability of P-NFM was assessed using scanning electron microscopy, UV-vis spectroscopy, ATR-FTIR techniques, water contact angle and ICP-MS analytical methods. The membrane was employed for the extraction of nanoparticles (Ag, Au, Pt, CuO and Fe3O4) from water. The nanoparticle extraction kinetic and adsorption isotherm perform the pseudo-second-order model and Langmuir isotherm model, respectively. The adsorption capacities of the membrane for the removal of NPs from water diverge in the order Pt>Au>Ag>CuO>Fe3O4. The high adsorption efficiency for the removal of NPs from water was compared with an untreated membrane. Physisorption, functional group interactions, complexation reactions between metal/metal oxide nanoparticles with various functional groups present in NFM and modified surface properties such as the balance of hydrophilicity/hydrophobicity, surface free energy, and the high surface area of the plasma treated membrane were possible mechanisms of NPs adsorption onto NFM. The regeneration and reusability were tested in five consecutive adsorption/desorption cycles.

  7. Synthesis and Optical Responses of Ag@Au/Ag@Au Double Shells

    NASA Astrophysics Data System (ADS)

    Li, Ying-Ying; Liu, Xiao-Li; Yang, Da-Jie; Hao, Zhong-Hua; Wang, Qu-Quan

    2015-02-01

    We synthesize hollow-structured Ag@Au nanoparticles with single porous shell and Ag@Au/Ag@Au double shells by using the galvanic replacement reaction and investigate their linear and nonlinear optical properties. Our results show that the surface plasmon resonance wavelength of the hollow porous nanoparticles could be easily tuned in a wide range in the visible and near infrared region by controlling the volume of HAuCl4. The nonlinear optical refraction of the double-shelled Ag@Au/Ag@Au nanoparticles is prominently enhanced by the plasmon resonance. Our findings may find applications in biosensors and nonlinear optical nanodevices.

  8. 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.

  9. 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.

  10. Reactivity of Two-Dimensional Au9, Pt9, and Au18Pt18 against Common Molecules.

    PubMed

    Takahashi, Lauren; Takahashi, Keisuke

    2016-09-19

    Adsorption of common molecules over two-dimensional Au9, Pt9, and Au18Pt18 is investigated with implementation of first-principles calculations. In general, it is found that Pt9 and Au18Pt18 exhibit low adsorption energies where Au18Pt18 preserves the structural integrity of the molecule and surface. In particular, adsorption of molecules onto Au18Pt18 frequently results in low adsorption energies and high reactivity with minor surface reconstruction of Au18Pt18 and average bond lengths of molecules. The decrease in adsorption energy can be attributed to the presence of platinum, while gold can be considered responsible for structural stability. In addition, molecule dissociation is observed in the cases of H2, HCl, CH4, SO, and SO2 when Pt atoms are involved. Thus, two-dimensional Au9, Pt9, and Au18Pt18 show low adsorption energies against common molecules, reflecting adsorption energies observed in small Au and Pt clusters. These results demonstrate that Au18Pt18 can successfully utilize the low adsorption energies associated with platinum while preserving the integrity of the surface structure using gold atoms, making it possible to adsorb desired molecules using select areas of the Au18Pt18 surface. PMID:27608367

  11. 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

  12. The role of charge transfer in the oxidation state change of Ce atoms in the TM13-CeO2(111) systems (TM = Pd, Ag, Pt, Au): a DFT + U investigation.

    PubMed

    Tereshchuk, Polina; Freire, Rafael L H; Ungureanu, Crina G; Seminovski, Yohanna; Kiejna, Adam; Da Silva, Juarez L F

    2015-05-28

    Despite extensive studies of transition metal (TM) clusters supported on ceria (CeO2), fundamental issues such as the role of the TM atoms in the change in the oxidation state of Ce atoms are still not well understood. In this work, we report a theoretical investigation based on static and ab initio molecular dynamics density functional theory calculations of the interaction of 13-atom TM clusters (TM = Pd, Ag, Pt, Au) with the unreduced CeO2(111) surface represented by a large surface unit cell and employing Hubbard corrections for the strong on-site Coulomb correlation in the Ce f-electrons. We found that the TM13 clusters form pyramidal-like structures on CeO2(111) in the lowest energy configurations with the following stacking sequence, TM/TM4/TM8/CeO2(111), while TM13 adopts two-dimensional structures at high energy structures. TM13 induces a change in the oxidation state of few Ce atoms (3 of 16) located in the topmost Ce layer from Ce(IV) (itinerant Ce f-states) to Ce(III) (localized Ce f-states). There is a charge flow from the TM atoms to the CeO2(111) surface, which can be explained by the electronegativity difference between the TM (Pd, Ag, Pt, Au) and O atoms, however, the charge is not uniformly distributed on the topmost O layer due to the pressure induced by the TM13 clusters on the underlying O ions, which yields a decrease in the ionic charge of the O ions located below the cluster and an increase in the remaining O ions. Due to the charge flow mainly from the TM8-layer to the topmost O-layer, the charge cannot flow from the Ce(IV) atoms to the O atoms with the same magnitude as in the clean CeO2(111) surface. Consequently, the effective cationic charge decreases mainly for the Ce atoms that have a bond with the O atoms not located below the cluster, and hence, those Ce atoms change their oxidation state from IV to III. This increases the size of the Ce(III) compared with the Ce(IV) cations, which builds-in a strain within the topmost Ce layer, and

  13. 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

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

    PubMed

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

    2014-06-01

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

  15. DSPRU Project at NSU: Evolution of Basic, Mantle-crust Granitoid Ore-magmatic Systems Resulting in Pt-Cu-Ni, Cu-Mo-porphiric and Epithermal Au-Ag Ore-bearing Mineralization.

    NASA Astrophysics Data System (ADS)

    Rakhmenkulova, I.; Sharapov, V.; Zhitova, L.

    2006-05-01

    Education and Human Resources are one of the most important priorities of the Russian Government policy nowadays. This work covers the principally new Project of the Ministry for Russian Science and Education: 'Development of Scientific Potential for Russian Universities' (DSPRU). The purposes of the Project are: 1) to involve university students to research in most urgent problems of fundamental science; 2) to enhance the professional development of Russian educators; 3) to interest the most perspective researches in education process at Russian universities; 4) to broaden the educational process involving to the Project foreign students, educators and researchers. All the State Universities in Russia could participate in the Project (with the exception of Moscow State University, whose employees were the Project experts). At Novosibirsk State University (NSU) research teams of 13 Departments applied for the Project. Only 5 Projects turned out to be successful. From the Department of Geology and Geophysics 9 Projects were applied and the only one won: 'Evolution of Basic, Mantle-crust Granitoid Ore-magmatic Systems Resulting in Pt-Cu-Ni, Cu-Mo-porphiric and Epithermal Au-Ag Ore-bearing Mineralization'. The team of the above-mentioned Project includes: - nine university educators - five researchers from the Institutes of Siberian Branch of Russian Academy of Sciences - four PhD students - eight undergraduate students. The expecting results of the Project are: 1) obtaining new data for natural objects covered by the Project (Siberia, Mongolia, China, South Africa, Morocco); 2) creation of mathematical models of evolution for fluid ore-magmatic systems of various geochemical character and productivity; 3) improving the education process at the Department of Geology and Geophysics of NSU (creation of new courses and publications, professional development of the educators, participation of students and young researchers in scientific conferences). The work was

  16. 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

  17. Isomorphism and solid solutions among Ag- and Au-selenides

    NASA Astrophysics Data System (ADS)

    Palyanova, Galina A.; Seryotkin, Yurii V.; Kokh, Konstantin A.; Bakakin, Vladimir V.

    2016-09-01

    Au-Ag selenides were synthesized by heating stoichiometric mixtures of elementary substances of initial compositions Ag2-xAuxSe with a step of x=0.25 (0≤x≤2) to 1050 °C and annealing at 500 °C. Scanning electron microscopy, optical microscopy, electron microprobe analysis and X-ray powder diffraction methods have been applied to study synthesized samples. Results of studies of synthesized products revealed the existence of three solid solutions with limited isomorphism Ag↔Au: naumannite Ag2Se - Ag1.94Au0.06Se, fischesserite Ag3AuSe2 - Ag3.2Au0.8Se2 and gold selenide AuSe - Au0.94Ag0.06Se. Solid solutions and AgAuSe phases were added to the phase diagram of Ag-Au-Se system. Crystal-chemical interpretation of Ag-Au isomorphism in selenides was made on the basis of structural features of fischesserite, naumannite, and AuSe.

  18. Sintering behavior of spin-coated FePt and FePtAu nanoparticles

    NASA Astrophysics Data System (ADS)

    Kang, Shishou; Jia, Zhiyong; Zoto, I.; Reed, D.; Nikles, David E.; Harrell, J. W.; Thompson, Gregory; Mankey, Gary; Krishnamurthy, Vemuru V.; Porcar, L.

    2006-04-01

    FePt and [FePt]95Au5 nanoparticles with an average size of about 4 nm were chemically synthesized and spin coated onto silicon substrates. Samples were subsequently thermally annealed at temperatures ranging from 250 to 500 °C for 30 min. Three-dimensional structural characterization was carried out with small-angle neutron scattering (SANS) and small-angle x-ray diffraction (SAXRD) measurements. For both FePt and [FePt]95Au5 particles before annealing, SANS measurements gave an in-plane coherence length parameter a=7.3 nm, while SAXRD measurements gave a perpendicular coherence length parameter c=12.0 nm. The ratio of c/a is about 1.64, indicating the as-made particle array has a hexagonal close-packed superstructure. For both FePt and FePtAu nanoparticles, the diffraction peaks shifted to higher angles and broadened with increasing annealing temperature. This effect corresponds to a shrinking of the nanoparticle array, followed by agglomeration and sintering of the nanoparticles, resulting in the eventual loss of positional order with increasing annealing temperature. The effect is more pronounced for FePtAu than for FePt. Dynamic coercivity measurements show that the FePtAu nanoparticles have both higher intrinsic coercivity and higher switching volume at the same annealing temperature. These results are consistent with previous studies that show that additive Au both lowers the chemical ordering temperature and promotes sintering.

  19. Visible light photoactivity of TiO2 loaded with monometallic (Au or Pt) and bimetallic (Au/Pt) nanoparticles

    NASA Astrophysics Data System (ADS)

    Gołąbiewska, Anna; Lisowski, Wojciech; Jarek, Marcin; Nowaczyk, Grzegorz; Zielińska-Jurek, Anna; Zaleska, Adriana

    2014-10-01

    TiO2 modified with monometallic (Au or Pt) and bimetallic (Au/Pt) nanoparticles have been prepared using a water-in-oil microemulsion system (water/AOT/cyclohexane) followed by calcination step. The effect of metal ratio, reducing agent type (NaBH4 or N2H4), TiO2 matrix type (P-25, ST-01, TiO-5, TiO2 nanotubes or TiO2 obtained by TIP hydrolysis) as well as calcination temperature (from 350 to 650 °C) were systematically investigated. Obtained photocatalysts were characterized by UV-vis diffuse-reflectance spectroscopy (DRS), BET surface area measurements, scanning transmission microscopy (STEM), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity under visible light (λ > 420 nm) has been estimated in phenol degradation reaction in aqueous phase. The results showed that phenol degradation rate under visible light in the presence of TiO2 loaded with Au/Pt nanoparticles differed from 0.7 to 2.2 μmol dm-3 min-1 for samples prepared using different reducing agent. Sodium borohydride (NaBH4) favors formation of smaller Au/Pt nanoparticles and higher amount gold in Au/Pt is in the form of electronegative species (Auδ-) resulted in higher photoactivity. TiO2 obtained by TIP hydrolysis in microemulsion system seems to be the best support for Au/Pt nanoparticles from all among investigated matrix. It was also observed that enhancement of calcination temperature from 450 to 650 °C resulted in rapid drop of Au/Pt-TiO2 photoactivity under visible light due to surface area shrinkage, crystal structure change and probably change in Au/Pt nanoparticles morphology.

  20. Controlling core/shell Au/FePt nanoparticle electrocatalysis via changing the core size and shell thickness.

    PubMed

    Sun, Xiaolian; Li, Dongguo; Guo, Shaojun; Zhu, Wenlei; Sun, Shouheng

    2016-02-01

    Using a modified seed-mediated method, we synthesized core/shell Au/FePt nanoparticles (NPs) with Au sizes of 4, 7, and 9 nm and the FePt shell was controlled to have similar FePt compositions and 0.5, 1, and 2 nm thickness. We studied both core and shell effects on electrochemical and electrocatalytic properties of the Au/FePt NPs, and found that the Au core did change the redox chemistry of the FePt shell and promoted its electrochemical oxidation of methanol. The catalytic activity was dependent on the FePt thicknesses, but not much on the Au core sizes, and the 1 nm FePt shell was found to be the optimal thickness for catalyzing methanol oxidation in 0.1 M HClO4 + 0.1 M methanol, offering not only high activity (1.19 mA cm(-2) at 0.5 V vs. Ag/AgCl), but also enhanced stability. Our studies demonstrate a general approach to the design and tuning of shell catalysis in the core/shell structure to achieve optimal catalysis for important electrochemical reactions.

  1. 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

  2. A Nanostructured Bifunctional platform for Sensing of Glucose Biomarker in Artificial Saliva: Synergy in hybrid Pt/Au surfaces.

    PubMed

    Raymundo-Pereira, Paulo A; Shimizu, Flávio M; Coelho, Dyovani; Piazzeta, Maria H O; Gobbi, Angelo L; Machado, Sergio A S; Oliveira, Osvaldo N

    2016-12-15

    We report on a bimetallic, bifunctional electrode where a platinum (Pt) surface was patterned with nanostructured gold (Au) fingers with different film thicknesses, which was functionalized with glucose oxidase (GOx) to yield a highly sensitive glucose biosensor. This was achieved by using selective adsorption of a self-assembled monolayer (SAM) onto Au fingers, which allowed GOx immobilization only onto the Au-SAM surface. This modified electrode was termed bifunctional because it allowed to simultaneously immobilize the biomolecule (GOx) on gold to catalyze glucose, and detect hydrogen peroxide on Pt sites. Optimized electrocatalytic activity was reached for the architecture Pt/Au-SAM/GOx with 50nm thickness of Au, where synergy between Pt and Au allowed for detection of hydrogen peroxide (H2O2) at a low applied potential (0V vs. Ag/AgCl). Detection was performed for H2O2 in the range between 4.7 and 102.7 nmol L(-1), with detection limit of 3.4×10(-9) mol L(-1) (3.4 nmol L(-1)) and an apparent Michaelis-Menten rate constant of 3.2×10(-6)molL(-1), which is considerably smaller than similar devices with monometallic electrodes. The methodology was validated by measuring glucose in artificial saliva, including in the presence of interferents. The synergy between Pt and Au was confirmed in electrochemical impedance spectroscopy measurements with an increased electron transfer, compared to bare Pt and Au electrodes. The approach for fabricating the reproducible bimetallic Pt/Au electrodes is entirely generic and may be explored for other types of biosensors and biodevices where advantage can be taken of the combination of the two metals. PMID:27399934

  3. A Nanostructured Bifunctional platform for Sensing of Glucose Biomarker in Artificial Saliva: Synergy in hybrid Pt/Au surfaces.

    PubMed

    Raymundo-Pereira, Paulo A; Shimizu, Flávio M; Coelho, Dyovani; Piazzeta, Maria H O; Gobbi, Angelo L; Machado, Sergio A S; Oliveira, Osvaldo N

    2016-12-15

    We report on a bimetallic, bifunctional electrode where a platinum (Pt) surface was patterned with nanostructured gold (Au) fingers with different film thicknesses, which was functionalized with glucose oxidase (GOx) to yield a highly sensitive glucose biosensor. This was achieved by using selective adsorption of a self-assembled monolayer (SAM) onto Au fingers, which allowed GOx immobilization only onto the Au-SAM surface. This modified electrode was termed bifunctional because it allowed to simultaneously immobilize the biomolecule (GOx) on gold to catalyze glucose, and detect hydrogen peroxide on Pt sites. Optimized electrocatalytic activity was reached for the architecture Pt/Au-SAM/GOx with 50nm thickness of Au, where synergy between Pt and Au allowed for detection of hydrogen peroxide (H2O2) at a low applied potential (0V vs. Ag/AgCl). Detection was performed for H2O2 in the range between 4.7 and 102.7 nmol L(-1), with detection limit of 3.4×10(-9) mol L(-1) (3.4 nmol L(-1)) and an apparent Michaelis-Menten rate constant of 3.2×10(-6)molL(-1), which is considerably smaller than similar devices with monometallic electrodes. The methodology was validated by measuring glucose in artificial saliva, including in the presence of interferents. The synergy between Pt and Au was confirmed in electrochemical impedance spectroscopy measurements with an increased electron transfer, compared to bare Pt and Au electrodes. The approach for fabricating the reproducible bimetallic Pt/Au electrodes is entirely generic and may be explored for other types of biosensors and biodevices where advantage can be taken of the combination of the two metals.

  4. Synthesis of thiolated Ag/Au bimetallic nanoclusters exhibiting an anti-galvanic reduction mechanism and composition-dependent fluorescence

    NASA Astrophysics Data System (ADS)

    Sun, Jian; Wu, Haoxi; Jin, Yongdong

    2014-04-01

    We report a direct one-pot approach, employing 11-mercaptoundecanoic acid (11-MUA) as a reducing and capping agent, for the preparation of fluorescent Ag/Au bimetallic nanoclusters (Ag/AuNCs) from HAuCl4 and AgNO3 in basic aqueous solution at room temperature. Unlike the monocomponent 11-MUA-AgNCs with negligible fluorescence, the as-prepared 11-MUA-Ag/AuNCs exhibit similar average diameters of ~1.8 nm but much stronger and tunable fluorescence by varying the concentration ratios of AgNO3 to HAuCl4 in the synthesis. The quantum yield of the 11-MUA-Ag/AuNCs can reach 6.81% at a Ag-to-Au molar ratio of 1 : 2, nearly 3-fold higher than the monocomponent 11-MUA-AuNCs (2.38%) of similar sizes. More importantly, the occurrence of the reaction between Ag+ ions and Au0 of 11-MUA-AuNCs (which is opposite to the classic galvanic theory) and the coexistence of Ag0 and Au+ in the final NC products, are revealed by thorough analysis of XPS data. The anti-galvanic reduction, that is, metal ions are replaced by less reactive metals, has been further demonstrated through the reaction between the as-obtained purified monocomponent 11-MUA-AuNCs and Ag+ ions. Direct electrochemical insights into the anti-galvanic reduction mechanism were provided by cyclic voltammetry characterizations of the NCs, and the universality of the anti-galvanic reduction was tested by preparing thiolated Pt/Au bimetallic NCs using platinum instead of silver in our synthetic system.We report a direct one-pot approach, employing 11-mercaptoundecanoic acid (11-MUA) as a reducing and capping agent, for the preparation of fluorescent Ag/Au bimetallic nanoclusters (Ag/AuNCs) from HAuCl4 and AgNO3 in basic aqueous solution at room temperature. Unlike the monocomponent 11-MUA-AgNCs with negligible fluorescence, the as-prepared 11-MUA-Ag/AuNCs exhibit similar average diameters of ~1.8 nm but much stronger and tunable fluorescence by varying the concentration ratios of AgNO3 to HAuCl4 in the synthesis. The quantum

  5. Sintering Behavior of Spin-coated FePt and FePtAu Nanoparticles

    SciTech Connect

    Kang, Shishou; Jia, Zhiyong; Zoto, Ilir; Reed, R. C.; Nikles, David E.; Harrell, J. W.; Vemuru, Krishnamurthy V; Porcar, L.

    2006-01-01

    FePt and [FePt]{sub 95}Au{sub 5} nanoparticles with an average size of about 4 nm were chemically synthesized and spin coated onto silicon substrates. Samples were subsequently thermally annealed at temperatures ranging from 250 to 500 C for 30 min. Three-dimensional structural characterization was carried out with small-angle neutron scattering (SANS) and small-angle x-ray diffraction (SAXRD) measurements. For both FePt and [FePt]{sub 95}Au{sub 5} particles before annealing, SANS measurements gave an in-plane coherence length parameter a = 7.3 nm, while SAXRD measurements gave a perpendicular coherence length parameter c = 12.0 nm. The ratio of c/a is about 1.64, indicating the as-made particle array has a hexagonal close-packed superstructure. For both FePt and FePtAu nanoparticles, the diffraction peaks shifted to higher angles and broadened with increasing annealing temperature. This effect corresponds to a shrinking of the nanoparticle array, followed by agglomeration and sintering of the nanoparticles, resulting in the eventual loss of positional order with increasing annealing temperature. The effect is more pronounced for FePtAu than for FePt. Dynamic coercivity measurements show that the FePtAu nanoparticles have both higher intrinsic coercivity and higher switching volume at the same annealing temperature. These results are consistent with previous studies that show that additive Au both lowers the chemical ordering temperature and promotes sintering.

  6. Level densities and thermodynamical properties of Pt and Au isotopes

    NASA Astrophysics Data System (ADS)

    Giacoppo, F.; Bello Garrote, F. L.; Bernstein, L. A.; Bleuel, D. L.; Eriksen, T. K.; Firestone, R. B.; Görgen, A.; Guttormsen, M.; Hagen, T. W.; Kheswa, B. V.; Klintefjord, M.; Koehler, P. E.; Larsen, A. C.; Nyhus, H. T.; Renstrøm, T.; Sahin, E.; Siem, S.; Tornyi, T.

    2014-11-01

    The nuclear level densities of Pt-196194 and Au,198197 below the neutron separation energy have been measured using transfer and scattering reactions. All the level density distributions follow the constant-temperature description. Each group of isotopes is characterized by the same temperature above the energy threshold corresponding to the breaking of the first Cooper pair. A constant entropy excess Δ S =1.9 kB and 1.1 kB is observed in 195Pt and 198Au with respect to 196Pt and 197Au, respectively, giving information on the available single-particle level space for the last unpaired valence neutron. The breaking of nucleon Cooper pairs is revealed by sequential peaks in the microcanonical caloric curve.

  7. Ion-irradiation induced chemical ordering of FePt and FePtAu nanoparticles

    NASA Astrophysics Data System (ADS)

    Seetala, Naidu V.; Harrell, J. W.; Lawson, Jeremy; Nikles, David E.; Williams, John R.; Isaacs-Smith, Tamara

    2005-12-01

    We have studied the effect of ion-beam irradiation on reducing the ordering temperature of FePt and FePtAu nanoparticles. FePt and FePt(Au14%) 4 nm particles dispersed on a Si-substrate were irradiated by 300 keV Al-ions with a dose of 1 × 1016 ions/cm2 at 43 °C using a water-cooled flange in order to minimize the vacancy migration and voids formation within the collision cascades. Partial chemical ordering has been observed in as-irradiated particles with coercivity of 60-130 Oe. Post-irradiation annealing at 220 °C enhanced chemical ordering in FePt nanoparticles with coercivity of 3500 Oe, magnetic anisotropy of 1.5 × 107 erg/cc, and thermal stability factor of 130. A much higher 375 °C post-irradiation annealing was required in FePtAu, presumably because Au atoms were trapped at Fe/Pt lattice sites at lower temperatures. As the annealing temperature increased, anomalous features in the magnetization reversal curves were observed that disappeared at higher annealing temperatures.

  8. 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

  9. 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

  10. 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.

  11. Robust Au-Ag-Au bimetallic atom-scale junctions fabricated by self-limited Ag electrodeposition at Au nanogaps.

    PubMed

    Hwang, Tai-Wei; Bohn, Paul W

    2011-10-25

    Atom-scale junctions (ASJs) exhibit quantum conductance behavior and have potential both for fundamental studies of adsorbate-mediated conductance in mesoscopic conductors and as chemical sensors. Electrochemically fabricated ASJs, in particular, show the stability needed for molecular detection applications. However, achieving physically robust ASJs at high yield is a challenge because it is difficult to control the direction and kinetics of metal deposition. In this work, a novel electrochemical approach is reported, in which Au-Ag-Au bimetallic ASJs are reproducibly fabricated from an initially prepared Au nanogap by sequential overgrowth and self-limited thinning. Applying a potential across specially prepared Au nanoelectrodes in the presence of aqueous Ag(I) leads to preferential galvanic reactions resulting in the deposition of Ag and the formation of an atom-scale junction between the electrodes. An external resistor is added in series with the ASJ to control self-termination, and adjusting solution chemical potential (concentration) is used to mediate self-thinning of junctions. The result is long-lived, mechanically stable ASJs that, unlike previous constructions, are stable in flowing solution, as well as to changes in solution media. These bimetallic ASJs exhibit a number of behaviors characteristic of quantum structures, including long-lived fractional conductance states, that are interpreted to arise from two or more quantized ASJs in series.

  12. Facile synthesis of PtAu alloy nanoparticles with high activity for formic acid oxidation

    SciTech Connect

    Zhang, Sheng; Shao, Yuyan; Yin, Geping; Lin, Yuehe

    2010-02-15

    We report the facile synthesis of carbon supported PtAu alloy nanoparticles with high electrocatalytic activity as the anode catalyst for direct formic acid fuel cells (DFAFCs). PtAu alloy nanopaticles are synthesized by co-reducing HAuCl4 and H2PtCl6 with NaBH4 in the presence of sodium citrate and then the nanoparticles are deposited on Vulcan XC-72R carbon support (PtAu/C). The obtained catalysts are characterized with X-ray diffraction (XRD) and transmission electron microscope (TEM), which reveal PtAu alloy formation with an average diameter of 4.6 nm. PtAu/C exhibits 8 times higher catalytic activity toward formic acid oxidation than Pt/C. The enhanced activity of PtAu/C catalyst is attributed to noncontinuous Pt sites formed in the presence of the neighbored Au sites, which promotes direct oxidation of formic acid by avoiding poison CO.

  13. Biosynthesis of Au, Ag and Au-Ag nanoparticles using edible mushroom extract

    NASA Astrophysics Data System (ADS)

    Philip, Daizy

    2009-07-01

    Integration of green chemistry principles to nanotechnology is one of the key issues in nanoscience research. There is growing need to develop environmentally benign metal nanoparticle synthesis process that do not use toxic chemicals in the synthesis protocols to avoid adverse effects in medical applications. Here, it is a report on extracellular synthesis method for the preparation of Au, Ag and Au-Ag nanoparticles in water, using the extract of Volvariella volvacea, a naturally occurring edible mushroom, as reducing and protecting agents. Gold nanoparticles of different sizes (20-150 nm) and shapes from triangular nanoprisms to nearly spherical and hexagonal are obtained by this novel method. The size and shape of gold nanoparticles are also found to depend on temperature of the extract. The silver nanoparticles are spherical with size ˜15 nm. There is increased productivity of nanoparticles as shown by sharp and intense surface plasmon resonance bands for the nanoparticles prepared using an excess of the extract. The Au-Ag nanoparticles prepared by co-reduction has only one plasmon band due to alloying of the constituents. All the synthesized nanoparticles are found to be photoluminescent and are highly crystalline as shown by SAED and XRD patterns with fcc phase oriented along the (1 1 1) plane. FTIR measurements were carried out to identify the possible biomolecules responsible for capping and efficient stabilization of the nanoparticles. It is found that Au nanoparticles are bound to proteins through free amino groups and silver nanoparticles through the carboxylate group of the amino acid residues. The position and intensity of the emission band is found to depend on composition of the nanoparticles indicating the possible use in therapeutic applications.

  14. Controlled Synthesis of Au@AgAu Yolk-Shell Cuboctahedra with Well-Defined Facets.

    PubMed

    Londono-Calderon, Alejandra; Bahena, Daniel; Yacaman, Miguel J

    2016-08-01

    The synthesis of Au@AgAu yolk-shell cuboctahedra nanoparticles formed by galvanic replacement in a seed-mediated method is described. Initially, single-crystal Au seeds are used for the formation of Au@Ag core-shell nanocubes, which serve as the template material for the deposition of an external Au layer. The well-controlled synthesis yields the formation of cuboctahedra nanoparticles with smooth inner and outer Au/Ag surfaces. The deposition/oxidation process is described to understand the formation of cuboctahedra and octahedra nanoparticles. The Au core maintains the initial morphology of the seed and remains static at the center of the yolk-shell because of residual Ag. Structural analysis of the shell indicates intrinsic stacking faults (SFs) near the surface. Energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) compositional analysis show an Au-Ag nonordered alloy forming the shell. The three-dimensional structure of the nanoparticles presented open facets on the [111] as observed by electron tomography SIRT reconstruction over a stack of high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images. The geometrical model was validated by analyzing the direction of streaks in coherent nanobeam diffraction (NBD). The catalytic activity was evaluated using a model reaction based on the reduction of 4-nitrophenol (4-NTP) by NaBH4 in the presence of Au@AgAu yolk-shell nanoparticles. PMID:27385583

  15. One pot aqueous synthesis of nanoporous Au85Pt15 material with surface bound Pt islands: an efficient methanol tolerant ORR catalyst

    NASA Astrophysics Data System (ADS)

    Anandha Ganesh, P.; Jeyakumar, D.

    2014-10-01

    For the first time, we are reporting the synthesis of Au100-xPtx nanoporous materials in the size range of 7-10 nm through the galvanic replacement of Ag by Pt from Au100-xAg2x spherical nano-alloys (x = 20, 15, 10 and 5) in an aqueous medium. The galvanic replacement reaction follows the `Volmer-Weber' growth mode, resulting in the formation of surface bound platinum islands on a nanoporous gold surface. The high angle annular dark field image and low angle X-ray diffraction studies confirm the presence of nanoporous Au100-xPtx NPs. The electrochemical studies using the Au85Pt15/C catalyst show excellent methanol tolerance behaviour and better performance towards oxygen reduction reaction (ORR) in terms of high mass activity, mass-specific activity and figure of merit (FOM) when compared to HiSPEC Pt/C commercial catalyst. Preliminary studies on a full cell using nanoporous Au85Pt15/C (loading 1.0 mg cm-2) as the cathode material and Pt-Ru/C (loading: 0.5 mg cm-2) as the anode material performed better (38 mW cm-2) than the HiSPEC Pt/C cathode material (16 mW cm-2).For the first time, we are reporting the synthesis of Au100-xPtx nanoporous materials in the size range of 7-10 nm through the galvanic replacement of Ag by Pt from Au100-xAg2x spherical nano-alloys (x = 20, 15, 10 and 5) in an aqueous medium. The galvanic replacement reaction follows the `Volmer-Weber' growth mode, resulting in the formation of surface bound platinum islands on a nanoporous gold surface. The high angle annular dark field image and low angle X-ray diffraction studies confirm the presence of nanoporous Au100-xPtx NPs. The electrochemical studies using the Au85Pt15/C catalyst show excellent methanol tolerance behaviour and better performance towards oxygen reduction reaction (ORR) in terms of high mass activity, mass-specific activity and figure of merit (FOM) when compared to HiSPEC Pt/C commercial catalyst. Preliminary studies on a full cell using nanoporous Au85Pt15/C (loading 1.0 mg

  16. 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.

  17. 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.

  18. Single-crystalline octahedral Au-Ag nanoframes.

    PubMed

    Hong, Xun; Wang, Dingsheng; Cai, Shuangfei; Rong, Hongpan; Li, Yadong

    2012-11-01

    We report the formation of single-crystalline octahedral Au-Ag nanoframes by a modified galvanic replacement reaction. Upon sequential addition of AgNO(3), CuCl, and HAuCl(4) to octadecylamine solution, truncated polyhedral silver nanoparticles formed first and then changed into octahedral Au-Ag nanoframes, without requiring a conventional Ag removal step with additional oxidation etchant. The nanoframes have 12 sides, and all of the eight {111} faces are empty. The side grows along the [110] direction, and the diameter is less than 10 nm. The selective gold deposition on the high-energy (110) surface, the diffusion, and the selective redeposition of Au and Ag atoms are the key reasons for the formation of octahedral nanoframes.

  19. Melting curve of metals Cu, Ag and Au under pressure

    NASA Astrophysics Data System (ADS)

    Tam, Pham Dinh; Hoc, Nguyen Quang; Tinh, Bui Duc; Tan, Pham Duy

    2016-01-01

    In this paper, the dependence of the melting temperature of metals Cu, Ag and Au under pressure in the interval from 0 kbar to 40 kbar is studied by the statistical moment method (SMM). This dependence has the form of near linearity and the calculated slopes of melting curve are 3.9 for Cu, 5.7 for Ag and 6 for Au. These results are in good agreement with the experimental data.

  20. Herringbone and triangular patterns of dislocations in Ag, Au, and AgAu alloy films on Ru(0001).

    SciTech Connect

    Thayer, Gayle Echo; de la Figuera, Juan; Bartelt, Norman Charles; Carter, C. Barrington; Hwang, R. Q.; Thurmer, Konrad; Ling, W. L.; Hamilton, John C.; McCarty, Kevin F.

    2008-10-01

    We have studied the dislocation structures that occur in films of Ag, Au, and Ag{sub 0.5}Au{sub 0.5} alloy on a Ru(0001) substrate. Monolayer (ML) films form herringbone phases while films two or more layers thick contain triangular patterns of dislocations. We use scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) to determine how the film composition affects the structure and periodicity of these ordered structures. One layer of Ag forms two different herringbone phases depending on the exact Ag coverage and temperature. Low-energy electron microscopy (LEEM) establishes that a reversible, first-order phase transition occurs between these two phases at a certain temperature. We critically compare our 1 ML Ag structures to conflicting results from an X-ray scattering study [H. Zajonz et al., Phys. Rev. B 67 (2003) 155417]. Unlike Ag, the herringbone phases of Au and AgAu alloy are independent of the exact film coverage. For two layer films in all three systems, none of the dislocations in the triangular networks thread into the second film layer. In all three systems, the in-plane atomic spacing of the second film layer is nearly the same as in the bulk. Film composition does, however, affect the details of the two layer structures. Ag and Au films form interconnected networks of dislocations, which we refer to as 'trigons.' In 2 ML AgAu alloy, the dislocations form a different triangular network that shares features of both trigon and moire structures. Yet another well-ordered structure, with square symmetry, forms at the boundaries of translational trigon domains in 2 ML Ag films but not in Au films.

  1. The extraction characteristic of Au-Ag from Au concentrate by thiourea solution

    NASA Astrophysics Data System (ADS)

    Kim, Bongju; Cho, Kanghee; On, Hyunsung; Choi, Nagchoul; Park, Cheonyoung

    2013-04-01

    The cyanidation process has been used commercially for the past 100 years, there are ores that are not amenable to treatment by cyanide. Interest in alternative lixiviants, such as thiourea, halogens, thiosulfate and malononitrile, has been revived as a result of a major increase in gold price, which has stimulated new developments in extraction technology, combined with environmental concern. The Au extraction process using the thiourea solvent has many advantages over the cyanidation process, including higher leaching rates, faster extraction time and less than toxicity. The purpose of this study was investigated to the extraction characteristic of Au-Ag from two different Au concentrate (sulfuric acid washing and roasting) under various experiment conditions (thiourea concentration, pH of solvent, temperature) by thiourea solvent. The result of extraction experiment showed that the Au-Ag extraction was a fast extraction process, reaching equilibrium (maximum extraction rate) within 30 min. The Au-Ag extraction rate was higher in the roasted concentrate than in the sulfuric acid washing. The higher the Au-Ag extraction rate (Au - 70.87%, Ag - 98.12%) from roasted concentrate was found when the more concentration of thiourea increased, pH decreased and extraction temperature increased. This study informs extraction method basic knowledge when thiourea was a possibility to eco-/economic resources of Au-Ag utilization studies including the hydrometallurgy.

  2. Pt- and Au-induced monodirectional nanowires on Ge(110)

    NASA Astrophysics Data System (ADS)

    Watanabe, T.; Yamada, Y.; Sasaki, M.; Sakai, S.; Yamauchi, Y.

    2016-11-01

    The adsorption of Pt or Au on Ge(110) and subsequent annealing resulted in formation of well-ordered monodirectional nanowires (NWs) throughout the surface over a cm-scale. The NWs were aligned along the [ 1 1 bar 0] direction, independent of the surface reconstruction of Ge(110). Metastable-atom deexcitation spectroscopy of Pt-NWs revealed that the topmost part of the NWs comprised Ge atoms, suggesting the exchange of the Ge and metal atoms, leaving an ultrathin Ge layer on top of the NWs. The increase in the electronic density of state near the Fermi energy was observed from both the MDS and UPS spectra of the Pt-NWs, suggesting a metallicity of the NWs.

  3. Photoreduction of Ag+ in Ag/Ag2S/Au memristor

    NASA Astrophysics Data System (ADS)

    Mou, N. I.; Tabib-Azar, M.

    2015-06-01

    Silver halides and chalcogenides are excellent memristor materials that have been extensively used in the past as photosensitive layers in photography. Here we examine the effect of illumination on the operating voltages and switching speed of Ag/Ag2S/Au memristors using a green laser (473-523 nm). Our results indicate that illumination decreases the average switching time from high to low resistance states by ∼19% and decreases the turn-off voltages dramatically from -0.8 V to -0.25 V that we attribute to the change in sulfur valency and a photo-induced change in its oxidation/reduction potential. Photo-induced reduction of silver in Ag2S may be used in three dimensional optical memories that can be electronically read and reset.

  4. Synthesis and electrocatalytic activity of Au/Pt bimetallic nanodendrites for ethanol oxidation in alkaline medium.

    PubMed

    Han, Xinyi; Wang, Dawei; Liu, Dong; Huang, Jianshe; You, Tianyan

    2012-02-01

    Gold/Platinum (Au/Pt) bimetallic nanodendrites were successfully synthesized through seeded growth method using preformed Au nanodendrites as seeds and ascorbic acid as reductant. Cyclic voltammograms (CVs) of a series of Au/Pt nanodendrites modified electrodes in 1M KOH solution containing 1M ethanol showed that the electrocatalyst with a molar ratio (Au:Pt) of 3 exhibited the highest peak current density and the lowest onset potential. The peak current density of ethanol electro-oxidation on the Au(3)Pt(1) nanodendrites modified glassy carbon electrode (Au(3)Pt(1) electrode) is about 16, 12.5, and 4.5 times higher than those on the polycrystalline Pt electrode, polycrystalline Au electrode, and Au nanodendrites modified glassy carbon electrode (Au dendrites electrode), respectively. The oxidation peak potential of ethanol electro-oxidation on the Au(3)Pt(1) electrode is about 299 and 276 mV lower than those on the polycrystalline Au electrode and Au dendrites electrode, respectively. These results demonstrated that the Au/Pt bimetallic nanodendrites may find potential application in alkaline direct ethanol fuel cells (ADEFCs).

  5. Virus-templated Au and Au/Pt Core/shell Nanowires and Their Electrocatalytic Activitives for Fuel Cell Applications

    PubMed Central

    LEE, YOUJIN; KIM, JUNHYUNG; YUN, DONG SOO; NAM, YOON SUNG; SHAO-HORN, YANG; BELCHER, ANGELA M.

    2014-01-01

    A facile synthetic route was developed to make Au nanowires (NWs) from surfactant-mediated bio-mineralization of a genetically engineered M13 phage with specific Au binding peptides. From the selective interaction between Au binding M13 phage and Au ions in aqueous solution, Au NWs with uniform diameter were synthesized at room temperature with yields greater than 98 % without the need for size selection. The diameters of Au NWs were controlled from 10 nm to 50 nm. The Au NWs were found to be active for electrocatalytic oxidation of CO molecules for all sizes, where the activity was highly dependent on the surface facets of Au NWs. This low-temperature high yield method of preparing Au NWs was further extended to the synthesis of Au/Pt core/shell NWs with controlled coverage of Pt shell layers. Electro-catalytic studies of ethanol oxidation with different Pt loading showed enhanced activity relative to a commercial supported Pt catalyst, indicative of the dual functionality of Pt for the ethanol oxidation and Au for the anti-poisoning component of Pt. These new one-dimensional noble metal NWs with controlled compositions could facilitate the design of new alloy materials with tunable properties. PMID:24910712

  6. Study on antibacterial activity of chemically synthesized PANI-Ag-Au nanocomposite

    NASA Astrophysics Data System (ADS)

    Boomi, Pandi; Prabu, Halliah Gurumallesh; Manisankar, Paramasivam; Ravikumar, Sundaram

    2014-05-01

    Pristine polyaniline (PANI), PANI-Ag, PANI-Au and PANI-Ag-Au nanocomposites have been successfully synthesized by chemical oxidative polymerization method using aniline as monomer, ammonium persulphate as oxidant and metal (Ag, Au and Ag-Au) colloids. UV-Vis analysis exhibited surface Plasmon resonances of Ag, Au, Ag-Au nanoparticles. FT-IR spectra revealed the shift in peak position of N-H stretching. X-ray diffraction (XRD) results confirm the presence of Ag, Au and Au-Ag nanoparticles. HR-TEM images show nanosizes of Ag, Au, Ag-Au and the incorporation of such nanoparticles into the PANI matrix. Pristine PANI, PANI-Ag, PANI-Au and PANI-Ag-Au nanocomposites were tested for antibacterial activity by agar well diffusion method. PANI-Ag-Au nanocomposite exhibited higher antibacterial activity against both gram-positive [Streptococcus sp. (MTCC 890), Staphylococcus sp. (MTCC 96)] and gram-negative bacteria [Escherichia coli (MTCC 1671) and Klebsiella sp. (MTCC 7407)] when compared with PANI-Ag nanocomposite, PANI-Au nanocomposite and pristine PANI. The novelty of this study is the polymer-bimetal synthesis and its antibacterial potential.

  7. Rationalization of Au concentration and distribution in AuNi@Pt core-shell nanoparticles for oxygen reduction reaction

    SciTech Connect

    An, Wei; Liu, Ping

    2015-09-18

    Improving the activity and stability of Pt-based core–shell nanocatalysts for proton exchange membrane fuel cells while lowering Pt loading has been one of the big challenges in electrocatalysis. Here, using density functional theory, we report the effect of adding Au as the third element to enhance the durability and activity of Ni@Pt core–shell nanoparticles (NPs) during the oxygen reduction reaction (ORR). Our results show that the durability and activity of a Ni@Pt NP can be finely tuned by controlling Au concentration and distribution. For a NiAu@Pt NP, the durability can be greatly promoted by thermodynamically favorable segregation of Au to replace the Pt atoms at vertex, edge, and (100) facets on the shell, while still keeping the ORR activity on the active Pt(111) shell as high as that of Ni@Pt nanoparticles. Such behavior strongly depends on a direct interaction with the Ni interlayer. The results not only highlight the importance of interplay between surface strain on the shell and the interlayer–shell interaction in determining the durability and activity but also provide guidance on how to maximize the usage of Au to optimize the performance of core–shell (Pt) nanoparticles. As a result, such understanding has allowed us to discover a novel NiAu@Pt nanocatalyst for the ORR.

  8. Rationalization of Au concentration and distribution in AuNi@Pt core-shell nanoparticles for oxygen reduction reaction

    DOE PAGES

    An, Wei; Liu, Ping

    2015-09-18

    Improving the activity and stability of Pt-based core–shell nanocatalysts for proton exchange membrane fuel cells while lowering Pt loading has been one of the big challenges in electrocatalysis. Here, using density functional theory, we report the effect of adding Au as the third element to enhance the durability and activity of Ni@Pt core–shell nanoparticles (NPs) during the oxygen reduction reaction (ORR). Our results show that the durability and activity of a Ni@Pt NP can be finely tuned by controlling Au concentration and distribution. For a NiAu@Pt NP, the durability can be greatly promoted by thermodynamically favorable segregation of Au tomore » replace the Pt atoms at vertex, edge, and (100) facets on the shell, while still keeping the ORR activity on the active Pt(111) shell as high as that of Ni@Pt nanoparticles. Such behavior strongly depends on a direct interaction with the Ni interlayer. The results not only highlight the importance of interplay between surface strain on the shell and the interlayer–shell interaction in determining the durability and activity but also provide guidance on how to maximize the usage of Au to optimize the performance of core–shell (Pt) nanoparticles. As a result, such understanding has allowed us to discover a novel NiAu@Pt nanocatalyst for the ORR.« less

  9. Ag on Pt(111): Changes in Electronic and CO Adsorption Properties upon PtAg/Pt(111) Monolayer Surface Alloy Formation.

    PubMed

    Diemant, Thomas; Schüttler, Konstantin M; Behm, R Jürgen

    2015-10-01

    The electronic and chemical (adsorption) properties of bimetallic Ag/Pt(111) surfaces and their modification upon surface alloy formation, that is, during intermixing of Ag and Pt atoms in the top atomic layer upon annealing, were studied by X-ray photoelectron spectroscopy (XPS) and, using CO as probe molecule, by temperature-programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRRAS), respectively. The surface alloys are prepared by deposition of sub-monolayer Ag amounts on a Pt(111) surface at room temperature, leading to extended Ag monolayer islands on the substrate, and subsequent annealing of these surfaces. Surface alloy formation starts at ≈600-650 K, which is evidenced by core-level shifts (CLSs) of the Ag(3d5/2 ) signal. A distinct change of the CO adsorption properties is observed when going to the intermixed PtAg surface alloys. Most prominently, we find the growth of a new desorption feature at higher temperature (≈550 K) in the TPD spectra upon surface alloy formation. This goes along with a shift of the COad -related IR bands to lower wave number. Surface alloy formation is almost completed after heating to 700 K.

  10. A comparative theoretical study for the methanol dehydrogenation to CO over Pt3 and PtAu2 clusters.

    PubMed

    Zhong, Wenhui; Liu, Yuxia; Zhang, Dongju

    2012-07-01

    The density functional theory (DFT) calculations are carried out to study the mechanism details and the ensemble effect of methanol dehydrogenation over Pt(3) and PtAu(2) clusters, which present the smallest models of pure Pt clusters and bimetallic PtAu clusters. The energy diagrams are drawn out along both the initial O-H and C-H bond scission pathways via the four sequential dehydrogenation processes, respectively, i.e., CH(3)OH → CH(2)OH → CH(2)O → CHO → CO and CH(3)OH → CH(3)O → CH(2)O → CHO → CO, respectively. It is revealed that the reaction kinetics over PtAu(2) is significantly different from that over Pt(3). For the Pt(3)-mediated reaction, the C-H bond scission pathway, where an ensemble composed of two Pt atoms is required to complete methanol dehydrogenation, is energetically more favorable than the O-H bond scission pathway, and the maximum barrier along this pathway is calculated to be 12.99 kcal mol(-1). In contrast, PtAu(2) cluster facilitates the reaction starting from the O-H bond scission, where the Pt atom acts as the active center throughout each elementary step of methanol dehydrogenation, and the initial O-H bond scission with a barrier of 21.42 kcal mol(-1) is the bottom-neck step of methanol decomposition. Importantly, it is shown that the complete dehydrogenation product of methanol, CO, can more easily dissociate from PtAu(2) cluster than from Pt(3) cluster. The calculated results over the model clusters provide assistance to some extent for understanding the improved catalytic activity of bimetal PtAu catalysts toward methanol oxidation in comparison with pure Pt catalysts. PMID:22160734

  11. Simultaneous tunable structure and composition of PtAg alloyed nanocrystals as superior catalysts.

    PubMed

    Fang, Caihong; Zhao, Jun; Zhao, Guili; Kuai, Long; Geng, Baoyou

    2016-08-11

    PtAg alloyed nanostructural catalysts were firstly prepared by co-reduction of AgNO3 and H2PtCl6 precursors in growth solution using a seed-mediated method. By simply changing the molar ratio of the metal precursors, the morphologies of the porous alloyed nanocrystals can be tuned from multipetals to multioctahedra. Simultaneously, the alloy composition can be varied from Pt76Ag24 to Pt66Ag34. The catalytic properties of the prepared PtAg alloyed nanocrystals with a tunable structure and composition were tentatively examined by choosing the reduction of 4-nitrophenol with NaBH4. The reaction rate normalized to the concentration of catalysts was calculated to be 318.9 s(-1) mol(-1) L and 277.4 s(-1) mol(-1) L for Pt70Ag30 and Pt66Ag34 porous catalysts, which is much higher than the pure Pt catalysts. Moreover, PtAg nanostructures can also serve as efficient electrocatalysts toward the methanol oxidation reaction, especially for Pt70Ag30 and Pt66Ag34 porous nanocrystals. The electrocatalytic activity and the durability were both highly enhanced compared to the commercial Pt/C catalyst. In addition, we also investigated the enhancement mechanism.

  12. Green synthesis and characterization of Au@Pt core-shell bimetallic nanoparticles using gallic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Guojun; Zheng, Hongmei; Shen, Ming; Wang, Lei; Wang, Xiaosan

    2015-06-01

    In this study, we developed a facile and benign green synthesis approach for the successful fabrication of well-dispersed urchin-like Au@Pt core-shell nanoparticles (NPs) using gallic acid (GA) as both a reducing and protecting agent. The proposed one-step synthesis exploits the differences in the reduction potentials of AuCl4- and PtCl62-, where the AuCl4- ions are preferentially reduced to Au cores and the PtCl62- ions are then deposited continuously onto the Au core surface as a Pt shell. The as-prepared Au@Pt NPs were characterized by transmission electron microscope (TEM); high-resolution transmission electron microscope (HR-TEM); scanning electron microscope (SEM); UV-vis absorption spectra (UV-vis); X-ray diffraction (XRD); Fourier transmission infrared spectra (FT-IR). We systematically investigated the effects of some experimental parameters on the formation of the Au@Pt NPs, i.e., the reaction temperature, the molar ratios of HAuCl4/H2PtCl6, and the amount of GA. When polyvinylpyrrolidone K-30 (PVP) was used as a protecting agent, the Au@Pt core-shell NPs obtained using this green synthesis method were better dispersed and smaller in size. The as-prepared Au@Pt NPs exhibited better catalytic activity in the reaction where NaBH4 reduced p-nitrophenol to p-aminophenol. However, the results showed that the Au@Pt bimetallic NPs had a lower catalytic activity than the pure Au NPs obtained by the same method, which confirmed the formation of Au@Pt core-shell nanostructures because the active sites on the surfaces of the Au NPs were covered with a Pt shell.

  13. Characterization of Pt-Au and Ni-Au Clusters on TiO(2)(110)

    SciTech Connect

    Chen, D. A.; Mullins, David R; Ratliff, J. S.; He, Wei; Tenney, Samuel

    2011-01-01

    The surface composition and properties of Pt-Au and Ni-Au clusters on TiO{sub 2}(110) have been studied by scanning tunneling microscopy (STM), low energy ion scattering (LEIS) and soft X-ray photoelectron spectroscopy (sXPS). STM studies show that bimetallic clusters are formed during sequential deposition of the two metals, regardless of the order of deposition. At the 2 ML of Au/2 ML of Pt or Ni coverages studied here, the second metal contributes to the growth of existing clusters rather than forming new pure metal clusters. LEIS experiments demonstrate that the surfaces of the bimetallic clusters are almost 100% Au when 2 ML of Au is deposited on top of 2 ML of Pt or Ni. However, a much larger fraction of Pt or Ni (50 and 20%, respectively) remains at the surface when 2 ML of Pt or Ni is deposited on 2 ML of Au, most likely due to limited diffusion of atoms within the clusters at room temperature. According to sXPS investigations, the binding energies of the metals in the bimetallic clusters are shifted from those observed for pure metal clusters; the Pt(4f{sub 7/2}) and Ni(3p{sub 3/2}) peaks are shifted to lower binding energies while the position of the Au(4f{sub 7/2}) peak is dominated by surface core level shifts. Pure Pt clusters as well as 0.4 ML of Au on 2 ML of Pt clusters reduce the titania support upon encapsulation after annealing to 800 K, whereas 2 ML of Au on 2 ML of Pt clusters do not reduce titania, presumably because there is no Pt at the surface of the clusters. Pure Ni clusters are also known to become encapsulated upon heating, but the reduction of titania is much less extensive compared to that of pure Pt clusters.

  14. Characterization of Pt-Au and Ni-Au Clusters on TiO2(110)

    SciTech Connect

    S Tenney; W He; J Ratliff; D Mullins; D Chen

    2011-12-31

    The surface composition and properties of Pt-Au and Ni-Au clusters on TiO{sub 2}(110) have been studied by scanning tunneling microscopy (STM), low energy ion scattering (LEIS) and soft X-ray photoelectron spectroscopy (sXPS). STM studies show that bimetallic clusters are formed during sequential deposition of the two metals, regardless of the order of deposition. At the 2 ML of Au/2 ML of Pt or Ni coverages studied here, the second metal contributes to the growth of existing clusters rather than forming new pure metal clusters. LEIS experiments demonstrate that the surfaces of the bimetallic clusters are almost 100% Au when 2 ML of Au is deposited on top of 2 ML of Pt or Ni. However, a much larger fraction of Pt or Ni (50 and 20%, respectively) remains at the surface when 2 ML of Pt or Ni is deposited on 2 ML of Au, most likely due to limited diffusion of atoms within the clusters at room temperature. According to sXPS investigations, the binding energies of the metals in the bimetallic clusters are shifted from those observed for pure metal clusters; the Pt(4f{sub 7/2}) and Ni(3p{sub 3/2}) peaks are shifted to lower binding energies while the position of the Au(4f{sub 7/2}) peak is dominated by surface core level shifts. Pure Pt clusters as well as 0.4 ML of Au on 2 ML of Pt clusters reduce the titania support upon encapsulation after annealing to 800 K, whereas 2 ML of Au on 2 ML of Pt clusters do not reduce titania, presumably because there is no Pt at the surface of the clusters. Pure Ni clusters are also known to become encapsulated upon heating, but the reduction of titania is much less extensive compared to that of pure Pt clusters.

  15. A Selective Blocking Method To Control the Overgrowth of Pt on Au Nanorods

    PubMed Central

    2013-01-01

    A method for the preparation of smooth deposits of Pt on Au nanorods is described, involving sequential deposition steps with selective blocking of surface sites that reduces Pt-on-Pt deposition. The Au–Pt nanorods prepared by this method have higher long-term stability than those prepared by standard Pt deposition. Electrochemical data show that the resulting structure has more extended regions of Pt surface and enhanced activity toward the carbon monoxide oxidation and oxygen reduction reactions. PMID:23594230

  16. Ru, Re, Os, Pt and Au in iron meteorites

    NASA Technical Reports Server (NTRS)

    Pernicka, Ernst; Wasson, John T.

    1987-01-01

    Neutron activation analysis is used to ascertain the proportions of Ru, Re, Os, and Pt refractory siderophiles, and moderately volatile Au, in 41 iron meteorites. The Ni-element trends defined for groups IID and IIIF support a magmatic origin; in addition, the results obtained for groups IAB and IIICD contrast with trends observed in magmatic groups, where the Ru and Pt slopes are substantially less steep. In group IIIAB, at Ni concentrations above 90 mg/g, the steep decrease of Re, Os, and Ir with Ni levels off, and the interelement ratios exhibit considerable scatter. These observations may be explained in terms of the contamination of the residual molten core with small amounts of late primitive melts draining from the mantle.

  17. Understanding the structural properties and thermal stabilities of Au-Pd-Pt trimetallic clusters

    NASA Astrophysics Data System (ADS)

    Zhao, Zheng; Li, Mingjiang; Cheng, Daojian; Zhu, Jiqin

    2014-09-01

    In this work, surface segregation phenomena of Au-Pd-Pt trimetallic clusters are investigated by using semi-grand Monte Carlo simulations based on the Gupta potential. It is found that Au atoms are systematically segregated on the surface of the Au-Pd-Pt clusters (6-24 at.% higher than the overall Au concentration), due to the competition among the surface energies of Au, Pd, and Pt. The melting properties of Au-Pd-Pt trimetallic clusters with different composition and size are investigated by using molecular dynamics simulations, based on the same Gupta potential. It is found that the Au-Pd-Pt trimetallic cluster with the highest melting point corresponds to the one with the most stable structure. In addition, linear decrease in cluster melting point with the inverse cluster diameter is predicted for both pure and trimetallic clusters, which is well-known as the Pawlow's law.

  18. Adaptive Crystal Structures: CuAu and NiPt

    NASA Astrophysics Data System (ADS)

    Sanati, M.; Wang, L. G.; Zunger, Alex

    2003-01-01

    We discover that Au-rich Cu1-xAux and Pt-rich Ni1-xPtx contain a composition range in which there is a quasicontinuum of stable, ordered “adaptive structures” made of (001) repeat units of simple structural motifs. This is found by searching ˜3×106 different fcc configurations whose energies are parametrized via a “cluster expansion” of first-principles-calculated total energies of just a few structures. This structural adaptivity is explained in terms of an anisotropic, long-range strain energy.

  19. Pt skin on AuCu intermetallic substrate: a strategy to maximize Pt utilization for fuel cells.

    PubMed

    Wang, Gongwei; Huang, Bing; Xiao, Li; Ren, Zhandong; Chen, Hao; Wang, Deli; Abruña, Héctor D; Lu, Juntao; Zhuang, Lin

    2014-07-01

    The dependence on Pt catalysts has been a major issue of proton-exchange membrane (PEM) fuel cells. Strategies to maximize the Pt utilization in catalysts include two main approaches: to put Pt atoms only at the catalyst surface and to further enhance the surface-specific catalytic activity (SA) of Pt. Thus far there has been no practical design that combines these two features into one single catalyst. Here we report a combined computational and experimental study on the design and implementation of Pt-skin catalysts with significantly improved SA toward the oxygen reduction reaction (ORR). Through screening, using density functional theory (DFT) calculations, a Pt-skin structure on AuCu(111) substrate, consisting of 1.5 monolayers of Pt, is found to have an appropriately weakened oxygen affinity, in comparison to that on Pt(111), which would be ideal for ORR catalysis. Such a structure is then realized by substituting the Cu atoms in three surface layers of AuCu intermetallic nanoparticles (AuCu iNPs) with Pt. The resulting Pt-skinned catalyst (denoted as Pt(S)AuCu iNPs) has been characterized in depth using synchrotron XRD, XPS, HRTEM, and HAADF-STEM/EDX, such that the Pt-skin structure is unambiguously identified. The thickness of the Pt skin was determined to be less than two atomic layers. Finally the catalytic activity of Pt(S)AuCu iNPs toward the ORR was measured via rotating disk electrode (RDE) voltammetry through which it was established that the SA was more than 2 times that of a commercial Pt/C catalyst. Taking into account the ultralow Pt loading in Pt(S)AuCu iNPs, the mass-specific catalytic activity (MA) was determined to be 0.56 A/mg(Pt)@0.9 V, a value that is well beyond the DOE 2017 target for ORR catalysts (0.44 A/mg(Pt)@0.9 V). These findings provide a strategic design and a realizable approach to high-performance and Pt-efficient catalysts for fuel cells.

  20. The mechanism of Ag top layer on the coercivity enhancement of FePt thin films

    SciTech Connect

    Zhao, Z.L.; Ding, J.; Yi, J.B.; Chen, J.S.; Zeng, J.H.; Wang, J.P.

    2005-05-15

    The magnetic properties of the FePt thin films with a Ag top layer prepared by magnetron sputtering have been studied. With 4 nm Ag layer deposited right after the deposition of FePt layer, the ordering temperature of the L1{sub 0} FePt phase decreased to 350 deg. C or below. X-ray photoelectron spectroscopy results indicate that Ag has diffused into the FePt layer when Ag was deposited at 350 deg. C, while Ag remains on the top of the FePt when Ag was deposited at room temperature. The Ag top layer deposited at 350 deg. C was also found to protect the FePt layer from oxidation.

  1. Hollow octahedral and cuboctahedral nanocrystals of ternary Pt-Ni-Au alloys

    NASA Astrophysics Data System (ADS)

    Shviro, Meital; Polani, Shlomi; Zitoun, David

    2015-08-01

    Hollow particles of Pt-Ni-Au alloys have been prepared through a two-step reaction with the synthesis of NiPt octahedral and cuboctahedral templates followed by a galvanic replacement reaction by Au(iii). Metal etching presents an efficient method to yield hollow particles and investigate the Au diffusion in the metallic Pt-Ni framework through macroscopic (X-ray diffraction and SQUID magnetic measurement) and microscopic (HRTEM and STEM) measurements. The hollow particles retain the shape of the original nanocrystals. The nucleation of Au is found to be induced preferentially on the tip of the polyhedral nanocrystals while the etching of Ni starts from the facets leaving hollow octahedral particles consisting of 2 nm thick edges. In the presence of oleylamine, the Au tip grows and yields a heterogeneous dimer hollow-NiPt/Au. Without oleylamine, the Au nucleation is followed by Au diffusion in the Ni/Pt framework to yield a hollow single crystal Pt-Ni-Au alloy. The Pt-Ni-Au alloyed particles display a superparamagnetic behavior at room temperature.

  2. Plasmon Mapping in Au@Ag Nanocube Assemblies

    PubMed Central

    2014-01-01

    Surface plasmon modes in metallic nanostructures largely determine their optoelectronic properties. Such plasmon modes can be manipulated by changing the morphology of the nanoparticles or by bringing plasmonic nanoparticle building blocks close to each other within organized assemblies. We report the EELS mapping of such plasmon modes in pure Ag nanocubes, Au@Ag core–shell nanocubes, and arrays of Au@Ag nanocubes. We show that these arrays enable the creation of interesting plasmonic structures starting from elementary building blocks. Special attention will be dedicated to the plasmon modes in a triangular array formed by three nanocubes. Because of hybridization, a combination of such nanotriangles is shown to provide an antenna effect, resulting in strong electrical field enhancement at the narrow gap between the nanotriangles. PMID:25067991

  3. Dependence of SERS enhancement on the chemical composition and structure of Ag/Au hybrid nanoparticles.

    PubMed

    Chaffin, Elise; O'Connor, Ryan T; Barr, James; Huang, Xiaohua; Wang, Yongmei

    2016-08-01

    Noble metal nanoparticles (NPs) such as silver (Ag) and gold (Au) have unique plasmonic properties that give rise to surface enhanced Raman scattering (SERS). Generally, Ag NPs have much stronger plasmonic properties and, hence, provide stronger SERS signals than Au NPs. However, Ag NPs lack the chemical stability and biocompatibility of comparable Au NPs and typically exhibit the most intense plasmonic resonance at wavelengths much shorter than the optimal spectral region for many biomedical applications. To overcome these issues, various experimental efforts have been devoted to the synthesis of Ag/Au hybrid NPs for the purpose of SERS detections. However, a complete understanding on how the SERS enhancement depends on the chemical composition and structure of these nanoparticles has not been achieved. In this study, Mie theory and the discrete dipole approximation have been used to calculate the plasmonic spectra and near-field electromagnetic enhancements of Ag/Au hybrid NPs. In particular, we discuss how the electromagnetic enhancement depends on the mole fraction of Au in Ag/Au alloy NPs and how one may use extinction spectra to distinguish between Ag/Au alloyed NPs and Ag-Au core-shell NPs. We also show that for incident laser wavelengths between ∼410 nm and 520 nm, Ag/Au alloyed NPs provide better electromagnetic enhancement than pure Ag, pure Au, or Ag-Au core-shell structured NPs. Finally, we show that silica-core Ag/Au alloy shelled NPs provide even better performance than pure Ag/Au alloy or pure solid Ag and pure solid Au NPs. The theoretical results presented will be beneficial to the experimental efforts in optimizing the design of Ag/Au hybrid NPs for SERS-based detection methods. PMID:27497571

  4. Dependence of SERS enhancement on the chemical composition and structure of Ag/Au hybrid nanoparticles

    NASA Astrophysics Data System (ADS)

    Chaffin, Elise; O'Connor, Ryan T.; Barr, James; Huang, Xiaohua; Wang, Yongmei

    2016-08-01

    Noble metal nanoparticles (NPs) such as silver (Ag) and gold (Au) have unique plasmonic properties that give rise to surface enhanced Raman scattering (SERS). Generally, Ag NPs have much stronger plasmonic properties and, hence, provide stronger SERS signals than Au NPs. However, Ag NPs lack the chemical stability and biocompatibility of comparable Au NPs and typically exhibit the most intense plasmonic resonance at wavelengths much shorter than the optimal spectral region for many biomedical applications. To overcome these issues, various experimental efforts have been devoted to the synthesis of Ag/Au hybrid NPs for the purpose of SERS detections. However, a complete understanding on how the SERS enhancement depends on the chemical composition and structure of these nanoparticles has not been achieved. In this study, Mie theory and the discrete dipole approximation have been used to calculate the plasmonic spectra and near-field electromagnetic enhancements of Ag/Au hybrid NPs. In particular, we discuss how the electromagnetic enhancement depends on the mole fraction of Au in Ag/Au alloy NPs and how one may use extinction spectra to distinguish between Ag/Au alloyed NPs and Ag-Au core-shell NPs. We also show that for incident laser wavelengths between ˜410 nm and 520 nm, Ag/Au alloyed NPs provide better electromagnetic enhancement than pure Ag, pure Au, or Ag-Au core-shell structured NPs. Finally, we show that silica-core Ag/Au alloy shelled NPs provide even better performance than pure Ag/Au alloy or pure solid Ag and pure solid Au NPs. The theoretical results presented will be beneficial to the experimental efforts in optimizing the design of Ag/Au hybrid NPs for SERS-based detection methods.

  5. Dependence of SERS enhancement on the chemical composition and structure of Ag/Au hybrid nanoparticles.

    PubMed

    Chaffin, Elise; O'Connor, Ryan T; Barr, James; Huang, Xiaohua; Wang, Yongmei

    2016-08-01

    Noble metal nanoparticles (NPs) such as silver (Ag) and gold (Au) have unique plasmonic properties that give rise to surface enhanced Raman scattering (SERS). Generally, Ag NPs have much stronger plasmonic properties and, hence, provide stronger SERS signals than Au NPs. However, Ag NPs lack the chemical stability and biocompatibility of comparable Au NPs and typically exhibit the most intense plasmonic resonance at wavelengths much shorter than the optimal spectral region for many biomedical applications. To overcome these issues, various experimental efforts have been devoted to the synthesis of Ag/Au hybrid NPs for the purpose of SERS detections. However, a complete understanding on how the SERS enhancement depends on the chemical composition and structure of these nanoparticles has not been achieved. In this study, Mie theory and the discrete dipole approximation have been used to calculate the plasmonic spectra and near-field electromagnetic enhancements of Ag/Au hybrid NPs. In particular, we discuss how the electromagnetic enhancement depends on the mole fraction of Au in Ag/Au alloy NPs and how one may use extinction spectra to distinguish between Ag/Au alloyed NPs and Ag-Au core-shell NPs. We also show that for incident laser wavelengths between ∼410 nm and 520 nm, Ag/Au alloyed NPs provide better electromagnetic enhancement than pure Ag, pure Au, or Ag-Au core-shell structured NPs. Finally, we show that silica-core Ag/Au alloy shelled NPs provide even better performance than pure Ag/Au alloy or pure solid Ag and pure solid Au NPs. The theoretical results presented will be beneficial to the experimental efforts in optimizing the design of Ag/Au hybrid NPs for SERS-based detection methods.

  6. Au-supported Pt-Au mixed atomic monolayer electrocatalyst with ultrahigh specific activity for oxidation of formic acid in acidic solution.

    PubMed

    Huang, Zhao; Liu, Yan; Xie, Fangyun; Fu, Yingchun; He, Yong; Ma, Ming; Xie, Qingji; Yao, Shouzhuo

    2012-12-25

    Au-supported Pt-Au mixed atomic monolayer electrocatalyst was prepared by underpotential deposition of Cu on Au and then redox replacement with noble metal atoms, which shows an ultrahigh Pt-mass (or Pt-area) normalized specific electrocatalytic activity of 102 mA μg(Pt)(-1) (124 mA cm(Pt)(-2)) for oxidation of formic acid in acidic aqueous solution.

  7. Cyclometalated heteronuclear Pt/Ag and Pt/Tl complexes: a structural and photophysical study.

    PubMed

    Jamali, Sirous; Ghazfar, Reza; Lalinde, Elena; Jamshidi, Zahra; Samouei, Hamidreza; Shahsavari, Hamid R; Moreno, M Teresa; Escudero-Adán, Eduardo; Benet-Buchholz, Jordi; Milic, Dalibor

    2014-01-21

    To investigate the factors influencing the luminescent properties of polymetallic cycloplatinated complexes a detailed study of the photophysical and structural properties of the heteronuclear complexes [Pt2Me2(bhq)2(μ-dppy)2Ag2(μ-acetone)](BF4)2, 2, [PtMe(bhq)(dppy)Tl]PF6, 3, and [Pt2Me2(bhq)2(dppy)2Tl]PF6, 4, [bhq = benzo[h]quinoline, dppy = 2-(diphenylphosphino)pyridine] was conducted. Complexes 3 and 4 synthesized by the reaction of [PtMe(bhq)(dppy)], 1, with TlPF6 (1 or 1/2 equiv.) and stabilized by unsupported Pt-Tl bonds as revealed by multinuclear NMR spectroscopy and confirmed by X-ray crystallography for 3. DFT calculations for the previously reported butterfly Pt2Ag2 cluster 2 reveal that in the optimized geometry the bridging acetone molecule is removed and the metal core displays a planar-shaped geometry in which according to a QTAIM calculation and natural bond orbital (NBO) analysis the Ag···Ag metallophilic interaction is strengthened. In contrast to the precursor 1, which is only emissive in glassy solutions ((3)MLCT 485 nm), all 2-4 heteropolynuclear complexes display intense emissions in the solid state and in glassy solutions. Time-dependent density functional theory (TD-DFT) is used to elucidate the origin of the electronic transitions in the heteronuclear complexes 2 and 3. The low energy absorption and intense orange emission for cluster 2 (solid 77 K and glass) are attributed to metal-metal to ligand charge transfer (MM'LCT) with a minor L'LCT contribution. For 3 and 4 two different bands are developed: the high energy band (602-630 nm) observed for 4 at 77 K (solid, glass) and in diluted glasses for 3 is ascribed to emission from discrete Pt2Tl units of mixed (3)L'LCT/(3)LM'CT origin. However, the low energy band (670-690 nm) observed at room temperature (solid) for both complexes and also in concentrated glasses for 3 is assigned to (3)ππ excited states arising from intermolecular interactions. PMID:24165802

  8. Evaluation of bimetallic catalyst PtAg/C as a glucose-tolerant oxygen reduction cathode

    NASA Astrophysics Data System (ADS)

    Guerra-Balcázar, M.; Cuevas-Muñiz, F. M.; Álvarez-Contreras, L.; Arriaga, L. G.; Ledesma-García, J.

    2012-01-01

    PtAg/C nanoparticles were synthesized by chemical reduction and evaluated for the oxygen reduction reaction (ORR) in the absence and presence of glucose. PtAg/C catalyst formed onion-like layered structures, which are uniformly distributed on the support. PtAg/C showed activity comparable to that of Pt/C ETEK for ORR. Further, the catalyst exhibited high selectivity for ORR in the presence of glucose. PtAg/C was evaluated as cathode in a microfluidic fuel cell operated with high concentration of glucose (100 mM) as fuel. The results demonstrated that the use of PtAg/C as cathode electrode achieved higher selectivity and better performance compared with Pt/C catalyst.

  9. Effect of (Ag, Sn) Doping on the Structure and Optical Properties of Au Nanocluster

    NASA Astrophysics Data System (ADS)

    Balu, Radhakrishnan; Karna, Shashi

    2014-03-01

    Noble metal nanoclusters (NCs) consisting of a few to 35 atoms in size in the sub 2 nm range dimension are considered to be nontoxic as opposed to nanoparticles that are cytotoxic. Also, due to the quantum confinement of electrons, these NCs exhibit atom-like energy spectrum and display fluorescent properties useful in a wide range of applications, including medical diagnosis. The unique features of NCs such as size-tunable optical properties, intense fluorescence in the visible, and biocompatibility have stimulated an active area of investigation of noble metal NCs comprised of Au, Ag, Cu, and Pt. Furthermore, the electronic properties of nanoclusters can be modified by combining them with other elements. In this study, we consider the space-filled configuration of Au32 NC and investigate the effects of Ag and Sn atom incorporation on geometry and electronic spectrum. Our study suggests that Ag and Sn doping of Au32 NC red-shifts the absorption maximum and also reduces the oscillator strength.

  10. Highly active PtAu alloy nanoparticle catalysts for the reduction of 4-nitrophenol.

    PubMed

    Zhang, Jianming; Chen, Guozhu; Guay, Daniel; Chaker, Mohamed; Ma, Dongling

    2014-02-21

    To enhance the catalytic activity of gold nanoparticles (AuNPs) for the hydrogenation of nitro-aromatic chemicals, Pt was introduced into AuNPs to form "bare" PtAu alloy NPs using a physical approach, pulsed laser ablation in liquid (PLAL), on single metal-mixture targets. These PLAL-NPs are deemed to favor catalysis due to the absence of any surfactant molecules on their unique "bare and clean" surface. The PLAL-NPs were facilely assembled onto CeO2 nanotubes (NTs) by simply mixing them without conducting any surface functionalization, representing another advantage of these NPs. Their catalytic activity was assessed in 4-nitrophenol (4-NP) hydrogenation. The reaction catalyzed by alloy-NP/CeO2-NT catalysts demonstrates a remarkably higher reaction rate in comparison with that catalyzed by pure Au and Pt NPs, and other similar Au and Pt containing catalysts reported recently. A "volcano-like" catalytic activity dependence of the alloy NPs on their chemical composition suggests a strong synergistic effect between Au and Pt in the 4-NP reduction, far beyond the simple sum of their individual contributions. It leads to the significantly enhanced catalytic activity of Pt30Au70 and Pt50Au50 alloy NPs, outperforming not only each single constituent, but also their physical mixtures and most recently reported AuNP based nanocatalysts. The favorable d-band center shift of Pt after alloying, and co-operative actions between Pt clusters and nearby Au (or mixed PtAu) sites were proposed as possible mechanisms to explain such a strong synergistic effect on catalysis.

  11. Surface restructuring of Pt films on Au stepped surfaces: effects on catalytic behaviour.

    PubMed

    Prieto, Mauricio J; Tremiliosi-Filho, Germano

    2013-08-21

    In this paper, the reconstruction of Pt films deposited on stepped Au(hkl) surfaces belonging to the [n(111) × (110)] family of planes has been studied. Pt films were deposited using the galvanic displacement procedure of a pre-deposited Cu monolayer. We experimentally found that the Pt film deposition onto Au(hkl) surfaces is not fully epitaxial suggesting an atomic arrangement different from the underlying substrate. Additionally, we found that even though voltammetric profiles are not much different from those reported in the literature for Pt single crystals having the same crystallographic orientation, there is a reconstruction of the Pt layers on all Pt/Au(hkl) surfaces upon CO adsorption/oxidation as indicated by comparing the active areas of the Pt films before and after stripping. Additional FTIR in situ experiments on ethanol oxidation confirm that film reconstruction affects the reaction by product yield modification.

  12. Communication: Kinetics of chemical ordering in Ag-Au and Ag-Ni nanoalloys

    NASA Astrophysics Data System (ADS)

    Calvo, F.; Fortunelli, A.; Negreiros, F.; Wales, D. J.

    2013-09-01

    The energy landscape and kinetics of medium-sized Ag-Au and Ag-Ni nanoalloy particles are explored via a discrete path sampling approach, focusing on rearrangements connecting regions differing in chemical order. The highly miscible Ag27Au28 supports a large number of nearly degenerate icosahedral homotops. The transformation from reverse core-shell to core-shell involves large displacements away from the icosahedron through elementary steps corresponding to surface diffusion and vacancy formation. The immiscible Ag42Ni13 naturally forms an asymmetric core-shell structure, and about 10 eV is required to extrude the nickel core to the surface. The corresponding transformation occurs via a long and smooth sequence of surface displacements. For both systems the rearrangement kinetics exhibit Arrhenius behavior. These results are discussed in the light of experimental observations.

  13. Growth of Au@Pt coreshell nanoparticles: Probed by in-situ XANES and UV-visible spectroscopy

    NASA Astrophysics Data System (ADS)

    Nayak, C.; Bhattacharyya, K.; Tripathi, A. K.; Jha, S. N.; Bhattacharyya, D.; Sahoo, N. K.

    2016-05-01

    Au@Pt core shell nanoparticles have been synthesized by reducing Au and Pt chloride precursors with Block Co-polymer and Ascorbic acid. The growth and nucleation of Au@Pt nanoparticles have been investigated by in-situ time resolved XANES measurement which gives the evolution of the reduction process of the precursors. Linear combination fitting of the XANES spectra has been carried out to find the fraction of Au and Pt cations reduced at a particular reaction time. UV-Visible spectroscopy is used as a complementary technique which gives the changes in the Au SPR peak as Au@Pt core shell nanoparticles are formed.

  14. Conversion of Ag nanowires to AgCI nanowires decorated with Au nanoparticles and their photocatalytic activity.

    SciTech Connect

    Sun, Y.; Center for Nanoscale Materials

    2010-02-11

    A two-step approach has been developed to synthesize AgCl nanowires decorated with Au nanoparticles by using Ag nanowires as chemical templates. In the first step, the Ag nanowires are oxidized with FeCl{sub 3} followed by a simultaneous precipitation reaction between Ag{sup +} and Cl{sup -} ions at room temperature, resulting in conversion of the Ag nanowires to AgCl nanowires as well as reduction of Fe{sup 3+} to Fe{sup 2+} ions. In the second step, the Fe{sup 2+} ions generated in the first step reduce Au precursors (e.g., NaAuCl{sub 4}) to deposit Au nanoparticles on the surfaces of the AgCl nanowires, resulting in the formation of AgCl:Au composite nanowires. Because of strong surface plasmon resonance and chemical inertness of Au nanoparticles, the as-synthesized AgCl:Au nanowires exhibit enhanced absorption coefficient in the visible region and enhanced chemical stability to prevent them from degradation and aggregation. These unique properties enable the AgCl:Au nanowires to be used as a class of promising plasmonic photocatalysts driven by visible light. Preliminary results demonstrate these composite nanowires can efficiently decompose organics, such as methylene blue molecules, under illumination of white light.

  15. Controlled synthesis of dendritic Au@Pt core-shell nanomaterials for use as an effective fuel cell electrocatalyst

    NASA Astrophysics Data System (ADS)

    Wang, Shuangyin; Kristian, Noel; Jiang, Sanping; Wang, Xin

    2009-01-01

    We report the controlled synthesis of dendritic Au@Pt core-shell nanomaterials. The size and morphology of the Au cores and the Pt shell thickness of the Au@Pt core-shell nanostructures could be easily tuned. It was found that the directing agent and the reducing agent play critical roles in the synthesis of dendritic Au@Pt core-shell nanomaterials. For comparison purposes, conventional Au@Pt core-shell nanoparticles and monometallic Pt nanoparticles were also synthesized by the successive reduction method. Transmission electron microscopy (TEM) observations demonstrated the dendritic surface of the products obtained. The UV-visible (UV-vis) spectroscopy results and a comparison of the average diameter between the dendritic Au@Pt and conventional Au@Pt confirmed the relatively loose Pt shells around Au cores for the dendritic Au@Pt. The as-prepared dendritic Au@Pt showed enhanced electrocatalytic activity for methanol oxidation in acid medium, compared to the conventional Au@Pt and monometallic Pt.

  16. Injection and acceleration of Au31+ in the BNL AGS.

    SciTech Connect

    Fischer,W.; Ahrens, L.; Brown, K.; Gardner, C.; Glenn, W.; Huang, H.; Mapes, M.; Smart, L.; Thieberger, P.; Tsoupas, N.; Zhang, S.Y.; Zeno, K.; Omet, C.; Spiller, P.

    2008-06-23

    Injection and acceleration of ions in a lower charge state reduces space charge effects, and, if further elcctron stripping is needed, may allow elimination of a stripping stage and the associated beam losses. The former is of interest to the accelerators in the GSI FAIR complex, the latter for BNL RHIC collider operation at energies lower than the current injection energy. Lower charge state ions, however, have a higher likelihood of electron stripping which can lead to dynamic pressures rises and subsequent beam losses. We report on experiments in the AGS where Au{sup 31+} ions were injected and accelerated instead of the normally used Au{sup 77+} ions. Beam intensities and the average pressure in the AGS ring are recorded, and compared with calculations for dynamic pressures and beam losses. The experimental results will be used to benchmark the StrahlSim dynamic vacuum code and will be incorporated in the GSI FAIR SIS100 design.

  17. Au-Ag-Cu nano-alloys: tailoring of permittivity.

    PubMed

    Hashimoto, Yoshikazu; Seniutinas, Gediminas; Balčytis, Armandas; Juodkazis, Saulius; Nishijima, Yoshiaki

    2016-01-01

    Precious metal alloys enables new possibilities to tailor materials for specific optical functions. Here we present a systematic study of the effects of a nanoscale alloying on the permittivity of Au-Ag-Cu metals at 38 different atomic mixing ratios. The permittivity was measured and analyzed numerically by applying the Drude model. X-ray diffraction (XRD) revealed the face centered cubic lattice of the alloys. Both, optical spectra and XRD results point towards an equivalent composition-dependent electron scattering behavior. Correlation between the fundamental structural parameters of alloys and the resulting optical properties is elucidated. Plasmonic properties of the Au-Ag-Cu alloy nanoparticles were investigated by numerical simulations. Guidelines for designing plasmonic response of nano- structures and their patterns are presented from the material science perspective. PMID:27118459

  18. Synthesis of triangular Au core-Ag shell nanoparticles

    SciTech Connect

    Rai, Akhilesh; Chaudhary, Minakshi; Ahmad, Absar; Bhargava, Suresh; Sastry, Murali . E-mail: msastry@tatachemicals.com

    2007-07-03

    In this paper, we demonstrate a simple and reproducible method for the synthesis of triangular Au core-Ag shell nanoparticles. The triangular gold core is obtained by the reduction of gold ions by lemongrass extract. Utilizing the negative charge on the gold nanotriangles, silver ions are bound to their surface and thereafter reduced by ascorbic acid under alkaline conditions. The thickness of the silver shell may be modulated by varying the pH of the reaction medium. The formation of the Au core-Ag shell triangular nanostructures has been followed by UV-vis-NIR Spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy (TEM) and atomic force microscopy (AFM) measurements. The sharp vertices of the triangles coupled with the core-shell structure is expected to have potential for application in surface enhanced Raman spectroscopy and in the sensitive detection of biomolecules.

  19. Au-Ag-Cu nano-alloys: tailoring of permittivity

    PubMed Central

    Hashimoto, Yoshikazu; Seniutinas, Gediminas; Balčytis, Armandas; Juodkazis, Saulius; Nishijima, Yoshiaki

    2016-01-01

    Precious metal alloys enables new possibilities to tailor materials for specific optical functions. Here we present a systematic study of the effects of a nanoscale alloying on the permittivity of Au-Ag-Cu metals at 38 different atomic mixing ratios. The permittivity was measured and analyzed numerically by applying the Drude model. X-ray diffraction (XRD) revealed the face centered cubic lattice of the alloys. Both, optical spectra and XRD results point towards an equivalent composition-dependent electron scattering behavior. Correlation between the fundamental structural parameters of alloys and the resulting optical properties is elucidated. Plasmonic properties of the Au-Ag-Cu alloy nanoparticles were investigated by numerical simulations. Guidelines for designing plasmonic response of nano- structures and their patterns are presented from the material science perspective. PMID:27118459

  20. Optical properties of Au-core Pt-shell nanorods studied using FDTD simulations

    NASA Astrophysics Data System (ADS)

    Liu, Jian-Bo; Long, Lin; Zhang, Yu-Shi; Wang, Yue-Ping; Liu, Feng-Shou; Xu, Wei-Yao; Zong, Ming-Ji; Ma, Lei; Liu, Wen-Qi; Zhang, Hui; Yan, Jiao; Chen, Jia-Qi; Ji, Ying-Lu; Wu, Xiao-Chun

    2016-06-01

    Au-core/Pt-shell nanorods (Au@Pt NRs) have been prepared by a Au nanorod-mediated growth method, and they exhibit high electromagnetic field enhancements under coupling conditions. Boosted by a long-range effect of the high electromagnetic field generated by the Au core, the electromagnetic field enhancement can be controlled by changing the morphology of the nanostructures. In this study, we report the results on the simulations of the electromagnetic field enhancement using a finite difference time domain (FDTD) method, taking the real shapes of the Au@Pt NRs into account. Due to the "hot spot" effect, the electromagnetic field can be localized between the Pt nanodots. The electromagnetic field enhancement is found to be rather independent of the Pt content, whereas the local roughness and small sharp features might significantly modify the near-field. As the electromagnetic field enhancement can be tuned by the distribution of Pt nanodots over the Au-core, Au@Pt NRs can find potential applications in related areas.

  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. Ag-Pt alloy nanoparticles with the compositions in the miscibility gap

    SciTech Connect

    Peng Zhenmeng; Yang Hong

    2008-07-15

    Silver platinum binary alloys with compositions between about Ag{sub 2}Pt{sub 98} and Ag{sub 95}Pt{sub 5} at <{approx} 400 deg. C have largely not been observed in bulk due to the large immiscibility between these two metals. We present in this paper that Ag-Pt alloy nanostructures can be made in a broad composition range. The formation of Ag-Pt nanostructures is studied by powder X-ray diffraction (PXRD) and energy-dispersive X-ray (EDX). Our results indicate that lattice parameter changes almost linearly with composition in these Ag-Pt nanomaterials. In another word, lattice parameter and composition relationship follows the Vegard's law, which is a strong indication for the formation of metal alloys. Our transmission electron microscopy (TEM) study shows that the silver-rich Ag-Pt alloy nanostructures have spherical shape, while the platinum-rich ones possess wire-like morphology. The stability and crystal phase are investigated by annealing the alloy nanostructures directly or on carbon supports. - Graphical abstract: While platinum and silver cannot form a solid solution with the composition between about Ag{sub 2}Pt{sub 98} and Ag{sub 95}Pt{sub 5} at 400 deg. C or below in bulk form, alloy particles and wires can be made within this miscibility gap at the nanometer scale.

  3. 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

  4. Growth of Au@Ag core-shell pentatwinned nanorods: tuning the end facets.

    PubMed

    Zhang, Weiqing; Goh, Hao Ying Johnny; Firdoz, Shaik; Lu, Xianmao

    2013-09-16

    Au@Ag core-shell nanorods with tunable end facets are obtained by coating Au bipyramids (BPs) with Ag. The resultant nanorods exhibit a pentatwinned crystal structure with tips terminated with either {110} or {111} facets. The control over the end facets is achieved by varying the capping agents and tuning the reduction rate of Ag. Specifically, when Ag is reduced slowly, Au@Ag nanorods with flat {110} end facets are formed with cetyltrimethylammonium bromide (CTAB) as the capping agent. If CTAB is replaced with cetyltrimethylammonium chloride (CTAC), Au@Ag nanorods with tips terminated with {111} facets are obtained. However, at a high Ag reduction rate, dumbbell-shaped Au@Ag nanorods are formed, with either CTAB or CTAC as the capping agent. The morphological evolution of the nanorods in each case is closely followed and a growth mechanism is proposed. PMID:23934938

  5. 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

  6. The synthesis of Pt/Ag bimetallic nanoparticles using a successive solution plasma process.

    PubMed

    Kim, Sung Min; Lee, Sang Yul; Lee, Min Hyung; Kim, Jung Wan

    2014-12-01

    A successive solution plasma process was developed for the synthesis of Pt/Ag bimetallic nanoparticles. Ag nanoparticles were made first by applying a high voltage of bipolar pulsed DC to anode and cathode electrodes composed of Ag rods. The solution containing Ag nanoparticles was discharged successively using Pt electrodes. The joule heating and electrolysis between electrodes generated vapors, and solution plasma was sustained due to progressive ionization and excitation in the vapor phase. The maximum current and voltage breakdown was observed at approximately 8.9 A and 900 V with an interval of 25 μs, which indicated that an intense solution plasma was sustained continuously. The Pt-on-Ag heterogeneous nanostructures formed, and finally, the Ag nanoparticles were completely covered by Pt nanoparticles after a discharge duration of 1,200 s. PMID:25970983

  7. 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.

  8. Synthesis, Study, and Discrete Dipole Approximation Simulation of Ag-Au Bimetallic Nanostructures

    NASA Astrophysics Data System (ADS)

    Hu, Yang; Zhang, An-Qi; Li, Hui-Jun; Qian, Dong-Jin; Chen, Meng

    2016-04-01

    Water-soluble Ag-Au bimetallic nanostructures were prepared via co-reduction and seed-mediated growth routes employing poly-(4-styrenesulfonic acid-co-maleic acid) (PSSMA) as both a reductant and a stabilizer. Ag-Au alloy nanoparticles were obtained by the co-reduction of AgNO3 and HAuCl4, while Ag-Au core-shell nanostructures were prepared through seed-mediated growth using PSSMA-Au nanoparticle seeds in a heated AgNO3 solution. The optical properties of the Ag-Au alloy and core-shell nanostructures were studied, and the growth mechanism of the bimetallic nanoparticles was investigated. Plasmon resonance bands in the range 422 to 517 nm were observed for Ag-Au alloy nanoparticles, while two plasmon resonances were found in the Ag-Au core-shell nanostructures. Furthermore, discrete dipole approximation theoretical simulation was used to assess the optical property differences between the Ag-Au alloy and core-shell nanostructures. Composition and morphology studies confirmed that the synthesized materials were Ag-Au bimetallic nanostructures.

  9. Synthesis, Study, and Discrete Dipole Approximation Simulation of Ag-Au Bimetallic Nanostructures.

    PubMed

    Hu, Yang; Zhang, An-Qi; Li, Hui-Jun; Qian, Dong-Jin; Chen, Meng

    2016-12-01

    Water-soluble Ag-Au bimetallic nanostructures were prepared via co-reduction and seed-mediated growth routes employing poly-(4-styrenesulfonic acid-co-maleic acid) (PSSMA) as both a reductant and a stabilizer. Ag-Au alloy nanoparticles were obtained by the co-reduction of AgNO3 and HAuCl4, while Ag-Au core-shell nanostructures were prepared through seed-mediated growth using PSSMA-Au nanoparticle seeds in a heated AgNO3 solution. The optical properties of the Ag-Au alloy and core-shell nanostructures were studied, and the growth mechanism of the bimetallic nanoparticles was investigated. Plasmon resonance bands in the range 422 to 517 nm were observed for Ag-Au alloy nanoparticles, while two plasmon resonances were found in the Ag-Au core-shell nanostructures. Furthermore, discrete dipole approximation theoretical simulation was used to assess the optical property differences between the Ag-Au alloy and core-shell nanostructures. Composition and morphology studies confirmed that the synthesized materials were Ag-Au bimetallic nanostructures. PMID:27094823

  10. Electrostatic assembles and optical properties of Au CdTe QDs and Ag/Au CdTe QDs

    NASA Astrophysics Data System (ADS)

    Yang, Dongzhi; Wang, Wenxing; Chen, Qifan; Huang, Yuping; Xu, Shukun

    2008-09-01

    Au-CdTe and Ag/Au-CdTe assembles were firstly investigated through the static interaction between positively charged cysteamine-stabilized CdTe quantum dots (QDs) and negatively charged Au or core/shell Ag/Au nano-particles (NCs). The CdTe QDs synthesized in aqueous solution were capped with cysteamine which endowed them positive charges on the surface. Both Au and Ag/Au NCs were prepared through reducing precursors with gallic acid obtained from the hydrolysis of natural plant poly-phenols and favored negative charges on the surface of NCs. The fluorescence spectra of CdTe QDs exhibited strong quenching with the increase of added Au or Ag/Au NCs. Railey resonance scattering spectra of Au or Ag/Au NCs increased firstly and decreased latter with the concentration of CdTe QDs, accompanied with the solution color changing from red to purple and colorless at last. Experimental results on the effects of gallic acid, chloroauric acid tetrahydrate and other reagents demonstrated the static interaction occurred between QDs and NCs. This finding reveals the possibilities to design and control optical process and electromagnetic coupling in hybrid structures.

  11. 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

  12. Ab initio study of He point defects in fcc Au-Ag alloys

    SciTech Connect

    Zhu, Zi Qiang; Yang, Li; Nie, JL; Peng, SM; Long, XG; Zhou, X. S.; Zu, Xiaotao; Gao, Fei

    2013-04-25

    The relative stabilities of He defects in two fcc Au-Ag alloys (Au3Ag2 and AuAg) are investigated using ab initio method based on density functional theory. The results show that the stabilities of He defects in the two alloys mainly depend on the atomic arrangements of the nearest neighboring host metals. A He interstitial prefers to stay at a site with more Ag neighboring atoms, while the favorable substitutional site has more Au neighboring atoms in Au-Ag alloys. Moreover, the substitutional He defects are the most stable configurations in both the alloys, and the octahedral He interstitials are energetically more favorable than the tetrahedral interstitials. It is of interest to note that the properties of He defects slightly depend on the mass-density of Au-Ag alloys. The results also demonstrate that the relative stabilities of He defects are primarily attributed to the hybridization between metals d states and He p states.

  13. Au@Pt nanostructures as oxidase and peroxidase mimetics for use in immunoassays.

    PubMed

    He, Weiwei; Liu, Ying; Yuan, Jinshan; Yin, Jun-Jie; Wu, Xiaochun; Hu, Xiaona; Zhang, Ke; Liu, Jianbo; Chen, Chunying; Ji, Yinglu; Guo, Yuting

    2011-02-01

    In this paper, we demonstrated that Au nanorods coated with a shell composed of Pt nanodots (Au@Pt nanostructures) exhibited intrinsic oxidase-like, peroxidase-like and catalase-like activity, catalyzing oxygen and hydrogen peroxide reduction and the dismutation decomposition of hydrogen peroxide to produce oxygen. Based on these findings, we established an Au@Pt nanostructures based enzyme linked immunosorbent assay (ELISA) for the detection of mouse interleukin 2 (IL-2). In comparison with natural enzymes, Au@Pt nanostructures have advantages of low cost, easy preparation, better stability, and tunable catalytic activity (compared with HRP), which make them a promising enzyme mimetic candidate and may find potential applications in biocatalysis, bioassays, and nano-biomedicine such as reactive oxygen species (ROS)-related fields (anti-aging and therapeutics for neurodegenerative diseases and cancers).

  14. Local structure of disordered Au-Cu and Au-Ag alloys

    NASA Astrophysics Data System (ADS)

    Frenkel, A. I.; Machavariani, V. Sh.; Rubshtein, A.; Rosenberg, Yu.; Voronel, A.; Stern, E. A.

    2000-10-01

    X-ray-absorption fine structure (XAFS) and x-ray-diffraction (XRD) measurements of disordered alloys AuxCu1-x and Au0.5Ag0.5 prepared by melt spinning were performed. In the Au0.5Ag0.5 alloy, no significant local deviations of the atoms from the average fcc lattice were detected while in AuxCu1-x alloys, significant deviations of atoms from the average fcc lattice were found. Mean-square vibrations of the Cu-Cu distances revealed by the XAFS in AuxCu1-x alloys indicate the weakening of contact between Cu atoms in the dilute limit. Our computer simulation for AuxCu1-x clusters of 105 atoms reproduces the main features of both the XAFS and XRD data.

  15. 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.

  16. Ultrafast processes in Ag and Au: A Monte Carlo study

    NASA Astrophysics Data System (ADS)

    van Hall, P. J.

    2001-03-01

    Monte Carlo simulations of ultrafast electron processes in Ag and Au have been used to analyze transient reflectivity as well as two-photon photoemission experiments. The model consisted of an electron Fermi gas coupled to longitudinal acoustic phonons. A laser pulse of finite width excited the electrons, after which the development of the distribution function was followed during 3-5 ps. In the electron-phonon coupling we used the full q dependence of the scattering together with a semirealistic phonon dispersion relation. The strength of the electron-phonon scattering is governed by the deformation potential. Its value was fixed to low-fluence transient reflection data. Also hot-phonon effects were included. For the electron-electron scattering we employed a Coulomb interaction screened according to the Thomas-Fermi prescription. We accounted for exchange effects in the total scattering probability. In a later stage we varied the screening. We analyzed a variety of data for Ag and Au. A good description of the temperature dependence of the transient reflectivity for various excitation powers could be obtained. Also the time evolution of the Fermi surface showed fair agreement with the experiment. In the case of Ag the lifetime of an electron above the Fermi sea was predicted correctly. For Au, however, it was necessary to increase the screening to obtain the correct lifetimes of electrons excited above the Fermi sea. Using this adjusted screening the description of the other experiments no longer was appropriate. Finally also the resistivity due to electron-phonon scattering was predicted quite well using the deformation potential extracted from the ultrafast reflectivity experiments.

  17. Highly accessible Pt nanodots homogeneously decorated on Au nanorods surface for sensing.

    PubMed

    Feng, Xun; Li, Xin; Shi, Hongyan; Huang, Hao; Wu, Xiaochun; Song, Wenbo

    2014-12-10

    Some nanostructures are reported to possess enzyme-mimetic activities similar to those of natural enzymes. Herein, highly-dispersed Pt nanodots on Au nanorods (HD-PtNDs@AuNRs) with mimetic peroxidase activity were designed as an active electrode modifier for fabrication of a hydrogen peroxide (H2O2) electrochemical sensor. The HD-PtNDs@AuNRs were synthesized by a seed-mediated growth approach and confirmed by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and UV-vis spectroscopy. The electrochemical and catalytical performances of HD-PtNDs@AuNRs towards H2O2 reduction were investigated in detail by cyclic voltammetry and amperometry. The HD-PtNDs@AuNRs modified electrode displayed a high catalytic activity to H2O2 at -0.10 V (versus SCE), a rapid response within 5 s, a wide linear range of 2.0-3800.0 μM, a detection limit of 1.2 μM (S/N=3), and a high sensitivity of 181 μA mM(-1) cm(-2). These results suggested a promising potential of fabricating H2O2 electrochemical sensor using HD-PtNDs@AuNRs. PMID:25441877

  18. Sum-frequency generation of acetate adsorption on Au and Pt surfaces: Molecular structure effects

    NASA Astrophysics Data System (ADS)

    Braunschweig, Björn; Mukherjee, Prabuddha; Kutz, Robert B.; Wieckowski, Andrzej; Dlott, Dana D.

    2010-12-01

    The reversible adsorption of acetate on polycrystalline Au and Pt surfaces was investigated with broadband sum-frequency generation (SFG) and cyclic voltammetry. Specifically adsorbed acetate as well as coadsorbed sulfuric acid anions are observed for the first time with SFG and give rise to dramatically different SFG intensities on Au and Pt surfaces. While similar coverages of acetate adlayers on Au and Pt surfaces are well established by previous studies, an identification of the interfacial molecular structure has been elusive. However, we have applied the high sensitivity of SFG for interfacial polar ordering to identify different acetate structures at Au and Pt surfaces in contact with HClO4 and H2SO4 electrolytes. Acetate competes with the formation of surface oxides and shifts the oxidation threshold of both Au and Pt electrodes anodically. Effects of the supporting electrolyte on the formation of acetate adlayers are revealed by comparing SFG spectra in HClO4 and H2SO4 solutions: Sulfuric acid anions modify the potential-dependent acetate adsorption, compete with adsorbed acetate on Au and coadsorb with acetate on Pt surfaces.

  19. Stable excited Au= and Pt= negative ions: A Regge-pole prediction

    NASA Astrophysics Data System (ADS)

    Felfli, Z.; Msezane, A. Z.; Sokolovski, D.

    2010-03-01

    Electron elastic scattering from Au and Pt atoms is investigated in the energy region E < 4.0 eV in search of the possibility of forming and observing stable excited Au= and Pt= negative ions as Regge resonances. Total elastic cross sections (TCSs) and differential cross sections (DCSs) in both impact energy and scattering angle for the excited Au and Pt atoms are calculated. The investigation uses the recent Regge-pole methodology [1] wherein is embedded the vital electron-electron correlations together with a Thomas-Fermi type potential that incorporates the crucial core-polarization interaction, essential for the existence and stability of most negative ions. From the characteristic dramatically sharp resonances in the elastic total and Mulholland partial cross sections we identify excited Au= and Pt= anions and extract their binding energies (BEs). Ramsauer-Townsend minima and shape resonances are also determined. The DCSs also yield the BEs of the Au= and Pt= anions [2]. The TCSs for the excited and ground Au= and Pt= anions are contrasted as well; they provide a clue to the significant catalytic properties of their nanoparticles. [1] D. Sokolovski et al, Phys. Rev. A 76, 012705 (2007); [2] Z. Felfli et al, NIMB, At Press (2010). Supported by U.S. DOE, AFOSR and CAU CFNM, NSF-CREST Program

  20. Syntheses and structural analyses of variable-stoichiometric Au-Pt-Ni carbonyl/phosphine clusters, Pt3(Pt(1-x)Ni(x))(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 and Pt2(Pt(2-y)Ni(y))(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2, with ligation-induced site-specific Pt/Ni substitutional disorder within butterfly-based Pt3(Pt(1-x)Ni(x))Au2 and Pt2(Pt(2-y)Ni(y))Au2 core-geometries.

    PubMed

    de Silva, Namal; Nichiporuk, Rita V; Dahl, Lawrence F

    2006-05-21

    In ongoing attempts of directed synthesis of high-nuclearity Au-Pt carbonyl/phosphine clusters with [Ni6(CO)12]2- used as reducing agent and CO source, we have isolated and characterized two new closely related variable-stoichiometric trimetallic clusters, Pt3(Pt(1-x)Ni(x))(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 (1) and Pt2(Pt(2-y)Ni(y))(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2). Their M4Au2 cores may be envisioned as substitutional disordered butterfly-based M4Au2 frameworks (M = Pt/Ni) formed by connections of the two basal M(B) atoms with both (Au-Au)-linked Au(PPh3) moieties. Based upon low-temperature CCD X-ray diffraction studies of eight crystals obtained from different samples, ligation-induced site-specific Pt/Ni substitutional disorder (involving formal insertion of Ni in place of Pt) in a given crystal was found to occur only at the one OC-attached basal M(B) site in 1 or at both OC-attached basal M(B) sites in 2 corresponding to a crystal composite of the Pt3(Pt(1-x)Ni(x))Au2 core in 1 or of the Pt2(Pt(2-y)Ni(y))Au2 core in 2; the Ph3P-attached M(B) site (M(B) = Pt) in 1 and two wingtip M(w) sites (M(w) = Pt) in 1 and 2 were not substitutionally disordered. The resulting variable stoichiometry of the M4Au2 core in 1 may be viewed as a crystal composite of two superimposed individual stereoisomers, Pt4(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 (1a) and Pt3Ni(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 (1b), in the averaged unit cell of a given crystal. Likewise, 2 represents the crystal-averaged composite of three individual stereoisomers, Pt4(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2a), Pt3Ni(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2b), and Pt2Ni2(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2c). Formal Ni substitution for Pt at only the basal M(B) site(s) in the four crystal composites each of 1 and 2 was found to vary widely from 17% to 79% Ni in 1 and from 21% to 95% Ni in 2. Nevertheless, reasonably close Pt/Ni occupancy factors were found within each of the four pairs of composite crystals selected from samples obtained from

  1. Bonding, Luminescence, Metallophilicity in Linear Au3 and Au2Ag Chains Stabilized by Rigid Diphosphanyl NHC Ligands.

    PubMed

    Ai, Pengfei; Mauro, Matteo; Gourlaouen, Christophe; Carrara, Serena; De Cola, Luisa; Tobon, Yeny; Giovanella, Umberto; Botta, Chiara; Danopoulos, Andreas A; Braunstein, Pierre

    2016-09-01

    The heterofunctional and rigid ligand N,N'-diphosphanyl-imidazol-2-ylidene (PCNHCP; P = P(t-Bu)2), through its phosphorus and two N-heterocyclic carbene (NHC) donors, stabilizes trinuclear chain complexes, with either Au3 or AgAu2 cores, and dinuclear Au2 complexes. The two oppositely situated PCNHCP (L) ligands that "sandwich" the metal chain can support linear and rigid structures, as found in the known tricationic Au(I) complex [Au3(μ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 (OTf = CF3SO3; [Au3L2](OTf)3; Chem. Commun. 2014, 50, 103-105) now also obtained by transmetalation from [Ag3(μ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 ([Ag3L2](OTf)3), or in the mixed-metal tricationic [Au2Ag(μ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 ([Au2AgL2](OTf)3). The latter was obtained stepwise by the addition of AgOTf to the digold(I) complex [Au2(μ2-PCNHCP,κP,κCNHC)2](OTf)2 ([Au2L2](OTf)2). The latter contains two dangling P donors and displays fluxional behavior in solution, and the Au···Au separation of 2.8320(6) Å in the solid state is consistent with metallophilic interactions. In the solvento complex [Au3Cl2(tht)(μ3-PCNHCP,κP,κCNHC,κP)](OTf)·MeCN ([Au3Cl2(tht)L](OTf)·MeCN), which contains only one L and one tht ligand (tht = tetrahydrothiophene), the metal chain is bent (148.94(2)°), and the longer Au···Au separation (2.9710(4) Å) is in line with relaxation of the rigidity due to a more "open" structure. Similar features were observed in [Au3Cl2(SMe2)L](OTf)·2MeCN. A detailed study of the emission properties of [Au3L2](OTf)3, [Au3Cl2(tht)L](OTf)·MeCN, [Au2L2](OTf)2, and [Au2AgL2](OTf)3 was performed by means of steady state and time-resolved photophysical techniques. The complex [Au3L2](OTf)3 displays a bright (photoluminescence quantum yield = 80%) and narrow emission band centered at 446 nm with a relatively small Stokes' shift and long-lived excited-state lifetime on the microsecond timescale, both in solution and in the solid state. In line with the very narrow emission

  2. Bonding, Luminescence, Metallophilicity in Linear Au3 and Au2Ag Chains Stabilized by Rigid Diphosphanyl NHC Ligands.

    PubMed

    Ai, Pengfei; Mauro, Matteo; Gourlaouen, Christophe; Carrara, Serena; De Cola, Luisa; Tobon, Yeny; Giovanella, Umberto; Botta, Chiara; Danopoulos, Andreas A; Braunstein, Pierre

    2016-09-01

    The heterofunctional and rigid ligand N,N'-diphosphanyl-imidazol-2-ylidene (PCNHCP; P = P(t-Bu)2), through its phosphorus and two N-heterocyclic carbene (NHC) donors, stabilizes trinuclear chain complexes, with either Au3 or AgAu2 cores, and dinuclear Au2 complexes. The two oppositely situated PCNHCP (L) ligands that "sandwich" the metal chain can support linear and rigid structures, as found in the known tricationic Au(I) complex [Au3(μ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 (OTf = CF3SO3; [Au3L2](OTf)3; Chem. Commun. 2014, 50, 103-105) now also obtained by transmetalation from [Ag3(μ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 ([Ag3L2](OTf)3), or in the mixed-metal tricationic [Au2Ag(μ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 ([Au2AgL2](OTf)3). The latter was obtained stepwise by the addition of AgOTf to the digold(I) complex [Au2(μ2-PCNHCP,κP,κCNHC)2](OTf)2 ([Au2L2](OTf)2). The latter contains two dangling P donors and displays fluxional behavior in solution, and the Au···Au separation of 2.8320(6) Å in the solid state is consistent with metallophilic interactions. In the solvento complex [Au3Cl2(tht)(μ3-PCNHCP,κP,κCNHC,κP)](OTf)·MeCN ([Au3Cl2(tht)L](OTf)·MeCN), which contains only one L and one tht ligand (tht = tetrahydrothiophene), the metal chain is bent (148.94(2)°), and the longer Au···Au separation (2.9710(4) Å) is in line with relaxation of the rigidity due to a more "open" structure. Similar features were observed in [Au3Cl2(SMe2)L](OTf)·2MeCN. A detailed study of the emission properties of [Au3L2](OTf)3, [Au3Cl2(tht)L](OTf)·MeCN, [Au2L2](OTf)2, and [Au2AgL2](OTf)3 was performed by means of steady state and time-resolved photophysical techniques. The complex [Au3L2](OTf)3 displays a bright (photoluminescence quantum yield = 80%) and narrow emission band centered at 446 nm with a relatively small Stokes' shift and long-lived excited-state lifetime on the microsecond timescale, both in solution and in the solid state. In line with the very narrow emission

  3. Unusual Metal-Metal Bonding in a Dinuclear Pt-Au Complex: Snapshot of a Transmetalation Process.

    PubMed

    Baya, Miguel; Belío, Úrsula; Fernández, Israel; Fuertes, Sara; Martín, Antonio

    2016-06-01

    The dinuclear Pt-Au complex [(CNC)(PPh3 )Pt Au(PPh3 )](ClO4 ) (2) (CNC=2,6-diphenylpyridinate) was prepared. Its crystal structure shows a rare metal-metal bonding situation, with very short Pt-Au and Au-Cipso (CNC) distances and dissimilar Pt-Cipso (CNC) bonds. Multinuclear NMR spectra of 2 show the persistence of the Pt-Au bond in solution and the occurrence of unusual fluxional behavior involving the [Pt(II) ] and [Au(I) ] metal fragments. The [Pt(II) ]⋅⋅⋅ [Au(I) ] interaction has been thoroughly studied by means of DFT calculations. The observed bonding situation in 2 can be regarded as a model for an intermediate in a transmetalation process.

  4. Mixed protein-templated luminescent metal clusters (Au and Pt) for H2O2 sensing

    PubMed Central

    2013-01-01

    A simple and cost-effective method to synthesize the luminescent noble metal clusters (Au and Pt) in chicken egg white aqueous solution at room temperature is reported. The red-emitting Au cluster is used as fluorescent probe for sensitive detection of H2O2. PMID:23601828

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

    SciTech Connect

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

    2005-06-15

    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.

  6. 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

  7. Substrate-Structure Dependence of Ag Electromigration on Au-Precovered Si(111) Surfaces

    NASA Astrophysics Data System (ADS)

    Shi, Fangxiao; Shiraki, Ichiro; Nagao, Tadaaki; Hasegawa, Shuji

    2000-07-01

    Electromigration of Ag on Au-precovered Si(111) surfaces was investigated by in-situ ultrahigh vacuum scanning electron microscopy and μ-probe reflection-high-energy electron diffraction (RHEED). Migration behaviors of a Ag-film patch strongly depended on Au coverage θAu and corresponding surface structures. When θAu<0.7 monolayer (ML), the patch expanded preferentially towards the cathode to attain a maximum area in which the sum of Ag and Au coverages were always about 1 ML irrespective of θAu, resulting in two-dimensional (2D) alloy phases (showing \\sqrt{3}×\\sqrt{3} RHEED patterns) with different Au/Ag concentration ratios. The largest expansion of the patch area was achieved on a (5× 2+α-\\sqrt{3}×\\sqrt{3})-Au mixed phase structure (θAu˜ 0.7 ML). However, when θAu>0.7 ML, the patch expansion was greatly reduced. Especially on the β-\\sqrt{3}×\\sqrt{3}-Au surface (θAu˜ 1.0 ML), the patch showed no directional expansion towards the cathode. But Ag atoms were observed to migrate inside the patches on all substrates (including the β-\\sqrt{3}×\\sqrt{3}-Au surface) to form 3D islands near terrace edges.

  8. Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

    2015-12-01

    Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

  9. Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction.

    PubMed

    Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

    2015-12-18

    Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

  10. Governing the morphology of Pt-Au heteronanocrystals with improved electrocatalytic performance

    NASA Astrophysics Data System (ADS)

    Mourdikoudis, Stefanos; Chirea, Mariana; Zanaga, Daniele; Altantzis, Thomas; Mitrakas, Manasis; Bals, Sara; Liz-Marzán, Luis M.; Pérez-Juste, Jorge; Pastoriza-Santos, Isabel

    2015-05-01

    Platinum-gold heteronanostructures comprising either dimer (Pt-Au) or core-satellite (Pt@Au) configurations were synthesized by means of a seeded growth procedure using platinum nanodendrites as seeds. Careful control of the reduction kinetics of the gold precursor can be used to direct the nucleation and growth of gold nanoparticles on either one or multiple surface sites simultaneously, leading to the formation of either dimers or core-satellite nanoparticles, respectively, in high yields. Characterization by electron tomography and high resolution electron microscopy provided a better understanding of the actual three-dimensional particle morphology, as well as the Au-Pt interface, revealing quasi-epitaxial growth of Au on Pt. The prepared Pt-Au bimetallic nanostructures are highly efficient catalysts for ethanol oxidation in alkaline solution, showing accurate selectivity, high sensitivity, and improved efficiency by generating higher current densities than their monometallic counterparts.Platinum-gold heteronanostructures comprising either dimer (Pt-Au) or core-satellite (Pt@Au) configurations were synthesized by means of a seeded growth procedure using platinum nanodendrites as seeds. Careful control of the reduction kinetics of the gold precursor can be used to direct the nucleation and growth of gold nanoparticles on either one or multiple surface sites simultaneously, leading to the formation of either dimers or core-satellite nanoparticles, respectively, in high yields. Characterization by electron tomography and high resolution electron microscopy provided a better understanding of the actual three-dimensional particle morphology, as well as the Au-Pt interface, revealing quasi-epitaxial growth of Au on Pt. The prepared Pt-Au bimetallic nanostructures are highly efficient catalysts for ethanol oxidation in alkaline solution, showing accurate selectivity, high sensitivity, and improved efficiency by generating higher current densities than their

  11. Investigation of the Phase Equilibria of Sn-Cu-Au Ternary and Ag-Sn-Cu-Au Quaternary Systems and Interfacial Reactions in Sn-Cu/Au Couples

    NASA Astrophysics Data System (ADS)

    Yen, Yee-Wen; Jao, Chien-Chung; Hsiao, Hsien-Ming; Lin, Chung-Yung; Lee, Chiapyng

    2007-02-01

    The phase equilibria of the Sn-Cu-Au ternary, Ag-Sn-Cu-Au quaternary systems and interfacial reactions between Sn-Cu alloys and Au were experimentally investigated at specific temperatures in this study. The experimental results indicated that there existed three ternary intermetallic compounds (IMCs) and a complete solid solubility between AuSn and Cu6Sn5 phases in the Sn-Cu-Au ternary system at 200°C. No quaternary IMC was found in the isoplethal section of the Ag-Sn-Cu-Au quaternary system. Three IMCs, AuSn, AuSn2, and AuSn4, were found in all couples. The same three IMCs and (Au,Cu)Sn/(Cu,Au)6Sn5 phases were found in all Sn-Cu/Au couples. The thickness of these reaction layers increased with increasing temperature and time. The mechanism of IMC growth can be described by using the parabolic law. In addition, when the reaction time was extended and the Cu content of the alloy was increased, the AuSn4 phase disappeared gradually. The (Au, Cu)Sn and (Cu,Au)6Sn5 layers played roles as diffusion barriers against Sn in Sn-Cu/Au reaction couple systems.

  12. Cu-Ag sulfides as indicators of pre-porphyritic epithermal Au-Ag deposits in Northeastern Russia

    NASA Astrophysics Data System (ADS)

    Savva, N. E.; Sidorov, A. A.; Volkov, A. V.

    2016-08-01

    Au-Ag mineralization of the Olcha and Teploe epithermal deposits underwent thermal metamorphism due to porphyritic intrusions. The presence of Bi-bearing galena and matildite in the ores (Teploe), Cu-Te-bearing naumannite (Olcha), the occurrence of middle- and high-temperature facies of metasomatic rocks (epidote and actinolite), and temperature formation conditions are related, firstly, to the influence of granitoids on the ore process, which supplied not only Cu and Mo, but also Bi, Te, and, secondly, to the heating of host rocks containing pre-porphyritic epithermal Au-Ag mineralization. The abundance of Cu-Ag sulfides and Cu-acanthite resulted from the enrichment of later mineral phases in Cu and Ag under the substance redistribution with the formation of Ag-acanthite ores. The data considered in the paper are of practical importance for regional forecasting of metallogenic constructions, exploration, and evaluation of the epithermal Au-Ag deposits.

  13. TUNING OF SIZE AND SHAPE OF AU-PT NANOCATALYST FOR DIRECT METHANOL FUEL CELLS

    SciTech Connect

    Murph, S.

    2011-04-20

    In this paper, we report the precise control of the size, shape and surface morphology of Au-Pt nanocatalysts (cubes, blocks, octahedrons and dogbones) synthesized via a seed-mediated approach. Gold 'seeds' of different aspect ratios (1 to 4.2), grown by a silver-assisted approach, were used as templates for high-yield production of novel Au-Pt nanocatalysts at a low temperature (40 C). Characterization by electron microscopy (SEM, TEM, HRTEM), energy dispersive X-ray analysis (EDX), UV-Vis spectroscopy, zeta-potential (surface charge), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS) were used to better understand their physico-chemical properties, preferred reactivities and underlying nanoparticle growth mechanism. A rotating disk electrode was used to evaluate the Au-Pt nanocatalysts electrochemical performance in the oxygen reduction reaction (ORR) and the methanol oxidation reaction (MOR) of direct methanol fuel cells. The results indicate the Au-Pt dogbones are partially and in some cases completely unaffected by methanol poisoning during the evaluation of the ORR. The ORR performance of the octahedron particles in the absence of MeOH is superior to that of the Au-Pt dogbones and Pt-black, however its performance is affected by the presence of MeOH.

  14. Magnetic susceptibility and hardness of Au-xPt-yNb alloys for biomedical applications.

    PubMed

    Uyama, Emi; Inui, Shihoko; Hamada, Kenichi; Honda, Eiichi; Asaoka, Kenzo

    2013-09-01

    Metal devices in the human body induce serious metal artifacts in magnetic resonance imaging (MRI). Metals artifacts are mainly caused by a volume magnetic susceptibility (χv) mismatch between a metal device and human tissue. In this research, Au-xPt-yNb alloys were developed for fabricating MRI artifact-free biomedical metal devices. The magnetic properties, hardness and phase constitutions of these alloys were investigated. The Au-xPt-8Nb alloys showed satisfactory χv values. Heat treatments did not clearly change the χv values for Au-xPt-8Nb alloys. The Vickers hardness (HV) of these two alloys was much higher than that of high-Pt alloys; moreover, aging at 700°C increased the HV values of these two alloys. A dual phase structure consisting of face-centered cubic α1 and α2 phases was observed and aging at 700°C promoted phase separation. The Au-5Pt-8Nb and Au-10Pt-8Nb alloys showed satisfactory χv values and high hardness and are thus suggested as candidates for MRI artifact-free alloys for biomedical applications.

  15. Oxygen reduction reaction activity and structural stability of Pt-Au nanoparticles prepared by arc-plasma deposition.

    PubMed

    Takahashi, Shuntaro; Chiba, Hiroshi; Kato, Takashi; Endo, Shota; Hayashi, Takehiro; Todoroki, Naoto; Wadayama, Toshimasa

    2015-07-28

    The oxygen reduction reaction (ORR) activity and durability of various Au(x)/Pt100 nanoparticles (where x is the atomic ratio of Au against Pt) are evaluated herein. The samples were fabricated on a highly-oriented pyrolytic graphite substrate at 773 K through sequential arc-plasma depositions of Pt and Au. The electrochemical hydrogen adsorption charges (electrochemical surface area), particularly the characteristic currents caused by the corner and edge sites of the Pt nanoparticles, decrease with increasing Au atomic ratio (x). In contrast, the specific ORR activities of the Au(x)/Pt100 samples were dependent on the atomic ratios of Pt and Au: the Au28/Pt100 sample showed the highest specific activity among all the investigated samples (x = 0-42). As for ORR durability evaluated by applying potential cycles between 0.6 and 1.0 V in oxygen-saturated 0.1 M HClO4, Au28/Pt100 was the most durable sample against the electrochemical potential cycles. The results clearly showed that the Au atoms located at coordinatively-unsaturated sites, e.g. at the corners or edges of the Pt nanoparticles, can improve the ORR durability by suppressing unsaturated-site-induced degradation of the Pt nanoparticles. PMID:26118789

  16. Enhanced electrocatalytic activity of the Au-electrodeposited Pt nanoparticles-coated conducting oxide for the quantum dot-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Yoon, Yeung-Pil; Kim, Jae-Hong; Kang, Soon-Hyung; Kim, Hyunsoo; Choi, Chel-Jong; Kim, Kyong-Kook; Ahn, Kwang-Soon

    2014-08-01

    Au was electrodeposited potentiostatically at 0.3 V for 5 min on nanoporous Pt nanoparticle-coated F-doped SnO2 (FTO/Pt) substrates. For comparison, Au-electrodeposited FTO (FTO/Au) and Au-uncoated FTO/Pt were prepared. FTO/Au showed large-sized Au clusters dispersed sparsely over FTO, which resulted in lower electrocatalytic activity than FTO/Pt. In contrast, FTO/Pt exhibited poor stability unlike FTO/Au due to poisoning by the adsorption of sulfur species. The Au-electrodeposited FTO/Pt (FTO/Pt/Au) consisted of small Au clusters deposited over the entire area of Pt due to the effective Au nucleation provided by nanoporous metallic Pt. FTO/Pt/Au exhibited enhanced electrocatalytic activity and excellent stability because the small Au particles well-dispersed over the nanoporous metallic Pt network provided numerous electrochemical reaction sites, and the Pt surface was not exposed to the electrolyte. When FTO/Pt/Au was used as the counter electrode (CE) of a quantum dot-sensitized solar cell, the significantly enhanced electrocatalytic activity of the FTO/Pt/Au CE facilitated the reduction reaction of Sn2- + 2e- (CE) → Sn-12- + S2- at the CE/electrolyte interface, resulting in a significantly hindered recombination reaction, Sn2- + 2e- (TiO2 in the photoanode) → Sn-12- + S2-, and significantly improved overall energy conversion efficiency.

  17. Electrochemical deposition of mesoporous Pt-Au alloy films in aqueous surfactant solutions: towards a highly sensitive amperometric glucose sensor.

    PubMed

    Li, Cuiling; Wang, Hongjing; Yamauchi, Yusuke

    2013-02-11

    Film star: The synthesis of mesoporous Pt-Au alloy films of varying composition by using a square-wave potential program is described. A Pt(51)Au(49) alloy film exhibits superior performance for the detection of glucose than those reported previously. The activity was found to be strongly dependent on the synergistic effects of the mesoporous structure and the Pt-Au alloy surface.

  18. PVP induce self-seeding process for growth of Au@Ag core@shell nanocomposites

    NASA Astrophysics Data System (ADS)

    Eisa, Wael H.; Al-Ashkar, Emad; El-Mossalamy, S. M.; Ali, Safaa S. M.

    2016-05-01

    A novel self-seeding route is developed for fabrication of metallic nanocomposites of gold (core) and silver (shell) (Au@Ag core@shell). Herein, polyvinylpyrrolidone (PVP) is used as both reducing and stabilizing agent. The surface plasmon resonance (SPR) of Au@Ag core@shell can be tuned by controlling the thickness of the Ag shell. The different growth stages of the Au@Ag core@shell have been traced by in situ UV-vis absorption spectra. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy are used for the characterization of the prepared samples.

  19. Enhancing the performance of catalytic AuPt nanoparticles in nonaqueous lithium-oxygen batteries

    NASA Astrophysics Data System (ADS)

    Lu, Meihua; Chen, Dongyun; Xu, Chaohe; Zhan, Yi; Lee, Jim Yang

    2015-07-01

    The deposition of catalytic AuPt (1 : 1) nanoparticles (NPs) into hollow mesoporous nitrogen-doped carbon microspheres (HMCMS) was found to significantly improve the effectiveness of the catalysis of oxygen reactions in nonaqueous lithium-oxygen batteries (LOBs); surpassing the performance of unsupported AuPt NPs or HMCMS in discharge and charge overpotentials (lower), specific capacity and rate performance (higher), and cycle life (longer). Specifically at a typical current density of 100 mA g-1, a LOB with the AuPt/HMCMS cathode catalyst could provide discharge and charge capacities of 6028 and 6000 mA h g-1 respectively and a charge-discharge voltage gap of only 1.27 V. The discharge capacity decreased by 5% when the current density was doubled, and by 23% when the current density was quintupled. The AuPt/HMCMS LOB could be cycled 75 times for a depth of discharge (DOD) of 1000 mA h g-1 without exceeding the charge cut-off voltage of 4.4 V. These measurements indicate that the HMCMS is an outstanding catalyst support to use for increasing the effectiveness of oxygen electrocatalysts in the LOBs.The deposition of catalytic AuPt (1 : 1) nanoparticles (NPs) into hollow mesoporous nitrogen-doped carbon microspheres (HMCMS) was found to significantly improve the effectiveness of the catalysis of oxygen reactions in nonaqueous lithium-oxygen batteries (LOBs); surpassing the performance of unsupported AuPt NPs or HMCMS in discharge and charge overpotentials (lower), specific capacity and rate performance (higher), and cycle life (longer). Specifically at a typical current density of 100 mA g-1, a LOB with the AuPt/HMCMS cathode catalyst could provide discharge and charge capacities of 6028 and 6000 mA h g-1 respectively and a charge-discharge voltage gap of only 1.27 V. The discharge capacity decreased by 5% when the current density was doubled, and by 23% when the current density was quintupled. The AuPt/HMCMS LOB could be cycled 75 times for a depth of discharge (DOD

  20. [Atomic emission spectrometry determination of Au, Pt and Pd after separation and enrichment by hyperbranched polymer].

    PubMed

    Li, Hui-Zhi; Zhai, Dian-Tang; Shou, Chong-Qi; Zhao, Shu-Ying; Wei, Qin

    2006-09-01

    The present paper shows that the trace amount of gold, platinum and palladium in hydrochloric acid solution can be concentrated by hyperbranched polymer. The new reagent has a rapid adsorption rate and big concentrating capacity. The determination of trace Au, Pt and Pd in sample using carbon powder and strontium carbonate as buffer was carried out by atomic emission spectrometry(AES). Zirconium was selected as internal standard line. The sample was directly loaded into ordinary electrode. The method is simple, rapid and accurate. The condition of determination, and factors of influence were studied. The analysis line of Au, Pt and Pd is 312.3, 306.5 and 311.4 nm respectively. The internal standard line of Zr is 310.7 nm. The linear range of the determination of Au, Pt and Pd is 0-0. 20%, 0-0. 40% and 0-0. 20% respectively. The detection limit of Au, Pt and Pd is 0.010%, 0.0030% and 0.0030% respectively. The method has been applied to the determination of Au, Pt and Pd with satisfactory results.

  1. Graphene decorated with PtAu alloy nanoparticles: facile synthesis and promising application for formic acid oxidation

    SciTech Connect

    Zhang, Sheng; Shao, Yuyan; Liao, Honggang; Liu, Jun; Aksay, Ilhan A.; Yin, Geping; Lin, Yuehe

    2011-03-01

    PtAu alloy nanoparticles (~ 3.2 nm in diameter) are synthesized in poly(diallyldimethylammonium chloride) (PDDA) aqueous solution and uniformly dispersed on graphene nanosheets. PtAu/graphene exhibits high electrocatalytic activity and stability for formic acid oxidation, which is attributed to the high dispersion of PtAu nanoparticles and the specific interaction between PtAu and graphene, indicating a promising catalyst for direct formic acid fuel cells. The facile method can be readily extended to the synthesis of other alloy nanoparticles.

  2. Role of Ag addition in L10 ordering of FePt-based nanocomposite magnets

    NASA Astrophysics Data System (ADS)

    Crisan, A. D.; Vasiliu, F.; Mercioniu, I.; Crisan, O.

    2014-01-01

    The FePt system has important perspectives as high-temperature corrosion-resistant magnets. In the form of rapidly solidified melt-spun ribbons, FePt-based magnets may exhibit in certain cases a two-phase hard-soft magnetic behaviour. The present paper deals with a microstructural and magnetic study of FePtAgB alloys with increasing Ag content. The aim is to identify and confirm the effect of Ag addition in decreasing the temperature of the FePt disorder-order structural phase transformation. A detailed high-resolution transmission electron microscopy study is employed, and the alternative disposal of hard and soft regions within the two-phase microstructure is observed and interpreted with respect to the X-ray diffraction results. In the as-cast Ag-containing samples, it is shown that there is an optimum of the Ag content for which best magnetic properties are obtained. Ag addition creates a nonlinear behaviour of the coercive field and the ordering parameter, similar to the RKKY interaction-induced interlayer exchange coupling (IEC) observed in magnetic layers separated by non-magnetic spacer layers. Direct formation of the L10 phase from the as-cast state in the FePtAgB alloys is reported with magnetic parameters compatible to other exchange spring permanent nanomagnets. These findings open novel perspectives into utilization of such alloys in applications requiring magnets operating in high-temperature industrial environments.

  3. Highly transparent Au-coated Ag nanowire transparent electrode with reduction in haze.

    PubMed

    Kim, Taegeon; Canlier, Ali; Cho, Changsoon; Rozyyev, Vepa; Lee, Jung-Yong; Han, Seung Min

    2014-08-27

    Ag nanowire transparent electrode has excellent transmittance and sheet resistance, yet its optical haze still needs to be improved in order for it to be suitable for display applications. Ag nanowires are known to have high haze because of the geometry of the nanowire and the high light scattering characteristic of the Ag. In this study, a Au-coated Ag nanowire structure was proposed to reduce the haze, where a thin layer of Au was coated on the surface of the Ag nanowires using a mild [Au(en)2]Cl3 galvanic displacement reaction. The mild galvanic exchange allowed for a thin layer of Au coating on the Ag nanowires with minimal truncation of the nanowire, where the average length and the diameter were 13.0 μm and 60 nm, respectively. The Au-coated Ag nanowires were suspended in methanol and then electrostatically sprayed on a flexible polycarbonate substrate that revealed a clear reduction in haze with a 2-4% increase in total transmittance, sheet resistance ranges of 80-90%, and 8.8-36.8 Ohm/sq. Finite difference time domain simulations were conducted for Au-coated Ag nanowires that indicated a significant reduction in the average scattering from 1 to 0.69 for Au layer thicknesses of 0-10 nm.

  4. Kinetics-controlled growth of bimetallic RhAg on Au nanorods and their catalytic properties

    NASA Astrophysics Data System (ADS)

    Ye, Wei; Guo, Xia; Xie, Fang; Zhu, Rui; Zhao, Qing; Yang, Jian

    2014-03-01

    Controlled growth of hybrid metallic nanocomposites for a desirable structure in a combination of selected components is highly important for their applications. Herein, the controllable growth of RhAg on the gold nanorods is achieved from the dumbbell-like RhAg-tipped nanorods to the brushy RhAg-coated nanorods, or the rod-like Au@Ag-Rh nanorattles. These different growth modes of RhAg on the gold nanorods are correlated with the reducing kinetics of RhCl3 and AgNO3. In view of the promising catalytic properties of Rh, the gold nanorods modified by RhAg in different structures are examined as catalysts for the oxidation of o-phenylenediamine. It is found that brushy RhAg-coated nanorods present a higher catalytic efficiency than dumbbell-like RhAg-tipped nanorods and rod-like Au@Ag-Rh nanorattles. These results would benefit the overgrowth control on the one-dimensional metallic nanorods and the rational design of new generation heterogeneous catalysts and optical devices.Controlled growth of hybrid metallic nanocomposites for a desirable structure in a combination of selected components is highly important for their applications. Herein, the controllable growth of RhAg on the gold nanorods is achieved from the dumbbell-like RhAg-tipped nanorods to the brushy RhAg-coated nanorods, or the rod-like Au@Ag-Rh nanorattles. These different growth modes of RhAg on the gold nanorods are correlated with the reducing kinetics of RhCl3 and AgNO3. In view of the promising catalytic properties of Rh, the gold nanorods modified by RhAg in different structures are examined as catalysts for the oxidation of o-phenylenediamine. It is found that brushy RhAg-coated nanorods present a higher catalytic efficiency than dumbbell-like RhAg-tipped nanorods and rod-like Au@Ag-Rh nanorattles. These results would benefit the overgrowth control on the one-dimensional metallic nanorods and the rational design of new generation heterogeneous catalysts and optical devices. Electronic

  5. Formation of one-dimensional Ag-Au solid solution colloids with Au nanorods as seeds, their alloying mechanisms, and surface plasmon resonances.

    PubMed

    Guo, Tao; Tan, Yiwei

    2013-01-21

    In this work, one dimensional (1D) Ag-Au solid solution nanoalloys were synthesized by rapidly diffusing Ag into the preformed Au nanorod (AuNR) seeds at ambient temperature in aqueous solution. By varying the molar ratio of AgCl/AuNR (in gold atoms), two kinds of 1D Ag-Au alloy nanostructures with a narrow size distribution--AgAu nanowires and Ag(33)Au(67) nanorods--could be obtained in high yields when NaCl and polyvinylpyrrolidone (PVP) were used as an additive and capping reagent, respectively. Based on HRTEM imaging combined with a series of control experiments, it is conceivable that vacancy/defect-motivated interdiffusion of Ag and Au atoms coupled with oxidative etching is a crucial stage in the mechanism responsible for this room-temperature alloying process, and the subsequent conjugation of the fused Ag-Au alloyed nanostructures is associated with the formation of the AgAu nanowires. The resulting 1D Ag-Au nanoalloys form stable colloidal dispersions and show unique localized surface plasmon resonance (LSPR) peaks in the ensemble extinction spectra.

  6. 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.

  7. Isolation and structural characterization of a silver-platinum nanocluster, Ag4Pt2(DMSA)4.

    PubMed

    Biltek, Scott R; Sen, Ayusman; Pedicini, Anthony F; Reber, Arthur C; Khanna, Shiv N

    2014-09-18

    We report the synthesis, isolation, and characterization of the ligand-protected bimetallic cluster, Ag4Pt2(DMSA)4 (DMSA = meso-2,3,-dimercaptosuccinic acid). The procedure is similar to the one employed for the synthesis of Ag4Ni2(DMSA)4. Theoretical studies suggest that the Pt and Ni atoms have square planar configurations. Because the crystal field splitting of 5d orbitals is typically larger than that for 3d orbitals, the Pt-based cluster has an optical spectrum that is significantly blue-shifted as compared to the Ni-based cluster.

  8. Transmission electron microscopy characterization of Au/Pt/Ti/Pt/GaAs ohmic contacts for high power GaAs/InGaAs semiconductor lasers.

    PubMed

    Łaszcz, A; Czerwinski, A; Ratajczak, J; Szerling, A; Phillipp, F; Van Aken, P A; Katcki, J

    2010-03-01

    We report on transmission electron microscopy studies of Au/Pt/Ti/Pt(10-30 nm) contact structures for high power GaAs/InGaAs semiconductor lasers. The studies showed that annealing at 450 degrees C of contact structures causes the reaction of whole Pt with substrate components (Ga and As) and the formation of Pt-GaAs interlayers with smooth interfaces as required for such structures. Annealing of the structures at 470 and 490 degrees C unfavourably affects the contact structure. At this condition, the strong downward diffusion of Au and Pt from the top layers causes a formation of Au-Pt pits, which break the Ti barrier. Transmission electron microscopy observation revealed that Au/Pt/Ti/Pt(10-30 nm) system annealed at 450 degrees C is appropriate for practical applications. The EDS technique used to identify the phase composition in the Pt(30 nm)/GaAs structure (specially produced for the EDS analysis) annealed at 450 degrees C showed that two layers were formed as a result of the reaction of the whole Pt layer with GaAs, and they consist of Ga, Pt and As. The top layer has the highest concentration of Ga. However, the bottom layer, which is close to the substrate, has the highest concentration of As.

  9. 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.

  10. A highly efficient phase transfer method for preparing alkylamine-stabilized Ru, Pt, and Au nanoparticles.

    PubMed

    Yang, J; Lee, Jim Yang; Deivaraj, T C; Too, Heng-Phon

    2004-09-01

    A highly efficient phase-transfer method was developed to prepare alkylamine-stabilized nanoparticles of several noble metals. This method involved first mixing the metal hydrosols and an ethanol solution of dodecylamine and then extracting the dodecylamine-stabilized metal nanoparticles into toluene. The efficiency of this phase-transfer method was nearly 100%. Alkylamine-stabilized Ru, Pt, and Au nanoparticles 3.45, 4.33, and 7.89 nm in diameter, respectively, could be prepared this way. The self-assembly of dodecylamine-stabilized Pt and Au particles was also detected by transmission electron microscopy (TEM).

  11. Trimetallic Au/Pt/Rh Nanoparticles as Highly Active Catalysts for Aerobic Glucose Oxidation

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    This paper reports the findings of an investigation of the correlations between the catalytic activity for aerobic glucose oxidation and the composition of Au/Pt/Rh trimetallic nanoparticles (TNPs) with average diameters of less than 2.0 nm prepared by rapid injection of NaBH4. The prepared TNPs were characterized by UV-Vis, TEM, and HR-TEM. The catalytic activity of the alloy-structured TNPs for aerobic glucose oxidation is several times higher than that of Au monometallic nanoparticles with nearly the same particle size. The catalytic activities of the TNP catalysts were dependent not only on the composition, but also on the electronic structure. The high catalytic activities of the Au/Pt/Rh TNPs can be ascribed to the formed negative-charged Au atoms due to electron donation of Rh neighboring atoms acting as catalytically active sites for aerobic glucose oxidation.

  12. 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.

  13. Label free detection of DNA on Au/ZnO/Ag hybrid structure based SERS substrate

    NASA Astrophysics Data System (ADS)

    Pal, Anil Kumar; Mohan, D. Bharathi

    2016-04-01

    Au/ZnO/Ag based SERS substrate was fabricated for the label free detection of DNA of Escherichia Coli bacteria. The SERS substrate was fabricated by growing ZnO nanorod arrays on thermally evaporated ultrathin Ag film of 5 nm thickness using hydrothermal process. Non-spherical like Au nanoparticles were decorated on ZnO nanorod arrays by sputtering technique with sputtering time of 45 sec. The surface of Au/ZnO/Ag was observed to be nearly superhydrophobic exhibiting the contact angle of 144 °. A low volume (5 µl) of aqueous solution of DNA of laboratory strain Escherichia Coli with very low concentration was adsorbed on fabricated SERS substrate by drop casting. The SERS detection of DNA molecules was achieved up to lower concentration of 10-8 M due to strong local electric field enhancement at the nanometer gap among Au nanoparticles and superhydrophobic nature of Au/ZnO/Ag surface.

  14. 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

  15. Luminescent, bimetallic AuAg alloy quantum clusters in protein templates.

    PubMed

    Mohanty, Jyoti Sarita; Xavier, P Lourdu; Chaudhari, Kamalesh; Bootharaju, M S; Goswami, N; Pal, S K; Pradeep, T

    2012-07-21

    We report the synthesis of luminescent AuAg alloy quantum clusters (QCs) in bovine serum albumin (BSA), for the first time, with experimentally determined atomic composition. Mixing of the as-synthesized protein-protected Au and Ag clusters resulted in the formation of alloy AuAg clusters within the BSA. Mass spectrometric analysis of the product of a 1 : 1 molar ratio reaction mixture of Au(QC)@BSA and Ag(QC)@BSA suggested that the alloy clusters could be Au(38-x)Ag(x)@BSA. Further analyses by standard techniques revealed that the alloy cluster core of ∼1.2 nm diameter is composed of nearly zero valent Au and Ag atoms that exhibit distinctly different steady state and time resolved excited state luminescence profiles compared to the parent clusters. Tuning of the alloy composition was achieved by varying the molar ratio of the parent species in the reaction mixture and compositional changes were observed by mass spectrometry. In another approach, mixing of Au(3+) ions with the as-synthesized Ag(QC)@BSA also resulted in the formation of alloy clusters through galvanic exchange reactions. We believe that alloy clusters with the combined properties of the constituents in versatile protein templates would have potential applications in the future. The work presents interesting aspects of the reactivity of the protein-protected clusters. PMID:22684267

  16. Structure and electronic behavior of 26-atom Cu-Ag and Cu-Au nanoalloys

    NASA Astrophysics Data System (ADS)

    Guzmán-Ramírez, Gregorio; Robles, Juvencio; Aguilera-Granja, Faustino

    2016-09-01

    We hereby present a density functional theory (DFT) study of the structural, energetic, and electronic properties of the binary clusters Cu n X26- n (with X = Ag and Au). Our electronic calculations were performed with the DFT package GAUSSIAN 09, and we chose the BPW91 exchange correlation functional in combination with an effective core potential LANL2DZ basis set as our level of theory. We find that in the case of these clusters and in a completely different way - as compared to the bulk chemical order observed in both alloys CuAg (segregation) and CuAu (ordering) -, for small n both Ag and Au clusters exhibit a similar chemical order, finding the Cu atoms in the center of the cluster with the tendency to form core shell structures. On the other hand, for large n values the Ag and Au atoms tend to occupy surface positions forming separated surface islands that keep the two metal atoms separated as long as the concentration allows it. Concerning the structural properties, a clear increase in the interatomic distance of the Ag-Ag and Au-Au surface pairs is observed, particularly in the equiatomic region. In conclusion, both nanoalloys CuAg and CuAu behave quite similarly in contrast to their respective bulk cases.

  17. Structural and Optical Properties of Discrete Dendritic Pt Nanoparticles on Colloidal Au Nanoprisms

    PubMed Central

    2016-01-01

    Catalytic and optical properties can be coupled by combining different metals into nanoscale architectures in which both the shape and the composition provide fine-tuning of functionality. Here, discrete, small Pt nanoparticles (diameter = 3–6 nm) were grown in linear arrays on Au nanoprisms, and the resulting structures are shown to retain strong localized surface plasmon resonances. Multidimensional electron microscopy and spectroscopy techniques (energy-dispersive X-ray spectroscopy, electron tomography, and electron energy-loss spectroscopy) were used to unravel their local composition, three-dimensional morphology, growth patterns, and optical properties. The composition and tomographic analyses disclose otherwise ambiguous details of the Pt-decorated Au nanoprisms, revealing that both pseudospherical protrusions and dendritic Pt nanoparticles grow on all faces of the nanoprisms (the faceted or occasionally twisted morphologies of which are also revealed), and shed light on the alignment of the Pt nanoparticles. The electron energy-loss spectroscopy investigations show that the Au nanoprisms support multiple localized surface plasmon resonances despite the presence of pendant Pt nanoparticles. The plasmonic fields at the surface of the nanoprisms indeed extend into the Pt nanoparticles, opening possibilities for combined optical and catalytic applications. These insights pave the way toward comprehensive nanoengineering of multifunctional bimetallic nanostructures, with potential applications in plasmon-enhanced catalysis and in situ monitoring of chemical processes via surface-enhanced spectroscopy. PMID:27688821

  18. Structural and Optical Properties of Discrete Dendritic Pt Nanoparticles on Colloidal Au Nanoprisms

    PubMed Central

    2016-01-01

    Catalytic and optical properties can be coupled by combining different metals into nanoscale architectures in which both the shape and the composition provide fine-tuning of functionality. Here, discrete, small Pt nanoparticles (diameter = 3–6 nm) were grown in linear arrays on Au nanoprisms, and the resulting structures are shown to retain strong localized surface plasmon resonances. Multidimensional electron microscopy and spectroscopy techniques (energy-dispersive X-ray spectroscopy, electron tomography, and electron energy-loss spectroscopy) were used to unravel their local composition, three-dimensional morphology, growth patterns, and optical properties. The composition and tomographic analyses disclose otherwise ambiguous details of the Pt-decorated Au nanoprisms, revealing that both pseudospherical protrusions and dendritic Pt nanoparticles grow on all faces of the nanoprisms (the faceted or occasionally twisted morphologies of which are also revealed), and shed light on the alignment of the Pt nanoparticles. The electron energy-loss spectroscopy investigations show that the Au nanoprisms support multiple localized surface plasmon resonances despite the presence of pendant Pt nanoparticles. The plasmonic fields at the surface of the nanoprisms indeed extend into the Pt nanoparticles, opening possibilities for combined optical and catalytic applications. These insights pave the way toward comprehensive nanoengineering of multifunctional bimetallic nanostructures, with potential applications in plasmon-enhanced catalysis and in situ monitoring of chemical processes via surface-enhanced spectroscopy.

  19. Growth of various Au Ag nanocomposites from gold seeds in amino acid solutions

    NASA Astrophysics Data System (ADS)

    Huang, Yu-Fen; Lin, Yang-Wei; Chang, Huan-Tsung

    2006-10-01

    In this paper, we describe an easy procedure for the preparation of differently shaped and sized Au-Ag nanocomposites from gold nanorod (AuNR) seeds in various amino acid solutions—arginine (Arg), cysteine (Cys), glycine (Gly), glutamate (Glu), glutamine (Gln), histidine (His), lysine (Lys), and methionine (Met), respectively—at values of pH ranging from 8.0 to 11.5. Our results suggest that the pH, the nature of the amino acid, and its concentration all have significant impact on the preparation of Au-Ag nanocomposites; these factors exhibit their effects mainly through control over the reducing ability of ascorbate and/or its recognition capability, as well as through control over the surface charges of the amino acids on the AuNRs. Depending on the value of pH, we were able to prepare I-shaped, dumbbell-shaped, and/or sphere-shaped Au-Ag nanocomposites in 0.1 M solutions of Arg, Gly, Glu, Gln, Lys, and Met. In His solutions at pH 8.0 and 9.0, we obtained peanut-shaped Au-Ag nanocomposites. Corn-shaped Au-Ag nanocomposites were prepared in 0.1 M Met solutions (pH 9.0 and 10.0). By controlling the Lys concentration at pH 10.0, we synthesized pearl-necklace-shaped Au-Ag nanoparticles and Au-Ag wires. Based on the TEM images, we conclude that this simple and reproducible synthetic approach allows preparation of high-quality (>87%, beside>77% in His solutions) Au-Ag nanocomposites with various shapes and sizes under different conditions.

  20. Highly Fluorescent Gene Carrier Based on Ag-Au Alloy Nanoclusters.

    PubMed

    Wang, Ping; Lin, Lin; Guo, Zhaopei; Chen, Jie; Tian, Huayu; Chen, Xuesi; Yang, Hua

    2016-01-01

    For systemic delivery of gene, gold nanoparticles (GNPs) have been exploited as novel gene carriers because of the excellent characteristics for "visible" in intracellular trafficking. Herein, a highly fluorescent gene carrier was prepared by conjugating polyethylenimines on Ag-Au alloy nanoclusters. This carrier exhibited remarkable high gene transfection efficiencies and relatively low cytotoxicity toward B16F10, HeLa, and CHO cells. More interestingly, the high fluorescent Ag-Au-PEI conjugates showed high quantum yield of 14.56%, which is much higher than most of the reported gold nanocluster-based quantum dots and Ag-Au-PEI possessed bioimaging capacity both in vitro and in vivo.

  1. Au and Ag/Au double-shells hollow nanoparticles with improved near infrared surface plasmon and photoluminescence properties.

    PubMed

    Ghosh Chaudhuri, Rajib; Paria, Santanu

    2016-01-01

    Metallic hollow nanoparticles have been continuously drawing researcher's attention because of their excellent improved performance compare to the spherical particles in catalysis, photonics, information storage, surface-enhanced Raman scattering, and sensors applications. In this article we demonstrate a novel route for the synthesis of single and double-shells Au and Ag/Au bimetallic hollow nanoparticles using elemental sulfur as a sacrificial core. We also investigate the optical properties of these new hollow particles and compare with that of pure spherical nanoparticles. The surface plasmon resonance spectra of solid Au, hollow single shell Au, and double shells Ag/Au nanoparticles show that there is gradual shifting of Au peak position towards the higher wavelengths for these three nanoparticles respectively. A similar observation was also found for photoluminescence spectra. In case of double-shells Ag/Au hollow nanoparticles the emission spectrum shifts towards the NIR region with significant higher intensity, which is beneficial for in vivo biomedical applications of these particles.

  2. Bimetallic PtAu superlattice arrays: Highly electroactive and durable catalyst for oxygen reduction and methanol oxidation reactions

    NASA Astrophysics Data System (ADS)

    Feng, Jiu-Ju; He, Li-Li; Fang, Rui; Wang, Qiao-Li; Yuan, Junhua; Wang, Ai-Jun

    2016-10-01

    Superlattice arrays, an important type of nanomaterials, have wide applications in catalysis, optic/electronics and energy storage for the synergetic effects determined by both individual metals and collective interactions. Herein, a simple one-pot solvothermal coreduction approach is developed for facile preparation of bimetallic PtAu alloyed superlattice arrays (PtAu SLAs) in oleylamine, with the assistance of urea via hydrogen bonding induced self-assembly. Urea is essential in morphology-controlled process and prevents PtAu nanoparticles from the disordered aggregation. The characterization and formation mechanism of PtAu SLAs are investigated in details. The as-synthesized hybrid nanocrystals exhibit enhanced electrocatalytic performances for oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) in alkaline electrolyte in comparison with commercial Pt-C (50%, wt.%) and Pt black catalysts.

  3. 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.

  4. Scanning tunneling microscopy of Cu, Ag, Au and Al adatoms, small clusters, and islands on graphite

    NASA Astrophysics Data System (ADS)

    Ganz, Eric; Sattler, Klaus; Clarke, John

    1989-09-01

    We have used a scanning tunneling microscope to study the static and dynamic behaviour of Cu, Ag, Au, and Al deposited in situ on highly oriented pyrolytic graphite in an ultra-high vacuum chamber. We have imaged static monomers of Ag, Au, and Al, dimers of Ag and Au, and clusters of 3 or more atoms of Ag, Al, and Au. From the lifetime of the monomers, we estimate the energy barrier against diffusion to be greater than 0.65 eV. We have studied two-dimensional islands of Ag and Au, containing up to 100 atoms, which are atomically resolved against the supporting graphite substrate. The interiors of the islands contain ordered rectangular lattices separated by grain boundaries, while the atoms at the periphery are disordered. We show a small three-dimensional Cu crystal, the decoration of a grain boundary by Cu particles with an average diameter of 44 Å, and two examples of granular films. Finally, we present examples of dynamic processes: the shrinking of a small Au island, the contraction of the lattice spacing of a rectangular two-dimensional Au lattice on a time scale of minutes, and the diffusion of a Ag cluster along a graphite step edge on a time scale of seconds.

  5. Core-size-dependent catalytic properties of bimetallic Au/Ag core-shell nanoparticles.

    PubMed

    Haldar, Krishna Kanta; Kundu, Simanta; Patra, Amitava

    2014-12-24

    Bimetallic core-shell nanoparticles have recently emerged as a new class of functional materials because of their potential applications in catalysis, surface enhanced Raman scattering (SERS) substrate and photonics etc. Here, we have synthesized Au/Ag bimetallic core-shell nanoparticles with varying the core diameter. The red-shifting of the both plasmonic peaks of Ag and Au confirms the core-shell structure of the nanoparticles. Transmission electron microscopy (TEM) analysis, line scan EDS measurement and UV-vis study confirm the formation of core-shell nanoparticles. We have examined the catalytic activity of these core-shell nanostructures in the reaction between 4-nitrophenol (4-NP) and NaBH4 to form 4-aminophenol (4-AP) and the efficiency of the catalytic reaction is found to be increased with increasing the core size of Au/Ag core-shell nanocrystals. The catalytic efficiency varies from 41.8 to 96.5% with varying core size from 10 to 100 nm of Au/Ag core-shell nanoparticles, and the Au100/Ag bimetallic core-shell nanoparticle is found to be 12-fold more active than that of the pure Au nanoparticles with 100 nm diameter. Thus, the catalytic properties of the metal nanoparticles are significantly enhanced because of the Au/Ag core-shell structure, and the rate is dependent on the size of the core of the nanoparticles.

  6. Selective Growth of Ag Nanodewdrop on Au Nanostructure: A New Type of Bimetallic Heterostructure

    PubMed Central

    Gao, Li

    2009-01-01

    A new type of bimetallic Au-Ag heterostructured material was prepared by a selective growing strategy of Ag nanodewdrop on the petal tip of Au flower using electrochemical method. The whole process was strictly controlled by forming the reactive tip of flower petal and passivating the facet along the body of metal petal using poly(vinyl pyrrolidone)(PVP) coating film. The formed Au-Ag HSFs were observed to be about 2 μm in diameter and have the Ag particles of about 50 nm settled on the tips of Au petals. The Au-Ag HSFs were found to display the superior properties on the surface-enhanced Raman scattering (SERS). The presence of Ag nanodewdrops could also facilitate the oxidation of Ru(bpy)32+ complex in electrogenerated chemiluminescence (ECL) measurements and dramatically enhance the emission intensity. The features of Au-Ag HSFs can promise a new type of heterogeneous bimetallic alloy material for the potential applications in chemical and biological sensors. PMID:19788230

  7. Uniform Au@Pt core-shell nanodendrites supported on molybdenum disulfide nanosheets for the methanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Su, Shao; Zhang, Chi; Yuwen, Lihui; Liu, Xingfen; Wang, Lihua; Fan, Chunhai; Wang, Lianhui

    2015-12-01

    Herein, we presented a facile seeded growth method to prepare high-quality three-dimensional (3D) Au@Pt bimetallic nanodendrite-decorated molybdenum disulfide (MoS2) nanosheets (Au@Pt/MoS2). Transmission electron microscopy (TEM) and high-resolution TEM exhibited that Au@Pt core-shell nanostructures were dispersed onto the surface of MoS2 nanosheets. More importantly, the thickness of the Pt shell of the Au@Pt bimetallic nanodendrites on the surface of the MoS2 nanosheets could be easily tuned via simply changing the synthesis parameters, such as the concentration of H2PtCl6, reaction time and temperature, which greatly influence the catalytic ability of Au@Pt/MoS2 nanohybrids. Both cyclic voltammetry (CV) and chronoamperometry (CA) demonstrated that the as-prepared Au@Pt/MoS2 nanohybrids possessed much higher electrocatalytic activity and stability than Pt/MoS2 or commercial Pt/C catalyst. The peak current mass density of the selected Au@Pt/MoS2 was 6.24 A mg-1, which was 3389 and 20.3 times those of Pt/C (0.00184 A mg-1) and Pt/MoS2 (0.307 A mg-1), respectively. The presented method may be a facile approach for the synthesis of MoS2-supported bimetallic nanocomposites, which is significant for the development of high performance MoS2-based sensors and catalysts.Herein, we presented a facile seeded growth method to prepare high-quality three-dimensional (3D) Au@Pt bimetallic nanodendrite-decorated molybdenum disulfide (MoS2) nanosheets (Au@Pt/MoS2). Transmission electron microscopy (TEM) and high-resolution TEM exhibited that Au@Pt core-shell nanostructures were dispersed onto the surface of MoS2 nanosheets. More importantly, the thickness of the Pt shell of the Au@Pt bimetallic nanodendrites on the surface of the MoS2 nanosheets could be easily tuned via simply changing the synthesis parameters, such as the concentration of H2PtCl6, reaction time and temperature, which greatly influence the catalytic ability of Au@Pt/MoS2 nanohybrids. Both cyclic voltammetry (CV

  8. Analogous Au-H and Pt-H Defects in Silicon

    NASA Astrophysics Data System (ADS)

    Evans, M. J.; Uftring, S. J.; Gornstein, M. G.; Stavola, Michael

    1997-03-01

    In recent years, several transition metals have been shown to form electrically active complexes with hydrogen in semiconductors. (Uftring et al)., Phys. Rev. B 51, 9612 (1995). (Sveinbjornsson et al)., Phys. Rev. B 52, 4884 (1995). (Jost et al)., Phys. Rev. B 54 R11038 (1996). The availability of structural information for such defects remains limited to a few cases. We report on the common characteristics of two defects formed by the hydrogenation of the substitutional transition metals Au and Pt in Si. Vibrational spectroscopy has been used to show that a Au-H complex and Pt-H complex have very similar properties. The Au-H defect gives rise to absorption bands at 1813.3 and 1827.1 cm(-1), and the corresponding Pt-H defect gives rise to bands at 1880.7 and 1897.2 cm(-1). In addition to their similar absorption frequencies, these defects each contain a single H atom and have a level in the gap. The two also behave similarly under uniaxial stress, having trigonal symmetry and exhibiting low temperature reorientation. We propose a structure for the Au-H and Pt-H defects, in which the substitutional transition metal atom and the H atom lie along a (<111>) direction. Supported by NSF Grant No. DMR-9415404

  9. Enhancing the performance of catalytic AuPt nanoparticles in nonaqueous lithium-oxygen batteries.

    PubMed

    Lu, Meihua; Chen, Dongyun; Xu, Chaohe; Zhan, Yi; Lee, Jim Yang

    2015-08-14

    The deposition of catalytic AuPt (1 : 1) nanoparticles (NPs) into hollow mesoporous nitrogen-doped carbon microspheres (HMCMS) was found to significantly improve the effectiveness of the catalysis of oxygen reactions in nonaqueous lithium-oxygen batteries (LOBs); surpassing the performance of unsupported AuPt NPs or HMCMS in discharge and charge overpotentials (lower), specific capacity and rate performance (higher), and cycle life (longer). Specifically at a typical current density of 100 mA g(-1), a LOB with the AuPt/HMCMS cathode catalyst could provide discharge and charge capacities of 6028 and 6000 mA h g(-1) respectively and a charge-discharge voltage gap of only 1.27 V. The discharge capacity decreased by 5% when the current density was doubled, and by 23% when the current density was quintupled. The AuPt/HMCMS LOB could be cycled 75 times for a depth of discharge (DOD) of 1000 mA h g(-1) without exceeding the charge cut-off voltage of 4.4 V. These measurements indicate that the HMCMS is an outstanding catalyst support to use for increasing the effectiveness of oxygen electrocatalysts in the LOBs. PMID:26165186

  10. Surface Plasmon Enhanced Photocatalysis of Au/Pt-decorated TiO2 Nanopillar Arrays

    PubMed Central

    Shuang, Shuang; Lv, Ruitao; Xie, Zheng; Zhang, Zhengjun

    2016-01-01

    The low quantum yields and lack of visible light utilization hinder the practical application of TiO2 in high-performance photocatalysis. Herein, we present a design of TiO2 nanopillar arrays (NPAs) decorated with both Au and Pt nanoparticles (NPs) directly synthesized through successive ion layer adsorption and reaction (SILAR) at room temperature. Au/Pt NPs with sizes of ~4 nm are well-dispersed on the TiO2 NPAs as evidenced by electron microscopic analyses. The present design of Au/Pt co-decoration on the TiO2 NPAs shows much higher visible and ultraviolet (UV) light absorption response, which leads to remarkably enhanced photocatalytic activities on both the dye degradation and photoelectrochemical (PEC) performance. Its photocatalytic reaction efficiency is 21 and 13 times higher than that of pure TiO2 sample under UV-vis and visible light, respectively. This great enhancement can be attributed to the synergy of electron-sink function of Pt and surface plasmon resonance (SPR) of Au NPs, which significantly improves charge separation of photoexcited TiO2. Our studies demonstrate that through rational design of composite nanostructures one can harvest visible light through the SPR effect to enhance the photocatalytic activities initiated by UV-light, and thus realize more effectively utilization of the whole solar spectrum for energy conversion. PMID:27215703

  11. Surface Plasmon Enhanced Photocatalysis of Au/Pt-decorated TiO2 Nanopillar Arrays.

    PubMed

    Shuang, Shuang; Lv, Ruitao; Xie, Zheng; Zhang, Zhengjun

    2016-01-01

    The low quantum yields and lack of visible light utilization hinder the practical application of TiO2 in high-performance photocatalysis. Herein, we present a design of TiO2 nanopillar arrays (NPAs) decorated with both Au and Pt nanoparticles (NPs) directly synthesized through successive ion layer adsorption and reaction (SILAR) at room temperature. Au/Pt NPs with sizes of ~4 nm are well-dispersed on the TiO2 NPAs as evidenced by electron microscopic analyses. The present design of Au/Pt co-decoration on the TiO2 NPAs shows much higher visible and ultraviolet (UV) light absorption response, which leads to remarkably enhanced photocatalytic activities on both the dye degradation and photoelectrochemical (PEC) performance. Its photocatalytic reaction efficiency is 21 and 13 times higher than that of pure TiO2 sample under UV-vis and visible light, respectively. This great enhancement can be attributed to the synergy of electron-sink function of Pt and surface plasmon resonance (SPR) of Au NPs, which significantly improves charge separation of photoexcited TiO2. Our studies demonstrate that through rational design of composite nanostructures one can harvest visible light through the SPR effect to enhance the photocatalytic activities initiated by UV-light, and thus realize more effectively utilization of the whole solar spectrum for energy conversion. PMID:27215703

  12. 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...

  13. Surface Plasmon Enhanced Photocatalysis of Au/Pt-decorated TiO2 Nanopillar Arrays

    NASA Astrophysics Data System (ADS)

    Shuang, Shuang; Lv, Ruitao; Xie, Zheng; Zhang, Zhengjun

    2016-05-01

    The low quantum yields and lack of visible light utilization hinder the practical application of TiO2 in high-performance photocatalysis. Herein, we present a design of TiO2 nanopillar arrays (NPAs) decorated with both Au and Pt nanoparticles (NPs) directly synthesized through successive ion layer adsorption and reaction (SILAR) at room temperature. Au/Pt NPs with sizes of ~4 nm are well-dispersed on the TiO2 NPAs as evidenced by electron microscopic analyses. The present design of Au/Pt co-decoration on the TiO2 NPAs shows much higher visible and ultraviolet (UV) light absorption response, which leads to remarkably enhanced photocatalytic activities on both the dye degradation and photoelectrochemical (PEC) performance. Its photocatalytic reaction efficiency is 21 and 13 times higher than that of pure TiO2 sample under UV-vis and visible light, respectively. This great enhancement can be attributed to the synergy of electron-sink function of Pt and surface plasmon resonance (SPR) of Au NPs, which significantly improves charge separation of photoexcited TiO2. Our studies demonstrate that through rational design of composite nanostructures one can harvest visible light through the SPR effect to enhance the photocatalytic activities initiated by UV-light, and thus realize more effectively utilization of the whole solar spectrum for energy conversion.

  14. Chemisorption and FTIR study of bimetallic Pt-Au/SiO sub 2 catalysts

    SciTech Connect

    Balakrishnan, K.; Sachdev, A.; Schwank, J. )

    1990-02-01

    Pt/SiO{sub 2}, Au/SiO{sub 2}, and bimetallic Pt-Au/SiO{sub 2} catalysts were prepared by incipient wetness impregnation of nonporous SiO{sub 2}. The catalysts were characterized after reduction in H{sub 2} by static volumetric chemisorption and infrared spectroscopy. For the monometallic and the bimetallic catalysts, H{sub 2}, O{sub 2} and CO were used as adsorbates at room temperature. Additionally, for the monometallic Au/SiO{sub 2} catalyst, O{sub 2} adsorption at 473 K was also used. Infrared spectra of adsorbed CO were obtained on all catalysts. Addition of gold decreased the uptake of all three adsorbates at room temperature, without significantly influencing the relative amounts of weakly held adsorbed species which could be removed upon pumping for 30 min. Agreeing with CO chemisorption data, the total integrated intensity of the linear CO band decreased with increasing Au content. The IR results indicated a predominantly geometric effect of Au causing a shift of the linear CO band to lower wavenumbers. The shift could be rationalized in terms of decreased dipole-dipole coupling of adsorbed CO species. The results are discussed within the context of a previous investigation using electron microscopy, TPR, and reactivity data. Portions of the bimetallic catalysts were subjected to three high-temperature oxidation/reduction cycles and characterized by static chemisorption of H{sub 2} to investigate the effect of this thermal treatment on Pt dispersion.

  15. Fungal biomolecules assisted biosynthesis of Au-Ag alloy nanoparticles and evaluation of their catalytic property.

    PubMed

    Tripathi, Ravi Mani; Gupta, Rohit Kumar; Bhadwal, Akhshay Singh; Singh, Priti; Shrivastav, Archana; Shrivastav, B R

    2015-08-01

    The catalytic reduction of methylene blue was studied using biosynthesised gold-silver (Au-Ag) alloy nanoparticles (NPs). The fungal biomass of Trichoderma harzianum was used as a reducing and stabilising agent in the synthesis of Au-Ag alloy NPs. The synthesised NPs were well characterised by UV-vis spectroscopy, dynamic light scattering, X-ray diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy. The plausible synthesis mechanism involved in the formation of Au-Ag alloy NPs was also discussed with diagrammatic representation. A series of experiments was performed to investigate the catalytic activity of the as-prepared Au-Ag alloy NPs and found that the alloy NPs show excellent catalytic activity. PMID:26224346

  16. Oxygen reduction kinetics on Pt monolayer shell highly affected by the structure of bimetallic AuNi cores

    DOE PAGES

    Chen, Guangyu; Kuttiyiel, Kurian A.; Su, Dong; Li, Meng; Wang, Chiu -Hui; Buceta, David; Du, Chunyu; Gao, Yunzhi; Yin, Geping; Sasaki, Kotaro; et al

    2016-07-12

    Here, we describe pronounced effects of structural changes of the AuNi cores on the oxygen reduction reaction (ORR) activity of a Pt monolayer shell. The study of alloyed AuNi nanoparticles compared with AuNi core–shell structured nanoparticles revealed configurations having different electronic and electrochemical properties. Controlled alloying of Au with Ni was essential to tune the electronic properties of Au interacting with the Pt monolayer shell to achieve suitable adsorption of O2 on Pt for expediting the ORR. The alloyed AuNi nanoparticles made the Pt shell more catalytically active for the ORR than the core–shell structured AuNi nanoparticles. The Pt monolayermore » supported on the alloyed AuNi nanoparticles showed the Pt mass and specific activities as high as 1.52 A mg–1 and 1.18 mA cm–2, respectively, with almost no loss over 5 000 cycles of stability test. This high ORR activity is ascribed to the role of nonspecific steric configuration of Ni atoms changing the electronic properties of the alloy that affect the oxygen and water interaction with the Pt shell and facilitate increased ORR kinetics.« less

  17. Templated Atom-Precise Galvanic Synthesis and Structure Elucidation of a [Ag24Au(SR)18](-) Nanocluster.

    PubMed

    Bootharaju, Megalamane S; Joshi, Chakra P; Parida, Manas R; Mohammed, Omar F; Bakr, Osman M

    2016-01-18

    Synthesis of atom-precise alloy nanoclusters with uniform composition is challenging when the alloying atoms are similar in size (for example, Ag and Au). A galvanic exchange strategy has been devised to produce a compositionally uniform [Ag24Au(SR)18](-) cluster (SR: thiolate) using a pure [Ag25(SR)18](-) cluster as a template. Conversely, the direct synthesis of Ag24Au cluster leads to a mixture of [Ag(25-x)Au(x)(SR)18](-), x=1-8. Mass spectrometry and crystallography of [Ag24Au(SR)18](-) reveal the presence of the Au heteroatom at the Ag25 center, forming Ag24Au. The successful exchange of the central Ag of Ag25 with Au causes perturbations in the Ag25 crystal structure, which are reflected in the absorption, luminescence, and ambient stability of the particle. These properties are compared with those of Ag25 and Ag24Pd clusters with same ligand and structural framework, providing new insights into the modulation of cluster properties with dopants at the single-atom level.

  18. Seeded growth of robust SERS-active 2D Au@Ag nanoparticulate films

    SciTech Connect

    Baker, Gary A; Dai, Sheng; Hagaman, Edward {Ed} W; Mahurin, Shannon Mark; Zhu, Haoguo; Bao, Lili

    2008-01-01

    We demonstrate herein a novel and versatile solution-based methodology for fabricating self-organized two-dimensional (2D) Au nanoparticle arrays on glass using in situ nucleation at an aminosilane monolayer followed by seeded, electroless growth; subsequent deposition of Ag produced Au{at}Ag core-shell nanoparticulate films which proved highly promising as surface-enhanced Raman scattering (SERS) platforms.

  19. 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

  20. A composition and size controllable approach for Au-Ag alloy nanoparticles

    PubMed Central

    2012-01-01

    A capillary micro-reaction was established for the synthesis of Au-Ag alloy nanoparticles (NPs) with a flexible and controllable composition and grain size by tuning the synthesis temperature, the residence time, or the mole ratio of Au3+:Ag+. By extending the residence time from 5 to 900 s, enhancing the temperature from 120°C to 160°C, or decreasing the mole ratio of Au3+:Ag+ from 1:1 to 1:20, the composition of samples was changed continuously from Au-rich to Ag-rich. The particles became large with the increase of the residence time; however, synthesis temperatures showed less effect on the particle size change. The particle size of the Au-Ag alloy NPs with various composition could be kept by adjusting the mole ratio of Au3+:Ag+. TEM observation displayed that the as-obtained NPs were sphere-like with the smallest average size of 4.0 nm, which is half of those obtained by the traditional flask method. PMID:22513005

  1. Necklace-shaped Au-Ag nanoalloys: laser-assisted synthesis and nonlinear optical properties

    NASA Astrophysics Data System (ADS)

    Jafarkhani, P.; Torkamany, M. J.; Dadras, S.; Chehrghani, A.; Sabbaghzadeh, J.

    2011-06-01

    Here in this paper, necklace-shaped Au-Ag nanoalloys (NAs) have been synthesized by a laser-based approach. A chain of Ag nanoparticles (NPs), which were joined together with Au junctions, was formed upon copper vapor laser (CVL) irradiation of a colloidal mixture of Ag and Au NPs; while the corresponding NPs were separately provided by laser ablation of gold and silver targets in deionized water by a 1064 nm Q-switched Nd:YAG laser. Dependence of the NAs development process on the CVL irradiation time in three distinct stages of as-mixed, nucleation and complete formation has been systematically studied by UV-vis optical absorption spectroscopy analysis as well as by transmission electron microscopy (TEM), which was exploited to visually confirm the NAs evolution through the process. Furthermore, the x-ray photoelectron spectroscopy (XPS) technique was accurately employed to determine the synthesized alloy content. On the other hand, using the open-and closed-aperture Z-scan technique, the nonlinear absorption (NLA) as well as nonlinear refraction (NLR) changes in Au-Ag NAs were investigated through their formation. The deduced results from the nonlinear optical properties of the colloidal NAs in the mentioned stages were interpreted considering the spectroscopic and microscopic observations. The total change of individual Au and Ag NPs saturable absorption (SA) into the reverse saturable absorption (RSA) behavior was concluded through the evolution into Au-Ag NAs.

  2. Bidirectional threshold switching characteristics in Ag/ZrO2/Pt electrochemical metallization cells

    NASA Astrophysics Data System (ADS)

    Du, Gang; Wang, Chao; Li, Hongxia; Mao, Qinan; Ji, Zhenguo

    2016-08-01

    A bidirectional threshold switching (TS) characteristic was demonstrated in Ag/ZrO2/Pt electrochemical metallization cells by using the electrochemical active Ag electrode and appropriate programming operation strategies The volatile TS was stable and reproducible and the rectify ratio could be tuned to ˜107 by engineering the compliance current. We infer that the volatile behavior is essentially due to the moisture absorption in the electron beam evaporated films, which remarkably improved the anodic oxidation as well as the migration of Ag+ ions. The resultant electromotive force would act as a driving force for the metal filaments dissolution, leading to the spontaneous volatile characteristics. Moreover, conductance quantization behaviors were also achieved owing to formation and annihilation of atomic scale metal filaments in the film matrix. Our results illustrate that the Ag/ZrO2/Pt device with superior TS performances is a promising candidate for selector applications in passive crossbar arrays.

  3. Comparative study of the alloying effect on the initial oxidation of Cu-Au(100) and Cu-Pt(100)

    SciTech Connect

    Luo, Langli; Zhou, Guangwen; Kang, Yihong; Yang, Judith C.; Su, Dong; Stach, Eric A.

    2014-03-24

    Using in situ transmission electron microscopy, we show that the oxidation of the Cu-Au(100) results in the formation of Cu{sub 2}O islands that deeply embed into the Cu-Au substrate while the oxidation of the Cu-Pt(100) leads to the formation of Cu{sub 2}O islands that highly protrude above the Cu-Pt substrate. Their difference is attributed to the different mobilities of Pt and Au in the Cu base alloys for which the sluggish mobility of Pt in Cu results in trapped Pt atoms at the oxide/alloy interface while the faster mobility of Au in Cu leads to enhanced rehomogenization of the alloy composition.

  4. Morphological control and evolution of octahedral and truncated trisoctahedral Pt-Au alloy nanocrystals under microwave irradiation

    NASA Astrophysics Data System (ADS)

    Dai, Lei; Zhao, Yanxi; Chi, Quan; Liu, Hanfan; Li, Jinlin; Huang, Tao

    2014-08-01

    Uniform and well-defined truncated trisoctahedral and octahedral Pt-Au alloy nanocrystals were fabricated by co-reducing H2PtCl6-HAuCl4 with tetraethylene glycol (TEG) under microwave irradiation for only 140 s. Iodide ions were critical to the morphological control and evolution of Pt-Au alloy nanostructures. The as-prepared Pt-Au alloy nanocrystals exhibited efficient electrocatalytic activities.Uniform and well-defined truncated trisoctahedral and octahedral Pt-Au alloy nanocrystals were fabricated by co-reducing H2PtCl6-HAuCl4 with tetraethylene glycol (TEG) under microwave irradiation for only 140 s. Iodide ions were critical to the morphological control and evolution of Pt-Au alloy nanostructures. The as-prepared Pt-Au alloy nanocrystals exhibited efficient electrocatalytic activities. Electronic supplementary information (ESI) available: Experimental details; SEM, TEM and HAADF-STEM images, UV-vis absorbance spectra, XRD. See DOI: 10.1039/c4nr01864h

  5. Direct electrochemical oxidation of S-captopril using gold electrodes modified with graphene-AuAg nanocomposites.

    PubMed

    Pogacean, Florina; Biris, Alexandru R; Coros, Maria; Lazar, Mihaela Diana; Watanabe, Fumiya; Kannarpady, Ganesh K; Al Said, Said A Farha; Biris, Alexandru S; Pruneanu, Stela

    2014-01-01

    In this paper, we present a novel approach for the electrochemical detection of S-captopril based on graphene AuAg nanostructures used to modify an Au electrode. Multi-layer graphene (Gr) sheets decorated with embedded bimetallic AuAg nanoparticles were successfully synthesized catalytically with methane as the carbon source. The two catalytic systems contained 1.0 wt% Ag and 1.0 wt% Au, while the second had a larger concentration of metals (1.5 wt% Ag and 1.5 wt% Au) and was used for the synthesis of the Gr-AuAg-1 and Gr-AuAg-1.5 multicomponent samples. High-resolution transmission electron microscopy analysis indicated the presence of graphene flakes that had regular shapes (square or rectangular) and dimensions in the tens to hundreds of nanometers. We found that the size of the embedded AuAg nanoparticles varied between 5 and 100 nm, with the majority being smaller than 20 nm. Advanced scanning transmission electron microscopy studies indicated a bimetallic characteristic of the metallic clusters. The resulting Gr-AuAg-1 and Gr-AuAg-1.5 samples were used to modify the surface of commonly used Au substrates and subsequently employed for the direct electrochemical oxidation of S-captopril. By comparing the differential pulse voltammograms recorded with the two modified electrodes at various concentrations of captopril, the peak current was determined to be well-defined, even at relatively low concentration (10(-5) M), for the Au/Gr-AuAg-1.5 electrode. In contrast, the signals recorded with the Au/Gr-AuAg-1 electrode were poorly defined within a 5×10(-6) to 5×10(-3) M concentration range, and many of them overlapped with the background. Such composite materials could find significant applications in nanotechnology, sensing, or nanomedicine.

  6. Direct electrochemical oxidation of S-captopril using gold electrodes modified with graphene-AuAg nanocomposites

    PubMed Central

    Pogacean, Florina; Biris, Alexandru R; Coros, Maria; Lazar, Mihaela Diana; Watanabe, Fumiya; Kannarpady, Ganesh K; Al Said, Said A Farha; Biris, Alexandru S; Pruneanu, Stela

    2014-01-01

    In this paper, we present a novel approach for the electrochemical detection of S-captopril based on graphene AuAg nanostructures used to modify an Au electrode. Multi-layer graphene (Gr) sheets decorated with embedded bimetallic AuAg nanoparticles were successfully synthesized catalytically with methane as the carbon source. The two catalytic systems contained 1.0 wt% Ag and 1.0 wt% Au, while the second had a larger concentration of metals (1.5 wt% Ag and 1.5 wt% Au) and was used for the synthesis of the Gr-AuAg-1 and Gr-AuAg-1.5 multicomponent samples. High-resolution transmission electron microscopy analysis indicated the presence of graphene flakes that had regular shapes (square or rectangular) and dimensions in the tens to hundreds of nanometers. We found that the size of the embedded AuAg nanoparticles varied between 5 and 100 nm, with the majority being smaller than 20 nm. Advanced scanning transmission electron microscopy studies indicated a bimetallic characteristic of the metallic clusters. The resulting Gr-AuAg-1 and Gr-AuAg-1.5 samples were used to modify the surface of commonly used Au substrates and subsequently employed for the direct electrochemical oxidation of S-captopril. By comparing the differential pulse voltammograms recorded with the two modified electrodes at various concentrations of captopril, the peak current was determined to be well-defined, even at relatively low concentration (10−5 M), for the Au/Gr-AuAg-1.5 electrode. In contrast, the signals recorded with the Au/Gr-AuAg-1 electrode were poorly defined within a 5×10−6 to 5×10−3 M concentration range, and many of them overlapped with the background. Such composite materials could find significant applications in nanotechnology, sensing, or nanomedicine. PMID:24596464

  7. Bimetallic Pt-Au Nanocatalysts on ZnO/Al2O3/Monolith for Air Pollution Control.

    PubMed

    Kim, Ki-Joong; Ahn, Ho-Geun

    2015-08-01

    The catalytic activity of a monolithic catalyst with nanosized Pt and Au particles on ZnO/Al2O3 (Pt-Au/ZnO/Al2O3/M) prepared by a wash-coat method was examined, specifically for toluene oxidation. Scanning electron microscopy image showed clearly the formation of a ZnO/Al2O3 layer on the monolith. Nanosized Pt-Au particles on ZnO/Al2O3/M with different sizes could be found in the Pt-Au/ZnO/Al2O3/M catalyst. The conversion of toluene decreased with increasing toluene concentration and was also largely affected by the feed flow rate. The Pt-Au/ZnO/Al2O3/M catalysts prepared in this work have almost the same activity (molecules of toluene per second) compared with a powder Pt-Au/ZnO/Al2O3 catalyst with the same loadings of Pt and Au components; thus this catalyst could be used in controlling air pollution with very low concentrations and high flow rate. PMID:26369207

  8. Electrocatalytic oxidation of small organic molecules on Pt-Au nanoparticles supported by POMAN-MWCNTs

    NASA Astrophysics Data System (ADS)

    Dong, Qi-Zhi; Li, Li-Li; Chen, Qian-Shan; Guo, Can-Cheng; Yu, Gang

    2015-08-01

    Poly ( o-methoxyaniline) and multi-wall carbon nanotube composite (POMAN-MWCNT) films were deposited onto the platinum (Pt) electrode surface by cyclic voltammetry (CV). Then, platinum and gold (Au) nano-particles were deposited by CV and the double potential deposition method to modify the composite film on the Pt electrode. The morphology of the composite film was characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and its electrocatalytic activity toward methanol and formaldehyde oxidation was studied by CV and other electrochemical methods. The results demonstrated that Pt-Au/POMAN-MWCNTs obtained by the double potential deposition method had a much higher catalytic activity and better anti-poisoning property for electrooxidation of methanol and formaldehyde. The improved catalytic performance could be attributed to the uniformly distribution of duel-metal nanoparticles and the synergistic effect between Pt and Au metals. The abstract should briefly state the problem or purpose of the research, indicate the methodology used, summarize the principal findings and major conclusions.

  9. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    NASA Astrophysics Data System (ADS)

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-08-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

  10. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters.

    PubMed

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-01-01

    Understanding of the "structure-activity" relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au(3+) ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size. PMID:27476577

  11. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    PubMed Central

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-01-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size. PMID:27476577

  12. Egg White Templated Synthesis of Ag and Au@Ag Alloy Microspheres for Surface-Enhanced Raman Spectroscopy Research.

    PubMed

    Li, Min; Zhang, Ying; Wang, Xiansong; Cui, Daxiang

    2016-01-01

    Herein, we report the green synthesis of Ag and Au@Ag microspheres by using the aqueous extracts of the egg white as well as their application as substrates for surface-enhanced Raman spectroscopy (SERS) detection. Both microspheres are prepared via the green synthesis method (room temperature, in aqueous solution and a benign reducer). The as-prepared urchin-like Ag microspheres have an average diameter of 600-800 nm, which is made up of some nanopricks with an average length of 10-40 nm. Meanwhile, the Au@Ag architectures prepared by galvanic replacement keep nearly similar size, which is also composed of some compact nanoparticles with an average diameter of about 10-40 nm. These products are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electronic microscopy (TEM), and Fourier transform infrared spectrophotometer (FTIR). The study on SERS activities is also carried out for both microspheres. It is found that Au@Ag microspheres possess much higher SERS activity than Ag microspheres. Our work may shed light on the design and synthesis of self-assembled 3D micro/nano-architectures for the use of SERS, catalysis, biosensors, nanomedicine, etc. PMID:27398550

  13. Egg White Templated Synthesis of Ag and Au@Ag Alloy Microspheres for Surface-Enhanced Raman Spectroscopy Research.

    PubMed

    Li, Min; Zhang, Ying; Wang, Xiansong; Cui, Daxiang

    2016-01-01

    Herein, we report the green synthesis of Ag and Au@Ag microspheres by using the aqueous extracts of the egg white as well as their application as substrates for surface-enhanced Raman spectroscopy (SERS) detection. Both microspheres are prepared via the green synthesis method (room temperature, in aqueous solution and a benign reducer). The as-prepared urchin-like Ag microspheres have an average diameter of 600-800 nm, which is made up of some nanopricks with an average length of 10-40 nm. Meanwhile, the Au@Ag architectures prepared by galvanic replacement keep nearly similar size, which is also composed of some compact nanoparticles with an average diameter of about 10-40 nm. These products are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electronic microscopy (TEM), and Fourier transform infrared spectrophotometer (FTIR). The study on SERS activities is also carried out for both microspheres. It is found that Au@Ag microspheres possess much higher SERS activity than Ag microspheres. Our work may shed light on the design and synthesis of self-assembled 3D micro/nano-architectures for the use of SERS, catalysis, biosensors, nanomedicine, etc.

  14. Phytosynthesis of stable Au, Ag and Au-Ag alloy nanoparticles using J. Sambac leaves extract, and their enhanced antimicrobial activity in presence of organic antimicrobials

    NASA Astrophysics Data System (ADS)

    Yallappa, S.; Manjanna, J.; Dhananjaya, B. L.

    2015-02-01

    A green chemistry approach for the synthesis of Au, Ag and Au-Ag alloy nanoparticles (NPs) using the corresponding metal precursors and Jasminum sambac leaves extract as both reducing and capping media, under microwave irradiation, is reported. During the formation, as expected, the reaction mixture shows marginal decrease in pH and an increase in solution potential. The formation of NPs is evident from their surface plasmon resonance (SPR) peak observed at ∼555 nm for Au, ∼435 nm for Ag and ∼510 nm for Au-Ag alloy. The XRD pattern shows fcc structure while the FTIR spectra indicate the presence of plant residues adsorbed on these NPs. Such a bio-capping of NPs is characterized by their weight loss, ∼35% due to thermal degradation of biomass, as observed in TG analysis. The colloidal dispersion of NPs is stable for about 6 weeks. The near spherical shape of NPs (ϕ20-50 nm) is observed by FE-SEM/TEM images and EDAX gives the expected elemental composition. Furthermore, these NPs showed enhanced antimicrobial activity (∼1-4-fold increase in zone of inhibition) in combination with antimicrobials against test strains. Thus, the phytosynthesized NPs could be used as effective growth inhibitors for various microorganisms.

  15. Synthesis and characterization of Au-core Ag-shell nanoparticles from unmodified apoferritin

    SciTech Connect

    Li, T.; Chattopadhyay, S.; Shibata, T.; Cook, R. E.; Miller, J. T.; Suthiwangcharoen, N.; Lee, S.; Winans, R. E.; Lee, B.

    2012-01-01

    Narrow-size distributed, water-soluble Au-core Ag-shell nanoparticles with a size range from 1 to 5 nm are synthesized using unmodified apoferritin as a template. Fast protein liquid chromatography reveals that the nanoparticles are formed inside the apoferritin cavity and are stable in aqueous solution. Electron microscopy shows that the particles are uniform in size and composed of both Au and Ag. In addition, extended X-ray absorption fine structure confirms that the particles have a core-shell structure with a Au core covered with a Ag shell. By varying the loading amounts of the silver precursor, the Ag shell thickness is controlled from one layer to several layers.

  16. Intriguing centrality dependence of the Au-Au source size at the AGS

    SciTech Connect

    Baker, M.D.; The E802 Collaboration

    1996-06-01

    One of the main goals of high energy heavy ion physics is to establish the existence of a deconfined phase of nuclear matter--the quark-gluon plasma--at high temperatures or densities. One possible signature of such a phase transition, especially if it were first order, would be a larger source size or lifetime than a similar hadronic system. At current AGS energies, we attempt to form a quark- gluon plasma by achieving a high baryon density for a period of time in the center of the collision region. For a given density threshold, the size of this high density region should be a strong function of the impact parameter: the more central the event, the larger the high density region. Therefore, one possible signature of a quark-gluon plasma would be a sudden change in system lifetime or size as a function of the centrality of the collision. In this talk we present an intriguing effect which was not predicted for simple hadronic systems: a rapid increase of the HBT-measured source radius parameter for pion pairs with increasing centrality for Au-Au collisions at a beam momentum of 11.45 A GeV/c on a fixed target. Experience has shown, however, that we must be cautious in our interpretation. A complete understanding of the collision dynamics at a given energy must be built up from several measurements and new, but conventional, hadronic explanations must be considered for such unexpected effects. More study is needed, therefore, before any strong conclusions can be reached.

  17. System size dependence of hadron pT spectra in p + p and Au+Au collisions at \\sqrt{s_{NN}} = 200 GeV

    NASA Astrophysics Data System (ADS)

    Khandai, P. K.; Sett, P.; Shukla, P.; Singh, V.

    2014-02-01

    We make a systematic study of transverse momentum (pT) spectra of hadrons produced in p + p and in different centralities of Au+Au collisions at center of mass energy of 200 GeV using phenomenological fit functions. The Tsallis distribution gives a very good description of hadron spectra in p + p collisions with just two parameters but does not produce the same in Au+Au collisions at intermediate pT. To explain the hadron spectra in heavy ion collisions in a wider pT range we propose a modified Tsallis function by introducing an additional parameter that accounts for collective flow. The new analytical function gives a very good description of both mesons and baryons spectra at all centralities of Au+Au collisions in terms of the parameters having a potential physics interpretation. With this modified Tsallis function we study the spectra of pions, kaons, protons, Λ and Ξ- as a function of system size at \\sqrt{s_{NN}} = 200 GeV. The parameter representing transverse flow increases with system size and is found to be more for baryons than that for mesons in central Au+Au collisions. The freeze-out temperature for baryons increases with centrality in Au+Au collisions more rapidly than for mesons.

  18. About the pre-Hispanic Au-Pt ``Sintering'' technique for making alloys

    NASA Astrophysics Data System (ADS)

    Noguez, M.; García, R.; Salas, G.; Robert, T.; Ramírez, J.

    2006-05-01

    The “sintering” technique to produce Au-Ptalloys in pre-Hispanic times in the South American region Tumaco-LaTolita (North Ecuador, South Colombia) is reviewed in this paper. Two Au-Pt alloys were made using small pieces of pure gold and platinum in an attempt to simulate some pre-Hispanic artisan alloys. A “sintering” process (950°C, cold and hot hammering) was done with metallurgical considerations. The results were analyzed with optical and scanning-electron microscopy and compared to the available microstructures of some similar pre-Hispanic composition alloys.

  19. Surface Plasmon-Mediated Energy Transfer in Hetero-Gap Au-Ag Nanowires

    PubMed Central

    Wei, Wei; Li, Shuzhou; Qin, Lidong; Xue, Can; Millstone, Jill E.; Xu, Xiaoyang; Schatz, George C.; Mirkin, Chad A.

    2011-01-01

    We report the observation of energy transfer from a gold (Au) nanodisk pair to a silver (Ag) nanowire across a 120 nm gap via surface plasmon resonance (SPR) excitation. The enhanced electromagnetic (EM) fields generated by Au SPR excitation induce oscillation of the conduction electrons in the Ag segment, transferring energy to it even though the Ag segment has only weak resonant interactions with the incident electromagnetic radiation. The induced Ag SPR produces strong EM fields at the position of the Ag segment, leading to a Raman signal ~15 times greater than when the Ag segment is alone (not adjacent to the Au nanodisk pair). The Raman intensity is found to depend nonlinearly on the incident laser intensity for laser power densities of 10 kW/cm2, which is consistent with the results of electromagnetic theory calculations which are not able to account for the factor of 15 enhancement based on a linear mechanism. This suggests that energy transfer from the Au disk pair to the Ag segment involves an enhanced nonlinear polarization mechanism such as can be produced by the electronic Kerr effect or stimulated Raman scattering. PMID:18767888

  20. 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.

  1. Tuning the SERS Response with Ag-Au Nanoparticle-Embedded Polymer Thin Film Substrates.

    PubMed

    Rao, V Kesava; Radhakrishnan, T P

    2015-06-17

    Development of facile routes to the fabrication of thin film substrates with tunable surface enhanced Raman scattering (SERS) efficiency and identification of the optimal conditions for maximizing the enhancement factor (EF) are significant in terms of both fundamental and application aspects of SERS. In the present work, polymer thin films with embedded bimetallic nanoparticles of Ag-Au are fabricated by a simple two-stage protocol. Ag nanoparticles are formed in the first stage, by the in situ reduction of silver nitrate by the poly(vinyl alcohol) (PVA) film through mild thermal annealing, without any additional reducing agent. In the second stage, aqueous solutions of chloroauric acid spread on the Ag-PVA thin film under ambient conditions, lead to the galvanic displacement of Ag by Au in situ inside the film, and the formation of Ag-Au particles. Evolution of the morphology of the bimetallic nanoparticles into hollow cage structures and the distribution of Au on the nanoparticles are revealed through electron microscopy and energy dispersive X-ray spectroscopy. The localized surface plasmon resonance (LSPR) extinction of the nanocomposite thin film evolves with the Ag-Au composition; theoretical simulation of the extinction spectra provides insight into the observed trends. The Ag-Au-PVA thin films are found to be efficient substrates for SERS. The EF follows the variation of the LSPR extinction vis-à-vis the excitation laser wavelength, but with an offset, and the maximum SERS effect is obtained at very low Au content; experiments with Rhodamine 6G showed EFs on the order of 10(8) and a limit of detection of 0.6 pmol. The present study describes a facile and simple fabrication of a nanocomposite thin film that can be conveniently deployed in SERS investigations, and the utility of the bimetallic system to tune and maximize the EF.

  2. Enhanced electrocatalytic activity of the Au-electrodeposited Pt nanoparticles-coated conducting oxide for the quantum dot-sensitized solar cells

    SciTech Connect

    Yoon, Yeung-Pil; Kim, Jae-Hong; Ahn, Kwang-Soon; Kang, Soon-Hyung; Kim, Hyunsoo; Choi, Chel-Jong; Kim, Kyong-Kook

    2014-08-25

    Au was electrodeposited potentiostatically at 0.3 V for 5 min on nanoporous Pt nanoparticle-coated F-doped SnO{sub 2} (FTO/Pt) substrates. For comparison, Au-electrodeposited FTO (FTO/Au) and Au-uncoated FTO/Pt were prepared. FTO/Au showed large-sized Au clusters dispersed sparsely over FTO, which resulted in lower electrocatalytic activity than FTO/Pt. In contrast, FTO/Pt exhibited poor stability unlike FTO/Au due to poisoning by the adsorption of sulfur species. The Au-electrodeposited FTO/Pt (FTO/Pt/Au) consisted of small Au clusters deposited over the entire area of Pt due to the effective Au nucleation provided by nanoporous metallic Pt. FTO/Pt/Au exhibited enhanced electrocatalytic activity and excellent stability because the small Au particles well-dispersed over the nanoporous metallic Pt network provided numerous electrochemical reaction sites, and the Pt surface was not exposed to the electrolyte. When FTO/Pt/Au was used as the counter electrode (CE) of a quantum dot-sensitized solar cell, the significantly enhanced electrocatalytic activity of the FTO/Pt/Au CE facilitated the reduction reaction of S{sub n}{sup 2− }+ 2e{sup −} (CE) → S{sub n−1}{sup 2−} + S{sup 2−} at the CE/electrolyte interface, resulting in a significantly hindered recombination reaction, S{sub n}{sup 2− }+ 2e{sup −} (TiO{sub 2} in the photoanode) → S{sub n-1}{sup 2−} + S{sup 2−}, and significantly improved overall energy conversion efficiency.

  3. Size effect on L10 ordering and magnetic properties of chemically synthesized FePt and FePtAu nanoparticles

    NASA Astrophysics Data System (ADS)

    Jia, Zhiyong; Kang, Shishou; Shi, Shifan; Nikles, David E.; Harrell, J. W.

    2005-05-01

    There is growing evidence that FePt nanoparticles become increasingly difficult to chemically order as the size approaches a few nanometers. We have studied the chemical ordering of FePt and FePtAu nanoparticle arrays as a function of particle size. Monodisperse Fe49Pt51 and Fe48Pt44Au8 nanoparticles with a size about 6nm were synthesized by the simultaneous decomposition of iron pentacarbonyl and reduction of platinum acetylacetonate and gold (III) acetate in a mixture of phenyl ether and hexadecylamine (HDA), with 1-adamantanecarboxylic acid and HDA as stabilizers. The nanoparticles were dispersed in toluene, films of the particles were cast onto silicon wafers from the dispersion, and the films were annealed in a tube furnace with flowing Ar +5%H2. The magnetic anisotropy and switching volumes were determined from time- and temperature-dependent coercivity measurements. By comparing with 3-nm FePt and FePtAu nanoparticles of comparable composition, the phase transformation is easier for the larger particles. Under the same annealing conditions, the larger particles have higher anisotropy and order parameter. Additive Au is very effective in enhancing the chemical ordering in both small and large particles, with x-ray diffraction superlattice peaks appearing after annealing at 350°C. Dynamic remnant coercivity measurements and magnetic switching volumes suggest particle aggregation at the higher annealing temperatures in both small and large particles.

  4. Low-energy electron elastic scattering cross sections for excited Au and Pt atoms

    NASA Astrophysics Data System (ADS)

    Felfli, Zineb; Eure, Amanda R.; Msezane, Alfred Z.; Sokolovski, Dmitri

    2010-05-01

    Electron elastic total cross sections (TCSs) and differential cross sections (DCSs) in both impact energy and scattering angle for the excited Au and Pt atoms are calculated in the electron impact energy range 0 ⩽ E ⩽ 4.0 eV. The cross sections are found to be characterized by very sharp long-lived resonances whose positions are identified with the binding energies of the excited anions formed during the collisions. The recent novel Regge-pole methodology wherein is embedded through the Mulholland formula the electron-electron correlations is used together with a Thomas-Fermi type potential incorporating the crucial core-polarization interaction for the calculations of the TCSs. The DCSs are evaluated using a partial wave expansion. The Ramsauer-Townsend minima, the shape resonances and the binding energies of the excited Au - and Pt - anions are extracted from the cross sections, while the critical minima are determined from the DCSs.

  5. High-frequency signal transmission through single-atom contacts of Au and Pt

    SciTech Connect

    Aoyama, Shodai; Kurokawa, Shu; Sakai, Akira

    2015-03-23

    Signal transmission through atom-sized contacts of Au and Pt has been studied at room temperature for frequencies from 9 kHz to 1 GHz and for conductances (1−10)G{sub 0} (G≡2e{sup 2}/h is the quantum unit of conductance). We measured the frequency spectrum of S parameter S{sub 21}=|S{sub 21}|e{sup iθ} and found θ∼0 up to 1 GHz for all contacts irrespective of their conductance. Our observations directly prove that the atom-sized contacts of Au and Pt, including their single-atom contacts, behave as a pure resistance in the RF regime.

  6. The protonation state of thiols in self-assembled monolayers on roughened Ag/Au surfaces and nanoparticles.

    PubMed

    Bandyopadhyay, Sabyasachi; Chattopadhyay, Samir; Dey, Abhishek

    2015-10-14

    The protonation state of thiols in self-assembled monolayers (SAMs) on Ag and Au surfaces and nanoparticles (NPs) has been an issue of contestation. It has been recently demonstrated that deuterating the thiol proton produces ostentatious changes in the Raman spectra of thiols and can be used to detect the presence of the thiol functional group. Surface enhanced Raman spectroscopy (SERS) of H/D substituted aliphatic thiols on Ag surfaces clearly shows the presence of S-H vibration between 2150-2200 cm(-1) which shifts by 400 cm(-1) upon deuteration and a simultaneous >20 cm(-1) shift in the C-S vibration of thiol deuteration. Large shifts (>15 cm(-1)) in the C-S vibration are also observed for alkyl thiol SAMs on Au surfaces. Alternatively, neither the S-H vibration nor the H/D isotope effect on the C-S vibration is observed for alkyl thiol SAMs on Ag/Au NPs. XPS data on Ag/Au surfaces bearing aliphatic thiol SAMs show the presence of both protonated and deprotonated thiols while on Ag/Au NPs only deprotonated thiols are detected. These data suggest that aliphatic thiol SAMs on Au/Ag surfaces are partially protonated whereas they are totally deprotonated on Au/Ag NPs. Aromatic PhSH SAMs on Ag/Au surfaces and Ag/Au NPs do not show these vibrations or H/D shifts as well indicating that the thiols are deprotonated at these interfaces.

  7. Luminescent, bimetallic AuAg alloy quantum clusters in protein templates

    NASA Astrophysics Data System (ADS)

    Mohanty, Jyoti Sarita; Xavier, P. Lourdu; Chaudhari, Kamalesh; Bootharaju, M. S.; Goswami, N.; Pal, S. K.; Pradeep, T.

    2012-06-01

    We report the synthesis of luminescent AuAg alloy quantum clusters (QCs) in bovine serum albumin (BSA), for the first time, with experimentally determined atomic composition. Mixing of the as-synthesized protein-protected Au and Ag clusters resulted in the formation of alloy AuAg clusters within the BSA. Mass spectrometric analysis of the product of a 1 : 1 molar ratio reaction mixture of AuQC@BSA and AgQC@BSA suggested that the alloy clusters could be Au38-xAgx@BSA. Further analyses by standard techniques revealed that the alloy cluster core of ~1.2 nm diameter is composed of nearly zero valent Au and Ag atoms that exhibit distinctly different steady state and time resolved excited state luminescence profiles compared to the parent clusters. Tuning of the alloy composition was achieved by varying the molar ratio of the parent species in the reaction mixture and compositional changes were observed by mass spectrometry. In another approach, mixing of Au3+ ions with the as-synthesized AgQC@BSA also resulted in the formation of alloy clusters through galvanic exchange reactions. We believe that alloy clusters with the combined properties of the constituents in versatile protein templates would have potential applications in the future. The work presents interesting aspects of the reactivity of the protein-protected clusters.We report the synthesis of luminescent AuAg alloy quantum clusters (QCs) in bovine serum albumin (BSA), for the first time, with experimentally determined atomic composition. Mixing of the as-synthesized protein-protected Au and Ag clusters resulted in the formation of alloy AuAg clusters within the BSA. Mass spectrometric analysis of the product of a 1 : 1 molar ratio reaction mixture of AuQC@BSA and AgQC@BSA suggested that the alloy clusters could be Au38-xAgx@BSA. Further analyses by standard techniques revealed that the alloy cluster core of ~1.2 nm diameter is composed of nearly zero valent Au and Ag atoms that exhibit distinctly different

  8. Centrality and collision system dependence of antiproton production from p+A to Au+Au collisions at AGS energies

    NASA Technical Reports Server (NTRS)

    Sako, H.; Ahle, L.; Akiba, Y.; Ashktorab, K.; Baker, M. D.; Beavis, D.; Britt, H. C.; Chang, J.; Chasman, C.; Chen, Z.; Chu, Y. Y.; Cianciolo, V.; Cole, B. A.; Crawford, H. J.; Cumming, J. B.; Debbe, R.; Dunlop, J. C.; Eldredge, W.; Engelage, J.; Fung, S.-Y.

    1997-01-01

    Antiproton production in heavy ion collisions reflects subtle interplay between initial production and absorption by nucleons. Because the AGS energies (10--20 A(center-dot)GeV/c) are close to the antiproton production threshold, antiproton may be sensitive to cooperative processes such as QGP and hadronic multi-step processes. On the other hand, antiproton has been proposed as a probe of baryon density due to large N(anti N) annihilation cross sections. Cascade models predict the maximum baryon density reaches about 10 times the normal nucleus density in central Au+Au collisions, where the strong antiproton absorption is expected. In this paper, the authors show systematic studies of antiproton production from p+A to Au+Au collisions.

  9. A comparative investigation of the behaviors of H in Au and Ag from first principles

    NASA Astrophysics Data System (ADS)

    Han, Quan-Fu; Zhou, Zhen-Yu; Ma, Yuming; Liu, Yue-Lin

    2016-05-01

    Hydrogen (H) is a common impurity in metals and has a significant effect on their purification, even at concentrations of only a few parts per million. Here we present a comparative analysis of the behaviors of H in Au and Ag based on first-principles calculations. In bulk Au and Ag, the results demonstrate that the tetrahedral position is energetically more stable for a single H atom than the octahedral site. The concentration of H dissolving in the interstitial sites as a function of temperature is calculated in both metals. To characterize the dynamic behaviors, in bulk Au and Ag we determine the theoretical diffusivity and permeation of H, which are in quantitative agreement with the experimental data. Further, we investigate the role of vacancy on the formation of the H n -vacancy (H n V) via a clustering reaction. One vacancy can accommodate up to 9 H atoms in Au and capture as many as 7 H atoms in Ag. The H2 molecule in the vacancy is energetically unstable in both metals. These research results will provide a very useful reference for the refinement of Ag/Au as noble metals in industry.

  10. Near infrared Ag/Au alloy nanoclusters: tunable photoluminescence and cellular imaging.

    PubMed

    Wang, Chuanxi; Xu, Lin; Xu, Xiaowei; Cheng, Hao; Sun, Hongchen; Lin, Quan; Zhang, Chi

    2014-02-15

    The fluorescent nanomaterials play an important role in cellular imaging. Although the synthesis of fluorescent metal nanoclusters (NCs) have been developing rapidly, there are many technical issues in preparing metal alloy NCs. Herein, we used a facile galvanic replacement reaction to prepare Ag/Au alloy NCs. The characterizations of UV, PL, HRTEM, EDX and XPS confirm one fact the Ag/Au alloy NCs are carried out. As-prepared Ag/Au alloy NCs display near-infrared (NIR) fluorescence centered at 716 nm and show tunable luminescence from visible red (614 nm) to NIR (716 nm) by controlling the experimental Ag/Au ratios. Moreover, as-prepared Ag/Au alloy NCs are protected by glutathione (GSH) whose some functional groups including thiol, carboxyl and amino groups make the as-prepared alloy NCs exhibit good dispersion in aqueous solution, high physiological stability and favorable biocompatibility. Together with NIR fluorescence, these advantages make alloy NCs be promising candidate in biological labeling.

  11. Bimetallic Pt-Au nanocatalysts electrochemically deposited on graphene and their electrocatalytic characteristics towards oxygen reduction and methanol oxidation.

    PubMed

    Hu, Yaojuan; Zhang, Hua; Wu, Ping; Zhang, Hui; Zhou, Bo; Cai, Chenxin

    2011-03-01

    The burgeoning demand for clean and energy-efficient fuel cell system requires electrocatalysts to deliver greater activity and selectivity. Bimetallic catalysts have proven superior to single metal catalysts in this respect. This work reports the preparation, characterization, and electrocatalytic characteristics of a new bimetallic nanocatalyst. The catalyst, Pt-Au-graphene, was synthesized by electrodeposition of Pt-Au nanostructures on the surface of graphene sheets, and characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray powder diffraction (XRD), and voltammetry. The morphology and composition of the nanocatalyst can be easily controlled by adjusting the molar ratio between Pt and Au precursors. The electrocatalytic characteristics of the nanocatalysts for the oxygen reduction reaction (ORR) and the methanol oxidation reaction (MOR) were systematically investigated by cyclic voltammetry. The Pt-Au-graphene catalysts exhibits higher catalytic activity than Au-graphene and Pt-graphene catalysts for both the ORR and the MOR, and the highest activity is obtained at a Pt/Au molar ratio of 2:1. Moreover, graphene can significantly enhance the long-term stability of the nanocatalyst toward the MOR by effectively removing the accumulated carbonaceous species formed in the oxidation of methanol from the surface of the catalyst. Therefore, this work has demonstrated that a higher performance of ORR and the MOR could be realized at the Pt-Au-graphene electrocatalyst while Pt utilization also could be greatly diminished. This method may open a general approach for the morphology-controlled synthesis of bimetallic Pt-M nanocatalysts, which can be expected to have promising applications in fuel cells. PMID:21229152

  12. Antibacterial activity of microstructured Ag/Au sacrificial anode thin films.

    PubMed

    Köller, Manfred; Sengstock, Christina; Motemani, Yahya; Khare, Chinmay; Buenconsejo, Pio J S; Geukes, Jonathan; Schildhauer, Thomas A; Ludwig, Alfred

    2015-01-01

    Ten different Ag dot arrays (16 to 625 microstructured dots per square mm) were fabricated on a continuous Au thin film and for comparison also on Ti film by sputter deposition and photolithographic patterning. To analyze the antibacterial activity of these microstructured films Escherichia coli and Staphylococcus aureus were placed onto the array surfaces and cultivated overnight. To analyze the viability of planktonic as well as surface adherent bacteria, the applied bacterial fluid was subsequently aspirated, plated on blood agar plates and adherent bacteria were detected by fluorescence microscopy. A particular antibacterial effect towards both bacterial strains was induced by Ag dot arrays on fabricated Au thin film (sacrificial anode system for Ag), due to the release of Ag ions from dissolution of Ag dots in contrast to Ag dot arrays fabricated on the Ti thin films (non-sacrificial anode system for Ag) which remained intact to the original dot shape. The required number of Ag dots on gold film to achieve complete bactericidal effects for both bacterial strains was seven times lower than that observed with Ag dot arrays on Ti film.

  13. DNA-templated synthesis of PtAu bimetallic nanoparticle/graphene nanocomposites and their application in glucose biosensor

    PubMed Central

    2014-01-01

    In this paper, single-stranded DNA (ss-DNA) is demonstrated to functionalize graphene (GR) and to further guide the growth of PtAu bimetallic nanoparticles (PtAuNPs) on GR with high densities and dispersion. The obtained nanocomposites (PtAuNPs/ss-DNA/GR) were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectrometer (EDS), and electrochemical techniques. Then, an enzyme nanoassembly was prepared by self-assembling glucose oxidase (GOD) on PtAuNP/ss-DNA/GR nanocomposites (GOD/PtAuNPs/ss-DNA/GR). The nanocomposites provided a suitable microenvironment for GOD to retain its biological activity. The direct and reversible electron transfer process between the active site of GOD and the modified electrode was realized without any extra electron mediator. Thus, the prepared GOD/PtAuNP/ss-DNA/GR electrode was proposed as a biosensor for the quantification of glucose. The effects of pH, applied potential, and temperature on the performance of the biosensor were discussed in detail and were optimized. Under optimal conditions, the biosensor showed a linearity with glucose concentration in the range of 1.0 to 1,800 μM with a detection limit of 0.3 μM (S/N = 3). The results demonstrate that the developed approach provides a promising strategy to improve the sensitivity and enzyme activity of electrochemical biosensors. PMID:24572068

  14. DNA-templated synthesis of PtAu bimetallic nanoparticle/graphene nanocomposites and their application in glucose biosensor

    NASA Astrophysics Data System (ADS)

    Leng, Jing; Wang, Wen-Min; Lu, Li-Min; Bai, Ling; Qiu, Xin-Lan

    2014-02-01

    In this paper, single-stranded DNA (ss-DNA) is demonstrated to functionalize graphene (GR) and to further guide the growth of PtAu bimetallic nanoparticles (PtAuNPs) on GR with high densities and dispersion. The obtained nanocomposites (PtAuNPs/ss-DNA/GR) were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectrometer (EDS), and electrochemical techniques. Then, an enzyme nanoassembly was prepared by self-assembling glucose oxidase (GOD) on PtAuNP/ss-DNA/GR nanocomposites (GOD/PtAuNPs/ss-DNA/GR). The nanocomposites provided a suitable microenvironment for GOD to retain its biological activity. The direct and reversible electron transfer process between the active site of GOD and the modified electrode was realized without any extra electron mediator. Thus, the prepared GOD/PtAuNP/ss-DNA/GR electrode was proposed as a biosensor for the quantification of glucose. The effects of pH, applied potential, and temperature on the performance of the biosensor were discussed in detail and were optimized. Under optimal conditions, the biosensor showed a linearity with glucose concentration in the range of 1.0 to 1,800 μM with a detection limit of 0.3 μM (S/N = 3). The results demonstrate that the developed approach provides a promising strategy to improve the sensitivity and enzyme activity of electrochemical biosensors.

  15. Core/shell Au/CuPt nanoparticles and their dual electrocatalysis for both reduction and oxidation reactions.

    PubMed

    Sun, Xiaolian; Li, Dongguo; Ding, Yong; Zhu, Wenlei; Guo, Shaojun; Wang, Zhong Lin; Sun, Shouheng

    2014-04-16

    We report a facile synthesis of monodisperse core/shell 5/1.5 nm Au/CuPt nanoparticles by coreduction of platinum acetylacetonate and copper acetylacetonate in the presence of 5 nm Au nanoparticles. The CuPt alloy effect and core/shell interactions make these Au/CuPt nanoparticles a promising catalyst for both oxygen reduction reaction and methanol oxidation reaction in 0.1 M HClO4 solution. Their specific (mass) reduction and oxidation activities reach 2.72 mA/cm(2) (1500 mA/mg Pt) at 0.9 V and 0.755 mA/cm(2) (441 mA/mg Pt) at 0.8 V (vs reversible hydrogen electrode), respectively. Our studies show that the existence of the Au nanoparticle core not only minimizes the Pt usage but also improves the stability of the Au/CuPt catalyst for fuel cell reactions. The results suggest that the core/shell design is indeed effective for optimizing nanoparticle catalysis. The same concept may be extended to other multimetallic nanoparticle systems, making it possible to tune nanoparticle catalysis for many different chemical reactions.

  16. Structural and electronic properties of Au{sub n−x}Pt{sub x} (n = 2–14; x ⩽ n) clusters: The density functional theory investigation

    SciTech Connect

    Yuan, H. K.; Kuang, A. L.; Tian, C. L.; Chen, H.

    2014-03-15

    The structural evolutions and electronic properties of bimetallic Au{sub n–x}Pt{sub x} (n = 2–14; x ⩽ n) clusters are investigated by using the density functional theory (DFT) with the generalized gradient approximation (GGA). The monatomic doping Au{sub n–1}Pt clusters are emphasized and compared with the corresponding pristine Au{sub n} clusters. The results reveal that the planar configurations are favored for both Au{sub n–1}Pt and Au{sub n} clusters with size up to n = 13, and the former often employ the substitution patterns based on the structures of the latter. The most stable clusters are Au{sub 6} and Au{sub 6}Pt, which adopt regular planar triangle (D{sub 3h}) and hexagon-ring (D{sub 6h}) structures and can be regarded as the preferential building units in designing large clusters. For Pt-rich bimetallic clusters, their structures can be obtained from the substitution of Pt atoms by Au atoms from the Pt{sub n} structures, where Pt atoms assemble together and occupy the center yet Au atoms prefer the apex positions showing a segregation effect. With respect to pristine Au clusters, Au{sub n}Pt clusters exhibit somewhat weaker and less pronounced odd-even oscillations in the highest occupied and lowest unoccupied molecular-orbital gaps (HOMO-LUMO gap), electron affinity (EA), and ionization potential (IP) due to the partially released electron pairing effect. The analyses of electronic structure indicate that Pt atoms in AuPt clusters would delocalize their one 6s and one 5d electrons to contribute the electronic shell closure. The sp-d hybridizations as well as the d-d interactions between the host Au and dopant Pt atoms result in the enhanced stabilities of AuPt clusters.

  17. Thermoelectric Scanning Study of Pt/Pd and Au/Pt Thermocouples up to 960 °C with a Pressure Controlled Sodium Heat-Pipe

    NASA Astrophysics Data System (ADS)

    Gotoh, Masahiko

    2003-09-01

    The performance of the Gold/Platinum (Au/Pt) thermocouple and the Platinum/Palladium (Pt/Pd) thermocouple has received considerable study and it is found that stability of these thermocouples approaches that of Standard Platinum Resistance Thermometers. However there is still some question on the uncertainties due to the different temperature profiles of the furnaces. In this paper results of the measurements on thermal emf variations by means of thermoelectric scanning are reported. Scanning is carried out in a pressure controlled heat pipe at 960 °C over 475 mm along the thermocouples. A Au/Pt thermocouple and three Pt/Pd thermocouples were tested. Pt/Pd thermocouples were subjected to 1000 hours exposure to 1200 °C in different furnaces. As the portion of thermocouple wire previously exposed to around 750 °C crossed the top of the heat-pipe, a 0.4 K apparent temperature drop was detected. It is found that with this thermoelectric scanning method, the effect of accumulated heat treatment on the Pt/Pd thermocouple can be detected at 960 °C. For Au/Pt no such irregularity is detected, but overall a 0.02 K deviation was observed.

  18. Ag@Au core-shell dendrites: a stable, reusable and sensitive surface enhanced Raman scattering substrate

    NASA Astrophysics Data System (ADS)

    Jun Yin, Hong; Yang Chen, Zhao; Mei Zhao, Yong; Yang Lv, Ming; An Shi, Chun; Long Wu, Zheng; Zhang, Xin; Liu, Luo; Li Wang, Ming; Jun Xu, Hai

    2015-09-01

    Surface enhanced Raman scattering (SERS) substrate based on fabricated Ag@Au core-shell dendrite was achieved. Ag dendrites were grown on Si wafer by the hydrothermal corrosion method and Au nanofilm on the surface of Ag dendritic nanostructure was then fabricated by chemical reduction. With the help of sodium borohydride in water, Au surface absorbates such as thiophene, adenine, rhodamine, small anions (Br- and I-), and a polymer (PVP, poly(N-vinylpyrrolidone)) can be completely and rapidly removed. After four repeatable experiments, the substrate SERS function did not decrease at all, indicating that the Ag@Au dendrite should be of great significance to SERS application because it can save much resource. Six-month-duration stability tests showed that the Ag@Au core-shell dendrite substrate is much more stable than the Ag dendrite substrates. We have also experimented on fast detection of Cd2+ at 10-8  M concentration by decorating single-stranded DNA containing adenine and guanine bases on the surface of this Ag@Au dendrite. Finite-difference time-domain simulations were carried out to investigate the influence of Au nanolayer on Ag dendrites, which showed that the local electric fields and enhancement factor are hardly affected when a 4 nm Au nanolayer is coated on Ag dendrite surface.

  19. Ag@Au core-shell dendrites: a stable, reusable and sensitive surface enhanced Raman scattering substrate

    PubMed Central

    Jun Yin, Hong; Yang Chen, Zhao; Mei Zhao, Yong; Yang Lv, Ming; An Shi, Chun; Long Wu, Zheng; Zhang, Xin; Liu, Luo; Li Wang, Ming; Jun Xu, Hai

    2015-01-01

    Surface enhanced Raman scattering (SERS) substrate based on fabricated Ag@Au core-shell dendrite was achieved. Ag dendrites were grown on Si wafer by the hydrothermal corrosion method and Au nanofilm on the surface of Ag dendritic nanostructure was then fabricated by chemical reduction. With the help of sodium borohydride in water, Au surface absorbates such as thiophene, adenine, rhodamine, small anions (Br– and I–), and a polymer (PVP, poly(N-vinylpyrrolidone)) can be completely and rapidly removed. After four repeatable experiments, the substrate SERS function did not decrease at all, indicating that the Ag@Au dendrite should be of great significance to SERS application because it can save much resource. Six-month-duration stability tests showed that the Ag@Au core-shell dendrite substrate is much more stable than the Ag dendrite substrates. We have also experimented on fast detection of Cd2+ at 10−8  M concentration by decorating single-stranded DNA containing adenine and guanine bases on the surface of this Ag@Au dendrite. Finite-difference time-domain simulations were carried out to investigate the influence of Au nanolayer on Ag dendrites, which showed that the local electric fields and enhancement factor are hardly affected when a 4 nm Au nanolayer is coated on Ag dendrite surface. PMID:26412773

  20. Highly Fluorescent Gene Carrier Based on Ag-Au Alloy Nanoclusters.

    PubMed

    Wang, Ping; Lin, Lin; Guo, Zhaopei; Chen, Jie; Tian, Huayu; Chen, Xuesi; Yang, Hua

    2016-01-01

    For systemic delivery of gene, gold nanoparticles (GNPs) have been exploited as novel gene carriers because of the excellent characteristics for "visible" in intracellular trafficking. Herein, a highly fluorescent gene carrier was prepared by conjugating polyethylenimines on Ag-Au alloy nanoclusters. This carrier exhibited remarkable high gene transfection efficiencies and relatively low cytotoxicity toward B16F10, HeLa, and CHO cells. More interestingly, the high fluorescent Ag-Au-PEI conjugates showed high quantum yield of 14.56%, which is much higher than most of the reported gold nanocluster-based quantum dots and Ag-Au-PEI possessed bioimaging capacity both in vitro and in vivo. PMID:26287567

  1. Fabrication of Au@Ag core-shell nanoparticles using polyelectrolyte multilayers as nanoreactors.

    PubMed

    Zhang, Xin; Wang, Hui; Su, Zhaohui

    2012-11-01

    A new synthetic strategy has been developed for the fabrication of Au-Ag bimetallic core-shell nanoparticles (NPs) using polyelectrolyte multilayers (PEMs) as unique nanoreactors. Bimetallic NPs composed of Au core and Ag shell were successively incorporated into PEMs by repeating anion/cation exchange/reduction cycle multiple times in a stepwise manner. The strategy described here allows for the facile preparation of Au@Ag core-shell NPs with well-controlled core and shell dimensions and geometrically tunable optical properties by simply varying the number of ion-exchange/reduction cycles in the PEM matrix. The strategy can be extended to synthesize in situ other core-shell NPs in polymer matrix.

  2. Development of Au-Ag nanowire mesh fabrication by UV-induced approach

    SciTech Connect

    Saggar, Siddhartha; Predeep, Padmanabhan

    2014-10-15

    In an attempt to overcome the limitations of the presently prevailing transparent conducting electrode (TCE) - indium tin oxide (ITO) - many materials have been considered for replacing ITO. Recently, a novel method has been reported for the synthesis of Au-Ag nanowire (NW) mesh, and tested successfully for organic-light-emitting-diodes (OLEDs). It employs UV-induced reduction of gold- and silver- precursors to form Au-Ag NW mesh. In this report, Au-Ag NW mesh thin films are synthesized on glass substrates with an objective for use as facing-electrode for Organic Photovoltaics. Various issues and factors affecting the fabrication-process have been improved, and are also discussed here. The electrode showed good transmitivity, of around 95% (excluding that of glass substrate). The advantage of the technique is its simple processing method and cost-effectiveness.

  3. 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

  4. Surface Segregated AgAu Tadpole-Shaped Nanoparticles Synthesized Via a Single Step Combined Galvanic and Citrate Reduction Reaction.

    PubMed

    da Silva, Anderson G M; Lewis, Edward A; Rodrigues, Thenner S; Slater, Thomas J A; Alves, Rafael S; Haigh, Sarah J; Camargo, Pedro H C

    2015-08-24

    New AgAu tadpole nanocrystals were synthesized in a one-step reaction involving simultaneous galvanic replacement between Ag nanospheres and AuCl4(-)(aq.) and AuCl4(-)(aq.) reduction to Au in the presence of citrate. The AgAu tadpoles display nodular polycrystalline hollow heads, while their undulating tails are single crystals. The unusual morphology suggests an oriented attachment growth mechanism. Remarkably, a 1 nm thick Ag layer was found to segregate so as to cover the entire surface of the tadpoles. By varying the nature of the seeds (Au NPs), double-headed Au tadpoles could also be obtained. The effect of a number of reaction parameters on product morphology were explored, leading to new insights into the growth mechanisms and surface segregation behavior involved in the synthesis of bimetallic and anisotropic nanomaterials.

  5. Catalytic Properties of AgPt Nanoshells as a Function of Size: Larger Outer Diameters Lead to Improved Performances.

    PubMed

    Rodrigues, Thenner S; da Silva, Anderson G M; Gonçalves, Mariana C; Fajardo, Humberto V; Balzer, Rosana; Probst, Luiz F D; da Silva, Alisson H M; Assaf, Jose M; Camargo, Pedro H C

    2016-09-13

    We report herein a systematic investigation on the effect of the size of silver (Ag) nanoparticles employed as starting materials over the morphological features and catalytic performances of AgPt nanoshells produced by a combination of galvanic replacement between Ag and PtCl6(2-) and PtCl6(2-) reduction by hydroquinone. More specifically, we focused on Ag nanoparticles of four different sizes as starting materials, and found that the outer diameter, shell thickness, and the number of Pt surface atoms of the produced nanoshells increased with the size of the starting Ag nanoparticles. The produced AgPt nanoshells were supported into SiO2, and the catalytic performances of the AgPt/SiO2 nanocatalysts toward the gas-phase oxidation of benzene, toluene, and o-xylene (BTX oxidation) followed the order: AgPt 163 nm/SiO2 > AgPt 133 nm/SiO2 > AgPt 105 nm/SiO2 > AgPt 95 nm/SiO2. Interestingly, bigger AgPt nanoshell sizes lead to better catalytic performances in contrast to the intuitive prediction that particles having larger outer diameters tend to present poorer catalytic activities due to their lower surface to volume ratios as compared to smaller particles. This is in agreement with the H2 chemisorption results, and can be assigned to the increase in the Pt surface area with size due to the presence of smaller NPs islands at the surface of the nanoshells having larger outer diameters. This result indicates that, in addition to the overall diameters, the optimization of the surface morphology may play an important role over the optimization of catalytic activities in metal-based nanocatalysts, which can be even more pronounced that the size effect. Our data demonstrate that the control over surface morphology play a very important role relative to the effect of size to the optimization of catalytic performances in catalysts based on noble-metal nanostructures. PMID:27556904

  6. Bimetallic Ag-Au nanoparticles: Extracting meaningful optical constants from the surface-plasmon extinction spectrum

    NASA Astrophysics Data System (ADS)

    Moskovits, M.; Srnova-Sloufova, I.; Vlckova, B.

    2002-06-01

    We report an approach for extracting the optical constants of bimetallic Ag-Au nanoparticles from the measured surface-plasmon (SP) extinction spectra. The dielectric function of the metal is expressed as an analytic function of the wavelength in which the interband (and all other non-Drude) contributions to the dielectric function are represented by a sum of Lorentz functions. This expression is then used to fit the experimental extinction spectra to appropriate functions based on Mie theory. Three Lorentz functions (plus a Drude term) were found to be sufficient to reproduce the dielectric functions of Ag and Au [P. B. Johnson and R. W. Christy, Phys. Rev. B 6, 4370 (1972)] over the entire 0.6-6.5 eV range reported. With functions of this type, an excellent multiparameter fit of the measured extinction spectrum of colloidal Ag was obtained. Extinction spectra of a series of (Ag)Au hydrosols, prepared by reducing a gold precursor in the presence of previously synthesized silver seed particles with Au mole fractions ranging from 0.1 to 0.8, were measured. The extinction spectra show a single band (attributed to the surface plasmon) for all of the colloids produced, suggesting alloy formation. Transmission electron microscopy (TEM) images, however, indicate clear core-shell contrast for nanoparticles with Au mole fractions 0.4 and higher. With a presumed particle structure consisting of Ag core and Ag/Au alloy shell, very good fits were obtained for all of the measured extinction spectra by using a fitting strategy that restricted the number of parameters allowed to vary freely in the aforementioned dielectric function. The values of the dielectric function of the presumed shells were extracted in this manner as a function of wavelength. For particles with Au mole fraction 0.1-0.3, the results suggest an incompletely formed shell. For particles with higher Au mole fractions, the dielectric function of the shell gradually approaches that of Au. Overall, the results

  7. Dissociative adsorption of water on Au/MgO/Ag(001) from first principles calculations

    NASA Astrophysics Data System (ADS)

    Nevalaita, J.; Häkkinen, H.; Honkala, K.

    2015-10-01

    The molecular and dissociative adsorption of water on a Ag-supported 1 ML, 2 ML and 3 ML-a six atomic layer-thick MgO films with a single Au adatom is investigated using density functional theory calculations. The obtained results are compared to a bulk MgO(001) surface with an Au atom. On thin films the negatively charged Au strengthens the binding of the polar water molecule due to the attractive Au-H interaction. The adsorption energy trends of OH and H with respect to the film thickness depend on an adsorption site. In the case OH or H binds atop Au on MgO/Ag(001), the adsorption becomes more exothermic with the increasing film thickness, while the reverse trend is seen when the adsorption takes place on bare MgO/Ag(001). This behavior can be explained by different bonding mechanisms identified with the Bader analysis. Interestingly, we find that the rumpling of the MgO film and the MgO-Ag interface distance correlate with the charge transfer over the thin film and the interface charge, respectively. Moreover, we employ a modified Born-Haber-cycle to analyze the effect of film thickness to the adsorption energy of isolated Au and OH species on MgO/Ag(001). The analysis shows that the attractive Coulomb interaction between the negatively charged adsorbate and the positive MgO-Ag-interface does not completely account for the weaker binding with increasing film thickness. The redox energy associated with the charge transfer from the interface to the adsorbate is more exothermic with the increasing film thickness and partly compensates the decrease in the attractive Coulomb interaction.

  8. The unusual effect of AgNO3 on the growth of Au nanostructures and their catalytic performance

    NASA Astrophysics Data System (ADS)

    Li, Xingliang; Yang, Yun; Zhou, Guangju; Han, Shuhua; Wang, Wenfang; Zhang, Lijie; Chen, Wei; Zou, Chao; Huang, Shaoming

    2013-05-01

    Au nanostructures attract much attention due to their potential applications in many fields. The controlled synthesis is critical to their properties modulation and applications. AgNO3-assisted synthesis is a widely used method for controllably preparing Au nanostructures in aqueous system. Herein, the effect of AgNO3 on the growth of Au nanostructures in polyol is studied. We observe an unusual effect that AgNO3 can induce the formation of pentatwinned Au nanostructures (nanorods and decahedra) and block the growth of Au nanorods. More interestingly, this blocking effect can be tuned through controlling the amount of AgNO3. A moderate amount of AgNO3 facilitates the formation of Au nanorods. A large amount of AgNO3 completely blocks the growth of nanorods and favors the formation of high quality decahedra (decahedra can be considered as nanorods with 0 nm longitudinal length). Besides, this blocking effect also allows preparation of different high-index-faceted Au nanobipyramids. These prepared Au nanostructures further serve as starting templates to fabricate other heterostructured Au/Ag nanomaterials, such as Ag-Au-Ag segmental nanorods, Au@Ag core-shelled nanostructures. The prepared nanostructures exhibit size- and structure-dependent catalytic performance in the reduction of p-nitrophenol to p-aminophenol by sodium borohydride.Au nanostructures attract much attention due to their potential applications in many fields. The controlled synthesis is critical to their properties modulation and applications. AgNO3-assisted synthesis is a widely used method for controllably preparing Au nanostructures in aqueous system. Herein, the effect of AgNO3 on the growth of Au nanostructures in polyol is studied. We observe an unusual effect that AgNO3 can induce the formation of pentatwinned Au nanostructures (nanorods and decahedra) and block the growth of Au nanorods. More interestingly, this blocking effect can be tuned through controlling the amount of AgNO3. A moderate

  9. Nanoalloy composition-temperature phase diagram for catalyst design: Case study of Ag-Au

    SciTech Connect

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

    2012-07-23

    By coupling a cluster expansion with density functional theory (DFT) calculations, we determine the configurational thermodynamics (site preferences and occupations) for alloyed nanoparticles (NPs) as functions of composition (c) and temperature (T), exemplified using a 55-atom Ag-Au truncated cuboctahedron NP. The c-T phase diagram for site occupations gives detailed design information for alloyed NP, especially the thermodynamically stable active sites for catalysis and how they change with stoichiometry and processing temperature. Generally, Ag prefers core and Au prefers shell, agreeing with our universal core-shell preference assessed from DFT impurity segregation energies but with interesting multishell configurations having specific active sites.

  10. Hollow Au/Ag nanostars displaying broad plasmonic resonance and high surface-enhanced Raman sensitivity

    NASA Astrophysics Data System (ADS)

    Garcia-Leis, Adianez; Torreggiani, Armida; Garcia-Ramos, Jose Vicente; Sanchez-Cortes, Santiago

    2015-08-01

    Bimetallic Au/Ag hollow nanostar (HNS) nanoparticles with different morphologies were prepared in this work. These nanoplatforms were obtained by changing the experimental conditions (concentration of silver and chemical reductors, hydroxylamine and citrate) and by using Ag nanostars as template nanoparticles (NPs) through galvanic replacement. The goal of this research was to create bimetallic Au/Ag star-shaped nanoparticles with advanced properties displaying a broader plasmonic resonance, a cleaner exposed surface, and a high concentration of electromagnetic hot spots on the surface provided by the special morphology of nanostars. The size, shape, and composition of Ag as well as their optical properties were studied by extinction spectroscopy, hyperspectral dark field microscopy, transmission and scanning electron microscopy (TEM and SEM), and energy dispersive X-ray spectroscopy (EDX). Finally, the surface-enhanced Raman scattering (SERS) activity of these HNS was investigated by using thioflavin T, a biomarker of the β-amyloid fibril formation, responsible for Alzheimer's disease. Lucigenin, a molecule displaying different SERS activities on Au and Ag, was also used to explore the presence of these metals on the NP surface. Thus, a relationship between the morphology, plasmon resonance and SERS activity of these new NPs was made.Bimetallic Au/Ag hollow nanostar (HNS) nanoparticles with different morphologies were prepared in this work. These nanoplatforms were obtained by changing the experimental conditions (concentration of silver and chemical reductors, hydroxylamine and citrate) and by using Ag nanostars as template nanoparticles (NPs) through galvanic replacement. The goal of this research was to create bimetallic Au/Ag star-shaped nanoparticles with advanced properties displaying a broader plasmonic resonance, a cleaner exposed surface, and a high concentration of electromagnetic hot spots on the surface provided by the special morphology of nanostars

  11. Effect of Au Content on Thermal Stability and Mechanical Properties of Au-Cu-Ag-Si Bulk Metallic Glasses

    NASA Astrophysics Data System (ADS)

    Guo, H.; Zhang, W.; Chen, M. W.; Saotome, Y.; Fukuhara, M.; Inoue, A.

    2011-06-01

    The thermal stability, glass-forming ability (GFA), and mechanical and electrical properties of Au-based Au x Si17Cu75.5- x Ag7.5 ( x = 40 to 75.5 at. pct) metallic glasses were investigated. The glass transition temperature ( T g ) and crystallization temperature ( T x ) decreased with increasing Au content. The ultralow T g values below 373 K (100 °C) were obtained for alloys with x = 55 to 75.5. The alloys with x = 45 to 70 exhibited a high stabilization of supercooled liquid and a high GFA, and the supercooled liquid region and critical sample diameter for glass formation were in the range of 31 K to 50 K and 2 to 5 mm, respectively. The compressive fracture strength ( σ c,f ), Young's modulus ( E), and Vicker's hardness ( H v ) of the bulk metallic glasses (BMGs) decreased with increasing Au content. A linear correlation between Au concentration and the characteristic temperature, i.e., T g and T x , and mechanical properties, i.e., σ c,f , E, and H v , as well as electrical resistivity can be found in the BMGs, which will be helpful for the composition design of the desirable Au-based BMGs with tunable physical properties.

  12. Sintered Cr/Pt and Ni/Au ohmic contacts to B12P2

    DOE PAGES

    Frye, Clint D.; Kucheyev, Sergei O.; Edgar, James H.; Voss, Lars F.; Conway, Adam M.; Shao, Qinghui; Nikolic, Rebecca J.

    2015-04-09

    With this study, icosahedral boron phosphide (B12P2) is a wide-bandgap semiconductor possessing interesting properties such as high hardness, chemical inertness, and the reported ability to self-heal from irradiation by high energy electrons. Here, the authors developed Cr/Pt and Ni/Au ohmic contacts to epitaxially grown B12P2 for materials characterization and electronic device development. Cr/Pt contacts became ohmic after annealing at 700 °C for 30 s with a specific contact resistance of 2×10–4 Ω cm2, as measured by the linear transfer length method. Ni/Au contacts were ohmic prior to any annealing, and their minimum specific contact resistance was ~l–4 × 10–4 Ωmore » cm2 after annealing over the temperature range of 500–800 °C. Rutherford backscattering spectrometry revealed a strong reaction and intermixing between Cr/Pt and B12P2 at 700 °C and a reaction layer between Ni and B12P2 thinner than ~25 nm at 500 °C.« less

  13. The deposition of Au-Pt core-shell nanoparticles on reduced graphene oxide and their catalytic activity

    NASA Astrophysics Data System (ADS)

    Cui, Xiu; Wu, Shengnan; Jungwirth, Scott; Chen, Zhibing; Wang, Zhenghua; Wang, Lun; Li, Yongxin

    2013-07-01

    Au-Pt core-shell nanoparticles have been synthesized on a reduced graphene oxide (RGO) surface by an under-potential deposition (UPD) redox replacement technique, which involves redox replacement of a copper UPD monolayer by {{PtCl}}_{4}^{2-} that could be reduced and deposited simultaneously. Scanning electron microscopy (SEM) and electrochemical methods have been used to characterize the graphene decorated with Au-Pt core-shell nanoparticles. The electrochemical experiments show that the materials exhibit excellent catalytic activity towards the oxygen reduction reaction and the methanol oxidation reaction. It is believed that the high-performance of this new catalyst is due to the ultrathin Pt shell on the Au nanoparticles surface and the oxygen-containing functional groups on the RGO surface.

  14. New Stable Crystal Structures for Cu-Au and Ni-Pt Alloy Systems

    NASA Astrophysics Data System (ADS)

    Sanati, Mahdi; Wang, L. G.; Zunger, A.

    2003-10-01

    Cu-Au and Ni-Pt are among the best studied fcc alloy systems, exhibiting the famous L10 (AB) and L12 (A_3B) phases. We were wondering if a complete configurational search of the T=0 LDA total energies would reveal any unexpected phases. Total-energy calculations of ˜ 30 arbitrarily chosen structures were used to construct a generalized (momentum-space) Ising Hamiltonian containing ˜ 20 pair-interactions, ˜ 5-10 many-body terms, as well as the long-range strain term. This Hamiltonian was tested carefully as to its ability to predict the LDA energies of other structures. We searched the energies of all fcc configurations with 20 or less atoms per primitive cell ( ˜ 2,700,000 structures), found known L1_0, L12 as well as new, unsuspected structures. The new ground state structures are NiPt_7, Cu_2Au, and Cu_2Au_3. We also found a composition range in which there is quasicontinuum of stable, ordered structures made of (001) repeat units of simple structural motifs. This structural adaptivity is explained in terms of anisotropic, long-range strain energy.

  15. Ellagic Acid Directed Growth of Au-Pt Bimetallic Nanoparticles and Their Catalytic Applications

    NASA Astrophysics Data System (ADS)

    Barnaby, Stacey N.; Sarker, Nazmul H.; Banerjee, Ipsita A.

    2013-02-01

    In this work, we report the facile formation of bimetallic nanoparticles of Au-Pt in the presence of the plant polyphenol ellagic acid (EA). It was found that EA formed micro-fibrillar assemblies, which aggregated into micro-bundles under aqueous conditions. Those micro-bundles acted as templates for the growth of Au nanoparticles, as well as bimetallic Au-Pt nanoparticles biomimetically. At higher concentrations of EA, it was observed that in addition to forming fibrous micro-bundles, columnar assemblies of EA were formed in the presence of the metal nanoparticles. The formation of the assemblies was found to be concentration dependent. It appears that upon binding to metal ions and subsequent formation of the nanoparticles, morphological changes occur in the case of EA assemblies. The morphological changes observed were probed by electron microscopy. Further, the ability of the materials to degrade the toxic aromatic nitro compound 2-methoxy-4-nitroaniline was explored, where 50% degradation was observed within 15 min, indicating that such hybrid materials may have potential applications in environmental remediation.

  16. 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.

  17. A silk derived carbon fiber mat modified with Au@Pt urchilike nanoparticles: A new platform as electrochemical microbial biosensor.

    PubMed

    Deng, Liu; Guo, Shaojun; Zhou, Ming; Liu, Ling; Liu, Chang; Dong, Shaojun

    2010-06-15

    We present here a facile and efficient route to prepare silk derived carbon mat modified with Au@Pt urchilike nanoparticles (Au@Pt NPs) and develop an Escherichia coli (E. coli)-based electrochemical sensor using this material. Silk is a natural protein fiber, and it is abundant with kinds of functionalities which are important in the development of the derived material. The S-derived carbon fiber mat have amino, pyridine and carbonyl functional groups, these natural existent functionalities allow the Au@Pt NPs to self-assemble on the carbon fiber surface and provide a biocompatible microenvironment for bacteria. The Au@Pt NPs modified S-derived carbon fiber is sensitive to detect the E. coli activities with a low detection limit, where glucose is used as a prelimiltary substrate to evaluate them. The performance of Au@Pt/carbon fiber mat based biosensor is much better than that of commercial carbon paper based biosensor. The high sensitivity of this biosensor stems from the unique electrocatalytic properties of Au@Pt urchilike NPs and quinone groups presented in S-derived carbon fiber. This biosensor is also tested for detection of organophosphate pesticides, fenamiphos. The relative inhibition of E. coli activity is linear with -log[fenamiphos] at the concentration range from 0.5mg/L to 36.6 mg/L with lowest observable effect concentration (LOEC) of 0.09 mg/L. The Au@Pt NPs modified S-derived carbon fiber mat possesses high conductivity, biocompatibility and high electrocatalytic activity and be can used as advanced electrode materials for microbial biosensor improvement. The microbial biosensor based on this material shows potential applications in environmental monitoring.

  18. Ag shell-Au satellite hetero-nanostructure for ultra-sensitive, reproducible, and homogeneous NIR SERS activity.

    PubMed

    Chang, Hyejin; Kang, Homan; Yang, Jin-Kyoung; Jo, Ahla; Lee, Ho-Young; Lee, Yoon-Sik; Jeong, Dae Hong

    2014-08-13

    It is critical to create isotropic hot spots in developing a reproducible, homogeneous, and ultrasensitive SERS probe. Here, an Ag shell-Au satellite (Ag-Au SS) nanostructure composed of an Ag shell and surrounding Au nanoparticles was developed as a near-IR active SERS probe. The heterometallic shell-satellite structure based SERS probe produced intense and uniform SERS signals (SERS enhancement factor ∼1.4 × 10(6) with 11% relative standard deviation) with high detectability (100% under current measurement condition) by 785 nm photoexcitation. This signal enhancement was independent of the laser polarizations, which reflects the isotropic feature of the SERS activity of Ag-Au SS from the three-dimensional (3D) distribution of SERS hot spots between the shell and the surrounding satellite particles. The Ag-Au SS nanostructure shows a great potential as a reproducible and quantifiable NIR SERS probe for in vivo targets.

  19. High-spin states and coexisting states in the Pt-Au transition region

    SciTech Connect

    Riedinger, L.L.; Carpenter, M.P.; Courtney, L.H.; Janzen, V.P.; Schmitz, W.

    1986-01-01

    High-spin states in the N = 104 to 108 region have been studied by in-beam spectroscopy techniques in a number of Ir, Pt, and Au nuclei. These measurements have been performed at tandem Van de Graaff facilities at the Oak Ridge National Laboratory and at McMaster University. Through comparison of band crossings in a variety of odd-A and even-A nuclei, we are able to assign the first neutron and first proton alignment processes, which are nearly degenerate for /sup 184/Pt. These measurements yield the trend of these crossing frequencies with N and Z in this region. Knowledge of this trend is important, since these crossing frequencies can give an estimate of how the shape parameters vary across this transitional region. 22 refs., 7 figs., 1 tab.

  20. The population genetic structure of Rhizoctonia solani AG-3PT from potato in the Colombian Andes.

    PubMed

    Ferrucho, Rosa L; Ceresini, Paulo C; Ramirez-Escobar, Ursula M; McDonald, Bruce A; Cubeta, Marc A; García-Domínguez, Celsa

    2013-08-01

    The soilborne fungus Rhizoctonia solani anastomosis group 3 (AG-3PT) is a globally important potato pathogen. However, little is known about the population genetic processes affecting field populations of R. solani AG-3PT, especially in the South American Colombian Andes, which is near the center of diversity of the two most common groups of cultivated potato, Solanum tuberosum and S. phureja. We analyzed the genetic structure of 15 populations of R. solani AG-3PT infecting potato in Colombia using 11 simple-sequence repeat (SSR) markers. In total, 288 different multilocus genotypes were identified among 349 fungal isolates. Clonal fractions within field populations were 7 to 33%. RST statistics indicated a very low level of population differentiation overall, consistent with high contemporary gene flow, though moderate differentiation was found for the most distant southern populations. Genotype flow was also detected, with the most common genotype found widely distributed among field populations. All populations showed evidence of a mixed reproductive mode, including both asexual and sexual reproduction, but two populations displayed evidence of inbreeding.

  1. Isolation and structural characterization of a silver-platinum nanocluster, Ag4Pt2(DMSA)4

    NASA Astrophysics Data System (ADS)

    Pedicini, Anthony; Reber, Arthur; Biltek, Scott; Sen, Ayusman; Khanna, Shiv

    2015-03-01

    Cluster assembled materials offer an attractive prospect of making nanoscale materials with tunable characteristics. Here, we report the synthesis, isolation, and characterization of the ligand-protected bimetallic cluster, Ag4Pt2(DMSA)4 (DMSA =meso-2,3,-dimercaptosuccinic acid) and its analogue, Ag4Pd2(DMSA)4. The procedure is similar to the one employed previously for the synthesis of Ag4Ni4(DMSA)4. Theoretical studies show that the Pt and Ni atoms are square planar in configuration. Furthermore, the dependence on the optical spectrum due to congener replacement of the transition metal is highlighted. Since the crystal field splitting of 5d orbitals is typically larger than that for 3d orbitals, we show the Pt-based cluster has an optical spectrum that is significantly blue shifted as compared to the Ni-based cluster. This work was supported by an Air Force Office of Scientific Research (AFOSR) Basic Research Initiative Grant FA9550-12-1-0481.

  2. 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.

  3. Optical properties of random alloys: application to CuAu and NiPt

    NASA Astrophysics Data System (ADS)

    Krishna Saha, Kamal; Mookerjee, Abhijit

    2005-07-01

    In an earlier paper we presented a formulation for the calculation of the configuration-averaged optical conductivity in random alloys. Our formulation is based on the augmented-space theorem introduced by one of us (Mookerjee 1973 J. Phys. C: Solid State Phys. 6 1340). In this communication we shall combine the augmented space methodology with the tight-binding linear muffin-tin orbital technique (TB-LMTO) to study the optical conductivities of two alloys, CuAu and NiPt.

  4. 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

  5. Ag@Au concave cuboctahedra: A unique probe for monitoring Au-catalyzed reduction and oxidation reactions by surface-enhanced Raman spectroscopy

    DOE PAGES

    Zhang, Jiawei; Winget, Sarah A.; Wu, Yiren; Su, Dong; Sun, Xiaojun; Xie, Zhao -Xiong; Qin, Dong

    2016-01-26

    In this paper, we report a facile synthesis of Ag@Au concave cuboctahedra by titrating aqueous HAuCl4 into a suspension of Ag cuboctahedra in the presence of ascorbic acid (AA), NaOH, and poly(vinylpyrrolidone) (PVP) at room temperature. Initially, the Au atoms derived from the reduction of Au3+ by AA are conformally deposited on the entire surface of a Ag cuboctahedron. Upon the formation of a complete Au shell, however, the subsequently formed Au atoms are preferentially deposited onto the Au{100} facets, resulting in the formation of a Ag@Au cuboctahedron with concave structures at the sites of {111} facets. The concave cuboctahedramore » embrace excellent SERS activity that is more than 70-fold stronger than that of the original Ag cuboctahedra at an excitation wavelength of 785 nm. The concave cuboctahedra also exhibit remarkable stability in the presence of an oxidant such as H2O2 because of the protection by a complete Au shell. These two unique attributes enable in-situ SERS monitoring of the reduction of 4-nitrothiophenol (4-NTP) to 4-aminothiophenol (4-ATP) by NaBH4 through a 4,4'-dimercaptoazobenzene (trans-DMAB) intermediate and the subsequent oxidation of 4-ATP back to trans-DMAB upon the introduction of H2O2.« less

  6. Ag@Au Concave Cuboctahedra: A Unique Probe for Monitoring Au-Catalyzed Reduction and Oxidation Reactions by Surface-Enhanced Raman Spectroscopy.

    PubMed

    Zhang, Jiawei; Winget, Sarah A; Wu, Yiren; Su, Dong; Sun, Xiaojun; Xie, Zhao-Xiong; Qin, Dong

    2016-02-23

    We report a facile synthesis of Ag@Au concave cuboctahedra by titrating aqueous HAuCl4 into a suspension of Ag cuboctahedra in the presence of ascorbic acid (AA), NaOH, and poly(vinylpyrrolidone) (PVP) at room temperature. Initially, the Au atoms derived from the reduction of Au(3+) by AA are conformally deposited on the entire surface of a Ag cuboctahedron. Upon the formation of a complete Au shell, however, the subsequently formed Au atoms are preferentially deposited onto the Au{100} facets, resulting in the formation of a Ag@Au cuboctahedron with concave structures at the sites of {111} facets. The concave cuboctahedra embrace excellent SERS activity that is more than 70-fold stronger than that of the original Ag cuboctahedra at an excitation wavelength of 785 nm. The concave cuboctahedra also exhibit remarkable stability in the presence of an oxidant such as H2O2 because of the protection by a complete Au shell. These two unique attributes enable in situ SERS monitoring of the reduction of 4-nitrothiophenol (4-NTP) to 4-aminothiophenol (4-ATP) by NaBH4 through a 4,4'-dimercaptoazobenzene (trans-DMAB) intermediate and the subsequent oxidation of 4-ATP back to trans-DMAB upon the introduction of H2O2.

  7. 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.

  8. Photothermal heating and mechanical properties of Au/PEO and Ag/PEO nanocomposites

    NASA Astrophysics Data System (ADS)

    Seyhan, Merve; Rickard, Katherine; Yarar, U. Ecem; Rende, Deniz; Baysal, Nihat; Ozisik, Rahmi; Bucak, Seyda

    2014-03-01

    In the current study, the photothermal effect of gold (Au) and silver (Ag) nanoparticles in poly(ethylene oxide) is investigated. Both Au and Ag nanoparticles were synthesized in-house and were characterized by dynamic light scattering, UV-Visible spectroscopy and transmission electron microscopy experiments. The average size of the Au and Ag nanoparticles was found to be on average 8.9 and 8.4 nm, respectively. The Au/PEO and Ag/PEO nanocomposites containing 0.01-2% nanoparticles (by weight) were prepared via solution mixing. Mechanical and thermo-mechanical properties were investigated by static and dynamic tests. The results indicate that the Young's modulus increases with increasing nanoparticle concentration, however, the modulus values reached a plateau at high concentrations. Both nanocomposites were heated via laser radiation at appropriate wavelengths and via traditional heating (using a heating stage). The temperature variations were measured through Raman spectroscopy experiments and by correlating Raman and traditional heating experiments. The material is partially based upon work supported by NSF under Grant Nos. 1200270 and 1003574, and TUBITAK 113M265.

  9. Investigation of the ratio of proton-stopping cross sections in Ag and Au

    SciTech Connect

    Semrad, D.; Golser, R.

    1987-06-01

    Knowledge of the ratio of stopping cross sections may help in determining best values from measurements. The case of Ag and Au is discussed, where theoretical considerations show that this ratio always has a value smaller than 1. This is confirmed experimentally for proton energies larger than 70 keV, in contradiction to all published stopping-power tabulations.

  10. Room temperature synthesis and optical studies on Ag and Au mixed nanocomposite polyvinylpyrrolidone polymer films.

    PubMed

    Udayabhaskar, R; Mangalaraja, R V; Manikandan, D; Arjunan, V; Karthikeyan, B

    2012-12-01

    Optical properties of silver, gold and bimetallic (Au:Ag) nanocomposite polymer films which are prepared by chemical method have been reported. The experimental data was correlated with the theoretical calculations using Mie theory. We adopt small change in the theoretical calculations of bimetallic/mixed particle nanocomposite and the theory agrees well with the experimental data. Polyvinylpyrrolidone (PVP) was used as reducing and capping agent. Fourier transform infrared spectroscopy (FTIR) study reveals the presence of different functional groups, the possible mechanism that leads to the formation of nanoparticles by using PVP alone as reducing agent. Optical absorption spectra of Ag and Au nanocomposite polymers show a surface plasmon resonance (SPR) band around 430 and 532 nm, respectively. Thermal annealing effect on the prepared samples at 60 °C for different time durations result in shift of SPR band maximum and varies the full width at half maximum (FWHM). Absorption spectra of Au:Ag bimetallic films show bands at 412 and 547 nm confirms the presence of Ag and Au nanoparticles in the composite.

  11. Biogenic synthesis of Au and Ag nanoparticles by Indian propolis and its constituents.

    PubMed

    Roy, Nayan; Mondal, Samiran; Laskar, Rajibul A; Basu, Saswati; Mandal, Debabrata; Begum, Naznin Ara

    2010-03-01

    In an attempt to find natural, environmentally benign, green-chemical agents for the synthesis of metal nanoparticles, we have demonstrated for the first time the excellent efficiency of ethanol and water extracts of a natural, non-toxic material, Indian propolis and two of its chemical constituents, pinocembrin and galangin in the rapid synthesis of stable Ag and Au nanoparticles having wide spectrum of fascinating morphologies. Both of these two extracts were found to be extremely efficient in the synthesis of Ag and Au nanoparticles under alkaline condition. For a given metal ion precursor, the kinetics of particle synthesis were remarkably similar in all the cases, as it is evident from the absorption spectra monitored over time. Moreover they exhibited similar redox behavior under alkaline condition (pH approximately 10.62). The efficiency of the ethanol and water extracts of Indian propolis towards Ag and Au nanoparticles synthesis was compared with that of naturally occurring hydroxyflavonoids, pinocembrin and galangin isolated from Indian propolis; which are equally efficient in the rapid synthesis of Ag and Au nanoparticles and stabilization of the resultant particles.

  12. Collagen-chitosan scaffold modified with Au and Ag nanoparticles: Synthesis and structure

    NASA Astrophysics Data System (ADS)

    Rubina, M. S.; Kamitov, E. E.; Zubavichus, Ya. V.; Peters, G. S.; Naumkin, A. V.; Suzer, S.; Vasil'kov, A. Yu.

    2016-03-01

    Nowadays, the dermal biomimetic scaffolds are widely used in regenerative medicine. Collagen-chitosan scaffold one of these materials possesses antibacterial activity, good compatibility with living tissues and has been already used as a wound-healing material. In this article, collagen-chitosan scaffolds modified with Ag and Au nanoparticles have been synthesized using novel method - the metal-vapor synthesis. The nanocomposite materials are characterized by XPS, TEM, SEM and synchrotron radiation-based X-ray techniques. According to XRD data, the mean size of the nanoparticles (NPs) is 10.5 nm and 20.2 nm in Au-Collagen-Chitosan (Au-CollCh) and Ag-Collagen-Chitosan (Ag-CollCh) scaffolds, respectively in fair agreement with the TEM data. SAXS analysis of the composites reveals an asymmetric size distribution peaked at 10 nm for Au-CollCh and 25 nm for Ag-CollCh indicative of particle's aggregation. According to SEM data, the metal-carrying scaffolds have layered structure and the nanoparticles are rather uniformly distributed on the surface material. XPS data indicate that the metallic nanoparticles are in their unoxidized/neutral states and dominantly stabilized within the chitosan-rich domains.

  13. Metallic influence on the atomic structure and optical activity of ligand-protected nanoparticles: a comparison between Ag and Au.

    PubMed

    Hidalgo, Francisco; Noguez, Cecilia; Olvera de la Cruz, Monica

    2014-03-21

    Using time-perturbed density functional theory the optical activity of metal-thiolate compounds formed by highly symmetric Ag and Au nanoparticles (NPs) and a methyl-thiol molecule is studied after performing atomic optimizations and electronic calculations upon adsorption. Many different sites and orientations of the adsorbed molecule on icosahedral Ag and Au NPs of 55 atoms are considered. Upon molecular adsorption atomic distortions on Au NPs are induced while not on Ag, which causes higher molecular adsorption energies in Au than in Ag. Structural distortions and the specific molecular adsorption site and orientation result in chiral metal-thiolate NPs. Ag and Au compounds with similar chirality, according to Hausdorff chirality measurements, show different optical activity signatures, where circular dichroism spectra of Au NPs are more intense. These dissimilarities are attributed in part to the differences in the electronic density of states, which are a consequence of relativistic effects and the atomic distortion. It is concluded that the optical activity of Ag and Au compounds is due to different mechanisms, while in Au it is mainly due to the atomic distortion of the metallic NPs induced after molecular adsorption, in Ag it is defined by the adsorption site and molecular orientation with respect to the NP symmetry.

  14. Ultra-thin L1{sub 0}-FePt for perpendicular anisotropy L1{sub 0}-FePt/Ag/[Co/Pd]{sub 30} pseudo spin valves

    SciTech Connect

    Ho, Pin; Chow, Gan Moog; Chen, Jing-Sheng; Han, Guchang; He, Kaihua

    2014-05-07

    Perpendicular anisotropy L1{sub 0}-FePt/Ag/[Co/Pd]{sub 30} pseudo spin valves (PSVs) with ultra-thin L1{sub 0}-FePt alloy free layer possessing high anisotropy and thermal stability have been fabricated and studied. The thickness of the L1{sub 0}-FePt layer was varied between 2 and 4 nm. The PSV became increasingly decoupled with reduced L1{sub 0}-FePt thickness due to the larger difference between the coercivity of the L1{sub 0}-FePt and [Co/Pd]{sub 30} films. The PSV with an ultra-thin L1{sub 0}-FePt free layer of 2 nm displayed a high K{sub u} of 2.21 × 10{sup 7} ergs/cm{sup 3}, high thermal stability of 84 and a largest giant magnetoresistance of 0.54%.

  15. Hollow Au/Ag nanostars displaying broad plasmonic resonance and high surface-enhanced Raman sensitivity.

    PubMed

    Garcia-Leis, Adianez; Torreggiani, Armida; Garcia-Ramos, Jose Vicente; Sanchez-Cortes, Santiago

    2015-08-28

    Bimetallic Au/Ag hollow nanostar (HNS) nanoparticles with different morphologies were prepared in this work. These nanoplatforms were obtained by changing the experimental conditions (concentration of silver and chemical reductors, hydroxylamine and citrate) and by using Ag nanostars as template nanoparticles (NPs) through galvanic replacement. The goal of this research was to create bimetallic Au/Ag star-shaped nanoparticles with advanced properties displaying a broader plasmonic resonance, a cleaner exposed surface, and a high concentration of electromagnetic hot spots on the surface provided by the special morphology of nanostars. The size, shape, and composition of Ag as well as their optical properties were studied by extinction spectroscopy, hyperspectral dark field microscopy, transmission and scanning electron microscopy (TEM and SEM), and energy dispersive X-ray spectroscopy (EDX). Finally, the surface-enhanced Raman scattering (SERS) activity of these HNS was investigated by using thioflavin T, a biomarker of the β-amyloid fibril formation, responsible for Alzheimer's disease. Lucigenin, a molecule displaying different SERS activities on Au and Ag, was also used to explore the presence of these metals on the NP surface. Thus, a relationship between the morphology, plasmon resonance and SERS activity of these new NPs was made.

  16. Resonances in Near-Threshold Electron Elastic Scattering Cross Sections for Au and Pt: Identification of Electron Affinities.

    NASA Astrophysics Data System (ADS)

    Felfli, Z.; Msezane, A. Z.; Sokolovski, D.

    2008-05-01

    The near-threshold electron attachment in Au and Pt atoms is investigated as Regge resonances using our recent Regge-pole methodology [1] together with a Thomas-Fermi potential which incorporates the crucial core-polarization interaction. The resultant stable negative ion states are found to have the discernable characteristic of very small imaginary parts of the Regge poles, which translates into long-lived resonances. The near-threshold electron elastic total cross sections for both Au and Pt are characterized by multiple resonances from which we extract the electron affinity (EA) values through the scrutiny of the imaginary part of the relevant complex angular momentum. For Au^- and Pt^- the extracted binding energies of 2.262 eV and 2.163 eV, respectively, are in excellent agreement with the most recently measured EA values for Au [2] and Pt [3]. Ramsauer-Townsend minima, shape resonances and the Wigner threshold behavior are identified in both Au^- and Pt^- ions.[1] D. Sokolovski et al, Phys. Rev. A 76, 012705 (2007)[2] H. Hotop and W. C. Lineberger, J. Chem. Ref. Data 14, 731 (1985)[3] R. C. Bilodeau et al, Phys. Rev. A 61, 012505 (1999)

  17. Preferential catalytic oxidation of carbon monoxide in presence of hydrogen over bimetallic AuPt supported on zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Naknam, Pattarasuda; Luengnaruemitchai, Apanee; Wongkasemjit, Sujitra; Osuwan, Somchai

    A series of AuPt/A zeolite and Pt/A zeolite catalysts prepared by incipient wetness impregnation are investigated for the preferential oxidation (PROX) of carbon monoxide in the presence of hydrogen over the temperature range of 50-310 °C under atmospheric pressure. The results indicate that when a small amount of gold is added to the Pt/A zeolite catalyst, the CO selectivity is improved at low temperatures, and 1% AuPt/A zeolite (at a weight ratio of Au:Pt = 1:2) gives the best performance, which provides a high CO conversion in combination with a high CO selectivity. In more realistic simulated reformate gases containing 10% CO 2 and 10% H 2O, there is not much difference between those in the presence and the absence of CO 2 and H 2O. Transmission electron microscopic and X-ray diffraction studies show that the two metals, Au and Pt, appear to be severely phase separated, which is confirmed by energy dispersive investigations.

  18. Evidence for rapid epithermal mineralization and coeval bimodal volcanism, Bruner Au-Ag property, NV USA

    NASA Astrophysics Data System (ADS)

    Baldwin, Dylan

    The character of Au-Ag mineralization and volcanic/hydrothermal relationships at the underexplored Miocene-age Bruner low-sulfidation epithermal Au-Ag deposit are elucidated using field and laboratory studies. Bruner is located in central Nevada within the Great Basin extensional province, near several major volcanic trends (Western Andesite, Northern Nevada Rift) associated with world-class Miocene-age epithermal Au-Ag provinces. Despite its proximity to several >1 Moz Au deposits, and newly discovered high-grade drill intercepts (to 117 ppm Au/1.5m), there is no published research on the deposit, the style of mineralization has not been systematically characterized, and vectors to mineralization remain elusive. By investigating the nature of mineralization and time-space relationships between volcanic/hydrothermal activity, the deposit has been integrated into a regional framework, and exploration targeting improved. Mineralization occurs within narrow quartz + adularia +/- pyrite veins that manifest as sheeted/stockwork zones, vein swarms, and rare 0.3-2 m wide veins hosted by two generations of Miocene high-K, high-silica rhyolite flow dome complexes overlying an andesite flow unit. The most prominent structural controls on veining are N­striking faults and syn-mineral basalt/rhyolite dikes. Productive veins have robust boiling indicators (high adularia content, bladed quartz after calcite, recrystallized colloform quartz bands), lack rhythmic banding, and contain only 1-2 stages; these veins overprint, or occur separately from another population of barren to weakly mineralized rhythmically banded quartz-only veins. Ore minerals consist of coarse Au0.5Ag 0.5 electrum, fine Au0.7Ag0.3 electrum, acanthite, uytenbogaardtite (Ag3AuS2) and minor embolite Ag(Br,Cl). Now deeply oxidized, veins typically contain <1% pyrite/goethite + Au-Ag minerals, with trace marcasite and microscopic Fe-poor sphalerite. Property-scale K-feldspar alteration related to a pre

  19. 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

  20. In situ biosynthesis of Ag, Au and bimetallic nanoparticles using Piper pedicellatum C.DC: green chemistry approach.

    PubMed

    Tamuly, Chandan; Hazarika, Moushumi; Borah, Sarat Ch; Das, Manash R; Boruah, Manas P

    2013-02-01

    The synthesis of Ag, Au and Ag-Au bimetallic nanoparticles using Piper pedicellatum C.DC leaf extract is demonstrated here. The rapid formation of stable Ag and Au nanoparticles has been found using P. pedicellatum C.DC leaf extract in aqueous medium at normal atmospheric condition. Competitive reduction of Ag(+) and Au(3+) ions present simultaneously in solution during exposure to P. pedicellatum C.DC leaf extract leads to the synthesis of bimetallic Ag-Au nanoparticles in solution. Transmission electron microscopy (TEM) analysis revealed that the Ag nanoparticles predominantly form spherical in shape with the size range of 2.0±0.5-30.0±1.2 nm. In case of Au nanoparticles, the particles are spherical in shape along with few triangular, hexagonal and pentagonal shaped nanoparticles also observed. X-ray diffraction (XRD) studies revealed that the nanoparticles were face centered cubic (fcc) in shape. Fourier transform infrared spectroscopy (FTIR) showed nanoparticles were capped with plant compounds. The chemical constituents, viz. catechin, gallic acid, courmaric acid and protocatechuic acid of the leaf extract were identified which may act as a reducing, stabilizing and capping agent. The expected reaction mechanism in the formation of Ag and Au nanoparticles is also reported. PMID:23107941

  1. A fluorometric biosensor based on functional Au/Ag nanoclusters for real-time monitoring of tyrosinase activity.

    PubMed

    Ao, Hang; Qian, Zhaosheng; Zhu, Yuyu; Zhao, Meizhi; Tang, Cong; Huang, Yuanyuan; Feng, Hui; Wang, Aijun

    2016-12-15

    Due to the vital role of tyrosinase in melanin biosynthesis and its function as an important biomarker for melanoma cancer, highly sensitive detection of its activity using biocompatible materials is in urgent demand. Herein we report a convenient and highly sensitive fluorometric biosensor for tyrosinase activity detection based on biocompatible dopamine-functionalized Au/Ag nanoclusters (Dopa-Au/Ag NCs). Dopamine with redox property was covalently linked to Au/Ag NCs surface and formed a Dopa-Au/Ag NCs bioconjugate with strong blue fluorescence. Dopamine is readily oxidized by molecular oxygen under the catalysis of tyrosinase. After dopamine is transformed to o-dopaquinone, an intraparticle photoinduced election transfer (PET) process occurs between Au/Ag NCs and o-dopaquinone moiety, leading to the fluorescence quenching of the Dopa-Au/Ag NCs bioconjugate. Thus, this biosensor was utilized for sensitive and selective detection of tyrosinase in terms of the relationship between fluorescence quenching efficiency and tyrosinase activity. This study discovers that Au/Ag NCs and dopaquinone can serve as a good electron acceptor and donor pair which results in an efficient intraparticle photoinduced electron transfer process, and also provides another alternative way for tyrosinase activity monitoring. PMID:27448544

  2. In situ biosynthesis of Ag, Au and bimetallic nanoparticles using Piper pedicellatum C.DC: green chemistry approach.

    PubMed

    Tamuly, Chandan; Hazarika, Moushumi; Borah, Sarat Ch; Das, Manash R; Boruah, Manas P

    2013-02-01

    The synthesis of Ag, Au and Ag-Au bimetallic nanoparticles using Piper pedicellatum C.DC leaf extract is demonstrated here. The rapid formation of stable Ag and Au nanoparticles has been found using P. pedicellatum C.DC leaf extract in aqueous medium at normal atmospheric condition. Competitive reduction of Ag(+) and Au(3+) ions present simultaneously in solution during exposure to P. pedicellatum C.DC leaf extract leads to the synthesis of bimetallic Ag-Au nanoparticles in solution. Transmission electron microscopy (TEM) analysis revealed that the Ag nanoparticles predominantly form spherical in shape with the size range of 2.0±0.5-30.0±1.2 nm. In case of Au nanoparticles, the particles are spherical in shape along with few triangular, hexagonal and pentagonal shaped nanoparticles also observed. X-ray diffraction (XRD) studies revealed that the nanoparticles were face centered cubic (fcc) in shape. Fourier transform infrared spectroscopy (FTIR) showed nanoparticles were capped with plant compounds. The chemical constituents, viz. catechin, gallic acid, courmaric acid and protocatechuic acid of the leaf extract were identified which may act as a reducing, stabilizing and capping agent. The expected reaction mechanism in the formation of Ag and Au nanoparticles is also reported.

  3. Hydroquinone-assisted synthesis of branched au-ag nanoparticles with polydopamine coating as highly efficient photothermal agents.

    PubMed

    Li, Jing; Wang, Wenjing; Zhao, Liang; Rong, Li; Lan, Shijie; Sun, Hongchen; Zhang, Hao; Yang, Bai

    2015-06-01

    Despite the success of galvanic replacement in preparing hollow nanostructures with diversified morphologies via the replacement reaction between sacrificial metal nanoparticles (NPs) seeds and less active metal ions, limited advances are made for producing branched alloy nanostructures. In this paper, we report an extended galvanic replacement for preparing branched Au-Ag NPs with Au-rich core and Ag branches using hydroquinone (HQ) as the reductant. In the presence of HQ, the preformed Ag seeds are replaceable by Au and, in turn, supply the growth of Ag branches. By altering the feed ratio of Ag seeds, HAuCl4, and HQ, the size and morphology of the NPs are tunable. Accordingly, the surface plasmon resonance absorption is tuned to near-infrared (NIR) region, making the branched NPs as potential materials in photothermal therapy. The branched NPs are further coated with polydopamine (PDA) shell via dopamine polymerization at room temperature. In comparison with bare NPs, PDA-coated branched Au-Ag (Au-Ag@PDA) NPs exhibit improved stability, biocompatibility, and photothermal performance. In vitro experiments indicate that the branched Au-Ag@PDA NPs are competitive agents for photothermal ablation of cancer cells. PMID:25969998

  4. Hydroquinone-assisted synthesis of branched au-ag nanoparticles with polydopamine coating as highly efficient photothermal agents.

    PubMed

    Li, Jing; Wang, Wenjing; Zhao, Liang; Rong, Li; Lan, Shijie; Sun, Hongchen; Zhang, Hao; Yang, Bai

    2015-06-01

    Despite the success of galvanic replacement in preparing hollow nanostructures with diversified morphologies via the replacement reaction between sacrificial metal nanoparticles (NPs) seeds and less active metal ions, limited advances are made for producing branched alloy nanostructures. In this paper, we report an extended galvanic replacement for preparing branched Au-Ag NPs with Au-rich core and Ag branches using hydroquinone (HQ) as the reductant. In the presence of HQ, the preformed Ag seeds are replaceable by Au and, in turn, supply the growth of Ag branches. By altering the feed ratio of Ag seeds, HAuCl4, and HQ, the size and morphology of the NPs are tunable. Accordingly, the surface plasmon resonance absorption is tuned to near-infrared (NIR) region, making the branched NPs as potential materials in photothermal therapy. The branched NPs are further coated with polydopamine (PDA) shell via dopamine polymerization at room temperature. In comparison with bare NPs, PDA-coated branched Au-Ag (Au-Ag@PDA) NPs exhibit improved stability, biocompatibility, and photothermal performance. In vitro experiments indicate that the branched Au-Ag@PDA NPs are competitive agents for photothermal ablation of cancer cells.

  5. Chloroplasts-mediated biosynthesis of nanoscale Au-Ag alloy for 2-butanone assay based on electrochemical sensor

    NASA Astrophysics Data System (ADS)

    Zhang, Yixia; Gao, Guo; Qian, Qirong; Cui, Daxiang

    2012-08-01

    We reported a one-pot, environmentally friendly method for biosynthesizing nanoscale Au-Ag alloy using chloroplasts as reducers and stabilizers. The prepared nanoscale Au-Ag alloy was characterized by UV-visible spectroscopy, X-ray diffraction (XRD) and high resolution transmission electron microscopy (HR-TEM). Fourier transform infrared spectroscopy (FTIR) analysis was further used to identify the possible biomolecules from chloroplasts that are responsible for the formation and stabilization of Au-Ag alloy. The FTIR results showed that chloroplast proteins bound to the nanoscale Au-Ag alloy through free amino groups. The bimetallic Au-Ag nanoparticles have only one plasmon band, indicating the formation of an alloy structure. HR-TEM images showed that the prepared Au-Ag alloy was spherical and 15 to 20 nm in diameter. The high crystallinity of the Au-Ag alloy was confirmed by SAED and XRD patterns. The prepared Au-Ag alloy was dispersed into multiwalled carbon nanotubes (MWNTs) to form a nanosensing film. The nanosensing film exhibited high electrocatalytic activity for 2-butanone oxidation at room temperature. The anodic peak current (Ip) has a linear relationship with the concentrations of 2-butanone over the range of 0.01% to 0.075% (v/v), when analyzed by cyclic voltammetry. The excellent electronic catalytic characteristics might be attributed to the synergistic electron transfer effects of Au-Ag alloy and MWNTs. It can reasonably be expected that this electrochemical biosensor provided a promising platform for developing a breath sensor to screen and pre-warn of early cancer, especially gastric cancer.

  6. Au@Ag Core-Shell Nanocubes with Finely Tuned and Well-Controlled Sizes, Shell Thicknesses, and Optical Properties

    PubMed Central

    Ma, Yanyun; Li, Weiyang; Cho, Eun Chul; Li, Zhiyuan; Yu, Taekyung; Zeng, Jie; Xie, Zhaoxiong; Xia, Younan

    2010-01-01

    This paper describes a facile method for generating Au@Ag core-shell nanocubes with edge lengths controllable in the range of 13.4 to 50 nm. The synthesis involved the use of single-crystal, spherical Au nanocrystals of 11 nm in size as the seeds in an aqueous system, with ascorbic acid serving as the reductant and cetyltrimethylammonium chloride (CTAC) as the capping agent. The thickness of the Ag shells could be finely tuned from 1.2 to 20 nm by varying the ratio of AgNO3 precursor to Au seeds. We also investigated the growth mechanism by examining the effects of seeds (capped by CTAC or CTAB) and capping agent (CTAC vs. CTAB) on both size and shape of the resultant core-shell nanocrystals. Our results clearly indicate that CTAC worked much better than CTAB as a capping agent in both the syntheses of Au seeds and Au@Ag core-shell nanocubes. We further studied the localized surface plasmon resonance properties of the Au@Ag nanocubes as a function of the Ag shell thickness. By comparing with the extinction spectra obtained from theoretical calculations, we derived a critical value around 3 nm for the shell thickness at which the plasmon excitation of the Au cores would be completely screened by the Ag shells. Moreover, these Au@Ag core-shell nanocubes could be converted into Au-based hollow nanostructures containing the original Au seeds in the interiors through a galvanic replacement reaction. PMID:20964400

  7. Low thermal conductive Bi-2223 tapes sheathed with Ag-Au alloys

    SciTech Connect

    Fujishiro, Hiroyuki; Ikebe, Manabu; Noto, Koshichi; Matsukawa, Michiaki,; Sasaoka, Takaaki; Nomura, Katsumi; Sato, Junichi; Kuma, Shoji,

    1994-07-01

    With the view of applying to power current leads for superconducting magnet systems and for other cryogenic power handling systems, low thermal conductive Bi-2223 superconducting tapes sheathed with Ag-Au alloy were measured from 12 to 260K. The critical current density (overall-J) was about 1,700A/cm{sup 2} at 77K, 0T and remained nearly constant irrespective of Au concentration up to 11 at %. The tape sheathed with Ag + 11at.% Au alloy, of which the superconductor cross-section ratio f{sub sc} was 0.65, had a thermal conductivity value about 0.2W/cmK at 77K. This value is as low as that of Cu-Zu. It was found that the thermal conductivity of the tape was close to the calculated one based on f{sub sc} and the independently measured thermal conductivities of the Ag-Au alloy and the Bi-2223 superconductor. The superconducting tapes sheathed with the alloy were confirmed to be suitable for the application as power current leads.

  8. Blood surface-enhanced Raman spectroscopy based on Ag and Au nanoparticles for nasopharyngeal cancer detection

    NASA Astrophysics Data System (ADS)

    Lin, Duo; Ge, Xiaosong; Lin, Xueliang; Chen, Guannan; Chen, Rong

    2016-05-01

    This study aims to evaluate and compare the utility of blood surface-enhanced Raman spectroscopy (SERS) based on Au or Ag nanoparticles (NPs), respectively, for detection of nasopharyngeal cancer (NPC). A rapid home-made Raman system was employed for SERS measurement, and high quality SERS spectra can be recorded from blood plasma samples belonging to 60 healthy volunteers and 100 NPC patients, using both metallic NPs. The spectral differences under Ag-SERS measurement between the normal and cancer groups are more significant than Au-SERS. Principal component analysis combined with linear discriminant analysis (PCA-LDA) was used for differentiating the two blood groups with a diagnostic sensitivity and specificity of 90% and 95%, respectively, using Ag-SERS method, which has almost a 20% improvement in diagnostic specificity in comparison to Au-SERS. This exploratory study demonstrates that blood SERS based on Ag NPs is capable of achieving a better diagnostic performance for NPC detection, and has promising potential for improving NPC screening.

  9. Spontaneous formation of Au-Pt alloyed nanoparticles using pure nano-counterparts as starters: a ligand and size dependent process.

    PubMed

    Usón, Laura; Sebastian, Victor; Mayoral, Alvaro; Hueso, Jose L; Eguizabal, Adela; Arruebo, Manuel; Santamaria, Jesus

    2015-06-14

    In this work we investigate the formation of PtAu monodisperse alloyed nanoparticles by ageing pure metallic Au and Pt small nanoparticles (sNPs), nanoparticle size <5 nm, under certain conditions. We demonstrate that those bimetallic entities can be obtained by controlling the size of the initial metallic sNPs separately prepared and by selecting their appropriate capping agents. The formation of this spontaneous phenomenon was studied using HR-STEM, EDS, ionic conductivity, UV-Vis spectroscopy and cyclic voltammetry. Depending on the type of capping agent used and the size of the initial Au sNPs, three different materials were obtained: (i) AuPt bimetallic sNPs showing a surface rich in Au atoms, (ii) segregated Au and Pt sNPs and (iii) a mixture of bimetallic nanoparticles as well as Pt sNPs and Au NPs. Surface segregation energies and the nature of the reaction environment are the driving forces to direct the distribution of atoms in the bimetallic sNPs. PtAu alloyed nanoparticles were obtained after 150 h of reaction at room temperature if a weak capping agent was used for the stabilization of the nanoparticles. It was also found that Au atoms diffuse towards Pt sNPs, producing a surface enriched in Au atoms. This study shows that even pure nanoparticles are prone to be modified by the surrounding nanoparticles to give rise to new nanomaterials if atomic diffusion is feasible. PMID:25985914

  10. Effects of Au content on the structure and magnetic properties of L1{sub 0}-FePt nanoparticles synthesized by the sol–gel method

    SciTech Connect

    Liu, Yang; Jiang, Yuhong; Kadasala, Naveen; Zhang, Xiaolong; Mao, Chenyi; Wang, Yaxin; Liu, Huilian; Liu, Yanqing; Yang, Jinghai; Yan, Yongsheng

    2014-07-01

    (FePt){sub 100−x}Au{sub x} (x=0, 5, 10, and 20) nanoparticles were synthesized by the sol–gel method, and effects of Au content on the structural and magnetic properties of samples were investigated. Au doping reduced the phase transition temperature from face-centered cubic (FCC) to face-centered tetragonal (FCT) structure. In addition, additive Au promotes the chemical ordering of L1{sub 0} FePt NPs and increases the grain size of L1{sub 0} FePt NPs. When Au content increased from 0 to 10 at%, the coercivity (H{sub c}) increased due to the increase in degree of ordering S and grain size of L1{sub 0} FePt NPs. By increasing the Au content to 20 at%, H{sub c} decreased. - Graphical abstract: (FePt){sub 100}Au{sub 0} NPs are the coexistence of FCT and FCC phases. However, no hints of FCC phase were found for the (FePt){sub 100−x}Au{sub x} NPs (x=5, 10 and 20), which indicates that addition of gold greatly promotes the FCC to FCT phase transition. - Highlights: • (FePt){sub 100−x}Au{sub x} (x=0, 5, 10 and 20) nanoparticles (NPs) were synthesized. • Au addition promotes the chemical ordering of L1{sub 0} FePt NPs. • Au addition reduces ordering temperature of L1{sub 0} FePt NPs from FCC to FCT phase. • (FePt){sub 90}Au{sub 10} NPs show a high coercivity of 9585 Oe at room temperature.

  11. Fabrication of two-dimensional Au at FePt core-shell nanoparticle arrays by photochemical metal deposition

    SciTech Connect

    Haertling, Thomas; Uhlig, Tino; Olk, Phillip; Eng, Lukas M.; Seidenstuecker, Axel; Wiedwald, Ulf; Han Luyang; Plettl, Alfred; Ziemann, Paul; Bigall, Nadja C.; Eychmueller, Alexander

    2010-05-03

    In this report, we experimentally demonstrate that single platinum nanoparticles exhibit the necessary catalytic activity for the optically induced reduction of H[AuCl{sub 4}] complexes to elemental gold. This finding is exploited for the parallel Au encapsulation of FePt nanoparticles arranged in a self-assembled two-dimensional array. Magnetic force microscopy reveals that the thin gold layer formed on the FePt particles leads to a strongly increased long-term stability of their magnetization under ambient conditions.

  12. Ferritin-mediated biomimetic synthesis of bimetallic Au-Ag nanoparticles on graphene nanosheets for electrochemical detection of hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Wang, Li; Wang, Jiku; Ni, Pengjuan; Li, Zhuang

    2015-03-01

    We demonstrated a biomimetic green synthesis of bimetallic Au-Ag nanoparticles (NPs) on graphene nanosheets (GNs). The spherical protein, ferritin (Fr), was bound onto GNs and served as the template for the synthesis of GN/Au-Ag nanohybrids. The created GN/Au-Ag nanohybrids were further utilized to fabricate a non-enzymatic amperometric biosensor for the sensitive detection of hydrogen peroxide (H2O2), and this biosensor displayed high performances to determine H2O2 with a detection limit of 20.0 × 10-6 M and a linear detection range from 2.0 μM to 7.0 mM.

  13. Fe-Au and Fe-Ag composites as candidates for biodegradable stent materials.

    PubMed

    Huang, Tao; Cheng, Jian; Bian, Dong; Zheng, Yufeng

    2016-02-01

    In this study, Fe-Ag and Fe-Au composites were fabricated by powder metallurgy using spark plasma sintering. Their microstructures, mechanical properties, and biocorrosion behavior were investigated by using optical microscopy, X-ray diffraction, environment scanning electronic microscopy, compressive test, electrochemical measurements, and immersion tests. Microstructure characterization indicated that the as-sintered iron-based materials obtained much finer grains than that of as-cast pure iron. Phase analysis showed that the Fe-Ag composites were composed of α-Fe and pure Ag phases, and Fe-Au composites consisted of α-Fe and Au phases. Compressive test showed that the improved mechanical strengths were obtained in as-sintered iron-based materials, among which the Fe-5 wt %Ag exhibited the best mechanical properties. The electrochemical and immersion tests revealed that the addition of Ag and Au could increase the corrosion rate of the iron matrix and change the corrosion mode into more uniform one. Based on the results of cytotoxicity evaluation, it was found that all the experimental material extracts performed no significant toxicity on the L-929 cells and EA. hy-926 cells, whereas a considerable inhibition on the proliferation of vascular smooth muscle cells was observed. The hemocompatibility tests showed that the hemolysis of all the experimental materials was within the range of 5%, which is the criteria value of biomaterials with good hemocomaptibility. The amount of platelet adhered on the surface of as-sintered iron-based materials was lower than that of as-cast pure iron, and the morphology of platelets kept smoothly spherical on the surface of all the experimental materials. PMID:25727071

  14. Fe-Au and Fe-Ag composites as candidates for biodegradable stent materials.

    PubMed

    Huang, Tao; Cheng, Jian; Bian, Dong; Zheng, Yufeng

    2016-02-01

    In this study, Fe-Ag and Fe-Au composites were fabricated by powder metallurgy using spark plasma sintering. Their microstructures, mechanical properties, and biocorrosion behavior were investigated by using optical microscopy, X-ray diffraction, environment scanning electronic microscopy, compressive test, electrochemical measurements, and immersion tests. Microstructure characterization indicated that the as-sintered iron-based materials obtained much finer grains than that of as-cast pure iron. Phase analysis showed that the Fe-Ag composites were composed of α-Fe and pure Ag phases, and Fe-Au composites consisted of α-Fe and Au phases. Compressive test showed that the improved mechanical strengths were obtained in as-sintered iron-based materials, among which the Fe-5 wt %Ag exhibited the best mechanical properties. The electrochemical and immersion tests revealed that the addition of Ag and Au could increase the corrosion rate of the iron matrix and change the corrosion mode into more uniform one. Based on the results of cytotoxicity evaluation, it was found that all the experimental material extracts performed no significant toxicity on the L-929 cells and EA. hy-926 cells, whereas a considerable inhibition on the proliferation of vascular smooth muscle cells was observed. The hemocompatibility tests showed that the hemolysis of all the experimental materials was within the range of 5%, which is the criteria value of biomaterials with good hemocomaptibility. The amount of platelet adhered on the surface of as-sintered iron-based materials was lower than that of as-cast pure iron, and the morphology of platelets kept smoothly spherical on the surface of all the experimental materials.

  15. Hierarchical paramecium-like hollow and solid Au/Pt bimetallic nanostructures constructed using goethite as template

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Repo, Eveliina; Heikkilä, Mikko; Leskelä, Markku; Sillanpää, Mika

    2010-10-01

    Novel hollow and solid paramecium-like hierarchical Au/Pt bimetallic nanostructures were constructed using goethite as template via a seed-mediated growth method. Transmission electron microscopy (TEM), ξ-potential measurement, UV-vis spectroscopy, energy dispersive x-ray spectroscopy (EDS), ICP-AES measurement, x-ray powder diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) were utilized to systematically characterize the bimetallic nanostructures. It is found that the core structure of the paramecium-like bimetallic nanomaterial is closely related to reducing agent. When ascorbic acid is used as reducing agent, goethite serves as in situ sacrificed template and hollow paramecium-like bimetallic structure is obtained. When NH2OH·HCl is used, solid nanostructure with preserved goethite core is produced. Heating the reaction solution is necessary to obtain the paramecium-like morphology with rough interconnected Pt cilia shell. The thickness of Pt cilia layer can be controlled by adjusting the molar ratio of H2PtCl6 to Au nanoseeds. The overgrowth of the rough Pt cilia is proposed to be via an autocatalytic and three-dimensional heterogeneous nucleation process first through flower-like morphology. Both the hollow and solid hierarchical paramecium-like Au/Pt bimetallic nanostructures show good catalytic activities.

  16. Hierarchical paramecium-like hollow and solid Au/Pt bimetallic nanostructures constructed using goethite as template.

    PubMed

    Liu, Wei; Repo, Eveliina; Heikkilä, Mikko; Leskelä, Markku; Sillanpää, Mika

    2010-10-01

    Novel hollow and solid paramecium-like hierarchical Au/Pt bimetallic nanostructures were constructed using goethite as template via a seed-mediated growth method. Transmission electron microscopy (TEM), xi-potential measurement, UV-vis spectroscopy, energy dispersive x-ray spectroscopy (EDS), ICP-AES measurement, x-ray powder diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) were utilized to systematically characterize the bimetallic nanostructures. It is found that the core structure of the paramecium-like bimetallic nanomaterial is closely related to reducing agent. When ascorbic acid is used as reducing agent, goethite serves as in situ sacrificed template and hollow paramecium-like bimetallic structure is obtained. When NH(2)OH.HCl is used, solid nanostructure with preserved goethite core is produced. Heating the reaction solution is necessary to obtain the paramecium-like morphology with rough interconnected Pt cilia shell. The thickness of Pt cilia layer can be controlled by adjusting the molar ratio of H(2)PtCl(6) to Au nanoseeds. The overgrowth of the rough Pt cilia is proposed to be via an autocatalytic and three-dimensional heterogeneous nucleation process first through flower-like morphology. Both the hollow and solid hierarchical paramecium-like Au/Pt bimetallic nanostructures show good catalytic activities.

  17. Au@Ag core/shell cuboids and dumbbells: Optical properties and SERS response

    NASA Astrophysics Data System (ADS)

    Khlebtsov, Boris N.; Liu, Zhonghui; Ye, Jian; Khlebtsov, Nikolai G.

    2015-12-01

    Recent studies have conclusively shown that the plasmonic properties of Au nanorods can be finely controlled by Ag coating. Here, we investigate the effect of asymmetric silver overgrowth of Au nanorods on their extinction and surface-enhanced Raman scattering (SERS) properties for colloids and self-assembled monolayers. Au@Ag core/shell cuboids and dumbbells were fabricated through a seed-mediated anisotropic growth process, in which AgCl was reduced by use of Au nanorods with narrow size and shape distribution as seeds. Upon tailoring the reaction rate, monodisperse cuboids and dumbbells were synthesized and further transformed into water-soluble powders of PEGylated nanoparticles. The extinction spectra of AuNRs were in excellent agreement with T-matrix simulations based on size and shape distributions of randomly oriented particles. The multimodal plasmonic properties of the Au@Ag cuboids and dumbbells were investigated by comparing the experimental extinction spectra with finite-difference time-domain (FDTD) simulations. The SERS efficiencies of the Au@Ag cuboids and dumbbells were compared in two options: (1) individual SERS enhancers in colloids and (2) self-assembled monolayers formed on a silicon wafer by drop casting of nanopowder solutions mixed with a drop of Raman reporters. By using 1,4-aminothiophenol Raman reporter molecules, the analytical SERS enhancement factor (AEF) of the colloidal dumbbells was determined to be 5.1×106, which is an order of magnitude higher than the AEF=4.0×105 for the cuboids. This difference can be explained by better fitting of the dumbbell plasmon resonance to the excitation laser wavelength. In contrast to the colloidal measurements, the AEF=5×107 of self-assembled cuboid monolayers was almost twofold higher than that for dumbbell monolayers, as determined with rhodamine 6G Raman reporters. According to TEM data and electromagnetic simulations, the better SERS response of the self-assembled cuboids is due to uniform

  18. Diffusion of Ag, Au and Cs implants in MAX phase Ti3SiC2

    SciTech Connect

    Jiang, Weilin; Henager, Charles H.; Varga, Tamas; Jung, Hee Joon; Overman, Nicole R.; Zhang, Chonghong; Gou, Jie

    2015-05-16

    MAX phases (M: early transition metal; A: elements in group 13 or 14; X: C or N), such as titanium silicon carbide (Ti3SiC2), have a unique combination of both metallic and ceramic properties, which make them attractive for potential nuclear applications. Ti3SiC2 has been considered as a possible fuel cladding material. This study reports on the diffusivities of fission product surrogates (Ag and Cs) and a noble metal Au (with diffusion behavior similar to Ag) in this ternary compound at elevated temperatures, as well as in dual-phase nanocomposite of Ti3SiC2/3C-SiC and polycrystalline CVD 3C-SiC for behavior comparisons. Samples were implanted with Ag, Au or Cs ions and characterized with various methods, including x-ray diffraction, electron backscatter diffraction, energy dispersive x-ray spectroscopy, Rutherford backscattering spectrometry, helium ion microscopy, and transmission electron microscopy. The results show that in contrast to immobile Ag in 3C-SiC, there is a significant outward diffusion of Ag in Ti3SiC2 within the dual-phase nanocomposite during Ag ion implantation at 873 K. Similar behavior of Au in polycrystalline Ti3SiC2 was also observed. Cs out-diffusion and release from Ti3SiC2 occurred during post-implantation thermal annealing at 973 K. This study suggests caution and further studies in consideration of Ti3SiC2 as a fuel cladding material for advanced nuclear reactors operating at very high temperatures.

  19. Diffusion of Ag, Au and Cs implants in MAX phase Ti3SiC2

    NASA Astrophysics Data System (ADS)

    Jiang, Weilin; Henager, Charles H.; Varga, Tamas; Jung, Hee Joon; Overman, Nicole R.; Zhang, Chonghong; Gou, Jie

    2015-07-01

    MAX phases (M: early transition metal; A: elements in group 13 or 14; X: C or N), such as titanium silicon carbide (Ti3SiC2), have a unique combination of both metallic and ceramic properties, which make them attractive for potential nuclear applications. Ti3SiC2 has been considered as a possible fuel cladding material. This study reports on the diffusivities of fission product surrogates (Ag and Cs) and a noble metal Au (with diffusion behavior similar to Ag) in this ternary compound at elevated temperatures, as well as in dual-phase nanocomposite of Ti3SiC2/3C-SiC and polycrystalline CVD 3C-SiC for behavior comparisons. Samples were implanted with Ag, Au or Cs ions and characterized with various methods, including X-ray diffraction, electron backscatter diffraction, energy dispersive X-ray spectroscopy, Rutherford backscattering spectrometry, helium ion microscopy, and transmission electron microscopy. The results show that in contrast to immobile Ag in 3C-SiC, there is a significant outward diffusion of Ag in Ti3SiC2 within the dual-phase nanocomposite during Ag ion implantation at 873 K. Similar behavior of Au in polycrystalline Ti3SiC2 was also observed. Cs out-diffusion and release from Ti3SiC2 occurred during post-implantation thermal annealing at 973 K. This study suggests caution and further studies in consideration of Ti3SiC2 as a fuel cladding material for advanced nuclear reactors operating at very high temperatures.

  20. An intermetallic Au24Ag20 superatom nanocluster stabilized by labile ligands.

    PubMed

    Wang, Yu; Su, Haifeng; Xu, Chaofa; Li, Gang; Gell, Lars; Lin, Shuichao; Tang, Zichao; Häkkinen, Hannu; Zheng, Nanfeng

    2015-04-01

    An intermetallic nanocluster containing 44 metal atoms, Au24Ag20(2-SPy)4(PhC≡C)20Cl2, was successfully synthesized and structurally characterized by single-crystal analysis and density funtional theory computations. The 44 metal atoms in the cluster are arranged as a concentric three-shell Au12@Ag20@Au12 Keplerate structure having a high symmetry. For the first time, the co-presence of three different types of anionic ligands (i.e., phenylalkynyl, 2-pyridylthiolate, and chloride) was revealed on the surface of metal nanoclusters. Similar to thiolates, alkynyls bind linearly to surface Au atoms using their σ-bonds, leading to the formation of two types of surface staple units (PhC≡C-Au-L, L = PhC≡C(-) or 2-pyridylthiolate) on the cluster. The co-presence of three different surface ligands allows the site-specific surface and functional modification of the cluster. The lability of PhC≡C(-) ligands on the cluster was demonstrated, making it possible to keep the metal core intact while removing partial surface capping. Moreover, it was found that ligand exchange on the cluster occurs easily to offer various derivatives with the same metal core but different surface functionality and thus different solubility. PMID:25803406

  1. An intermetallic Au24Ag20 superatom nanocluster stabilized by labile ligands.

    PubMed

    Wang, Yu; Su, Haifeng; Xu, Chaofa; Li, Gang; Gell, Lars; Lin, Shuichao; Tang, Zichao; Häkkinen, Hannu; Zheng, Nanfeng

    2015-04-01

    An intermetallic nanocluster containing 44 metal atoms, Au24Ag20(2-SPy)4(PhC≡C)20Cl2, was successfully synthesized and structurally characterized by single-crystal analysis and density funtional theory computations. The 44 metal atoms in the cluster are arranged as a concentric three-shell Au12@Ag20@Au12 Keplerate structure having a high symmetry. For the first time, the co-presence of three different types of anionic ligands (i.e., phenylalkynyl, 2-pyridylthiolate, and chloride) was revealed on the surface of metal nanoclusters. Similar to thiolates, alkynyls bind linearly to surface Au atoms using their σ-bonds, leading to the formation of two types of surface staple units (PhC≡C-Au-L, L = PhC≡C(-) or 2-pyridylthiolate) on the cluster. The co-presence of three different surface ligands allows the site-specific surface and functional modification of the cluster. The lability of PhC≡C(-) ligands on the cluster was demonstrated, making it possible to keep the metal core intact while removing partial surface capping. Moreover, it was found that ligand exchange on the cluster occurs easily to offer various derivatives with the same metal core but different surface functionality and thus different solubility.

  2. Enzymatic biosensor of horseradish peroxidase immobilized on Au-Pt nanotube/Au-graphene for the simultaneous determination of antioxidants.

    PubMed

    Wu, Long; Yin, Wenmin; Tang, Kun; Li, Dian; Shao, Kang; Zuo, Yunpeng; Ma, Jing; Liu, Jiawei; Han, Heyou

    2016-08-24

    A new electrochemical method has been proposed for the simultaneous determination of butylated hydroxyanisole (BHA) and propyl gallate (PG) in food matrices based on enzymatic biosensors. Spiny Au-Pt nanotubes (SAP NTs) was first synthesized and demonstrated to exhibit intrinsic peroxidase and catalase-like activity. The structure of SAP NTs provides large surface area and favorable medium for electron transfer, on which HRP were immobilized and acted as enzymatic biosensor for the simultaneous detection of BHA and PG. The results revealed that BHA and PG both have well-defined oxidation waves with peak potentials of 624 and 655 mV, respectively. Under the optimal conditions, the method behaved satisfactory analytical performance towards BHA and PG with a wide linear range of 0.3-50 mg L(-1) and 0.1-100 mg L(-1), as well as a detection limit of 0.046 mg L(-1) and 0.024 mg L(-1) (3σ/slope), respectively. Besides, the proposed method exhibits good sensitivity, stability and reproducibility, providing an alternative to fabricate electrode and construct sensitive biosensors. PMID:27497001

  3. Highly sensitive immunoassay based on SERS using nano-Au immune probes and a nano-Ag immune substrate.

    PubMed

    Shu, Lei; Zhou, Jun; Yuan, Xiaocong; Petti, Lucia; Chen, Jinping; Jia, Zhenhong; Mormile, Pasquale

    2014-06-01

    A super-high-sensitivity immunoassay based on surface-enhanced Raman scattering (SERS) was implemented using the nano-Au immune probes and nano-Ag immune substrate. Ultraviolet-visible extinction spectra, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) images, and SERS spectra were used to characterise the nano-Au immune probes and the nano-Ag immune substrate. The nano-Ag immune substrate was prepared by the in situ growth of Ag nanoparticles and the subsequent linkage of these nanoparticles with anti-apolipoprotein B on a silicon wafer. The nano-Ag immune substrate exhibited strong SERS activity, excellent reproducibility, and high biospecificity. The nano-Au immune probes were prepared by immobilising 4-mercaptobenzoic acid (4MBA) molecules as a Raman reporter and anti-apolipoprotein B onto the surfaces of Au nanoparticles. It was found that 4MBA induced the aggregation of Au nanoparticles, resulting in the generation of vast hot spots. Moreover, the nano-Au immune probes exhibited strong SERS activity and high biospecificity. A sandwich-type immunoassay structure consisting of the nano-Au immune probes and nano-Ag immune substrate was used to detect the concentration of apolipoprotein B, where the detection limit was as low as 2 fg/mL (3.878×10(-18) mol/L). Taken together, the experimental results indicate that the proposed immunoassay protocol has a great potential application in biological sensing and clinical diagnostics.

  4. Ordered arrays of Au-nanobowls loaded with Ag-nanoparticles as effective SERS substrates for rapid detection of PCBs

    NASA Astrophysics Data System (ADS)

    Chen, Bensong; Meng, Guowen; Zhou, Fei; Huang, Qing; Zhu, Chuhong; Hu, Xiaoye; Kong, Mingguang

    2014-04-01

    Large-scale hexagonally close-packed arrays of Au-nanobowls (Au-NBs) with tens of Ag-nanoparticles (Ag-NPs) dispersed in each bowl (denoted as Ag-NPs@Au-NB arrays) are achieved and utilized as effective surface-enhanced Raman scattering (SERS) substrates. The field enhancement benefiting from the special particle-in-cavity geometrical structure as well as the high density of SERS hot spots located in the sub-10 nm gaps between adjacent Ag-NPs and at the particle-cavity junctions all together contribute to the high SERS activity of the Ag-NPs@Au-NB arrays; meanwhile the ordered morphological features of the Ag-NPs@Au-NB arrays guarantee uniformity and reproducibility of the SERS signals. By modifying the Ag-NPs@Au-NB arrays with mono-6-thio-β-cyclodextrin, the SERS detection sensitivity to 3,3‧,4,4‧-tetrachlorobiphenyl (PCB-77, one congener of polychlorinated biphenyls (PCBs, kinds of persistent organic pollutants which represent a global environmental hazard)) can be further improved and a low concentration down to 5 × 10-7 M can still be examined, showing promising potential for application in rapid detection of trace-level PCBs in the environment.

  5. Double Detection of Mycotoxins Based on SERS Labels Embedded Ag@Au Core-Shell Nanoparticles.

    PubMed

    Zhao, Yuan; Yang, Yaxin; Luo, Yaodong; Yang, Xuan; Li, Manli; Song, Qijun

    2015-10-01

    A sensitive surface-enhanced Raman scattering (SERS) signal dependent double detection of mycotoxins is achieved for the first time, without the aid of nucleic acid amplification strategies. SERS labels embedded Ag@Au core-shell (CS) nanoparticles (NPs) as novel SERS tags are successfully prepared through a galvanic replacement-free deposition. SERS tags produce stable and quantitative SERS signal, emerging from the plasmonic coupling at the junction of Ag core and Au shell. SERS tags engineered Raman aptasensors are developed for the double detection of ochratoxin A (OTA) and aflatoxin B1 (AFB1) in maize meal. The limits of detection (LODs) are as low as 0.006 ng/mL for OTA and 0.03 ng/mL for AFB1. The developed protocol can be extended to a large set of different SERS tags for the sensitive detection of multiple targets that possess different lengths of aptamers.

  6. Optical and electronic properties of mixed Ag-Au tetramer cations

    SciTech Connect

    Shayeghi, A. Schäfer, R.; Heard, C. J.; Johnston, R. L.

    2014-02-07

    We present experimental and theoretical studies of the optical response of mixed Ag {sub n} Au {sub 4−n}{sup +} (n=1–3) clusters in the photon energy range ℏω = 1.9–3.5 eV. Absorption spectra are recorded by a newly built longitudinal molecular beam depletion spectroscopy apparatus providing lower limits to absolute photodissociation cross sections. The experimental data are compared to optical response calculations in the framework of long-range corrected time-dependent density functional theory with initial cluster geometries obtained by the unbiased Birmingham Cluster Genetic Algorithm coupled with density functional theory. Experiments and excited state calculations shed light on the structural and electronic properties of the mixed Ag-Au tetramer cations.

  7. Fabrication of AgAu alloy-TiO2 core-shell nanoparticles and their photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao-yu; Yuan, Shu-long; Yuan, Yu-zhen; Li, Xue

    2015-01-01

    In this paper, for improving the photocatalytic efficiency of titania (TiO2) nanoparticles (NPs), AgAu alloy-TiO2 core-shell NPs are fabricated via a sol-gel (SG) process in the presence of AgAu alloy NPs with block copolymer shells as templates. The photocatalytic activities of the AgAu-TiO2 NPs on the photodecomposition of methylene blue (MB) are investigated. The AgAu-TiO2 composite NPs coated with 5.0% titania related to block copolymers show higher photocatalytic activity than the other samples in which the titania contents are larger than 5.0%. The results indicate that the increase of the thickness of the TiO2 shell leads to the decrease of the photocatalytic activity.

  8. Au and Pt nanoparticle supported catalysts tailored for H-2 production: From models to powder catalysts

    DOE PAGES

    T. D. Nguyen-Phan; Baber, A. E.; Rodriguez, J. A.; Senanayake, S. D.

    2015-12-10

    The use of metal nanoparticles (NPs), including Au and Pt, supported over oxides has been pivotal, and is ever increasing in enabling catalytic reactions which target the production of hydrogen. We review here the most recent works pertaining to the fundamental understanding of the structure, morphology, growth, characterization, and intrinsic phenomenological properties of Au– and Pt– based catalysts that influence the reactivity and selectivity to target hydrogen production. We draw on surface science and theoretical methods of model and powder catalysts using high resolution imaging, spectroscopy, scattering experiments, and theoretical studies. Based on these insights we identify key aspects ofmore » studies of supported metal nanoparticle (NP) catalysts for several reactions. The main focus of this review is on the intersection of catalytic chemistry related to the water-gas shift (WGS), oxygenate steam reforming (OSR), and solarassisted reactions (SAR).« less

  9. Self-assembled arrays of high anisotropy FePt-Au nanoparticles

    NASA Astrophysics Data System (ADS)

    Butera, A.; Kang, S. S.; Nikles, D. E.; Harrell, J. W.

    2004-12-01

    We have studied the ferromagnetic resonance response of as-made and annealed Fe 46Pt 46Au 8 self-ordered nanoparticles forming a film. As-made particles, which crystallize in a low magnetic anisotropy FCC phase, show a single isotropic resonance line close to g=2.1. Particles annealed at 450C for 30 min are composed of a mixture of the FCC and the high anisotropy L 10 phases. In this sample the resonant spectra are anisotropic when the external applied field is rotated from the in-plane to the out-of-plane direction. This absorption also seems to be related to the minority FCC particles which have a better degree of surface order due to the surrounding ferromagnetic environment. From the line width angular dependence we obtained a large dispersion in the anisotropy constant, probably arising from the different degree of atomic ordering of particles in the L1 0 phase.

  10. Au and Pt nanoparticle supported catalysts tailored for H-2 production: From models to powder catalysts

    SciTech Connect

    T. D. Nguyen-Phan; Baber, A. E.; Rodriguez, J. A.; Senanayake, S. D.

    2015-12-10

    The use of metal nanoparticles (NPs), including Au and Pt, supported over oxides has been pivotal, and is ever increasing in enabling catalytic reactions which target the production of hydrogen. We review here the most recent works pertaining to the fundamental understanding of the structure, morphology, growth, characterization, and intrinsic phenomenological properties of Au– and Pt– based catalysts that influence the reactivity and selectivity to target hydrogen production. We draw on surface science and theoretical methods of model and powder catalysts using high resolution imaging, spectroscopy, scattering experiments, and theoretical studies. Based on these insights we identify key aspects of studies of supported metal nanoparticle (NP) catalysts for several reactions. The main focus of this review is on the intersection of catalytic chemistry related to the water-gas shift (WGS), oxygenate steam reforming (OSR), and solarassisted reactions (SAR).

  11. Polynuclear Gold [AuI]4, [AuI]8, and Bimetallic [AuI 4AgI] Complexes: C−H Functionalization of Carbonyl Compounds and Homogeneous Carbonylation of Amines

    PubMed Central

    Smirnova, Ekaterina S.; Muñoz Molina, José M.; Johnson, Alice; Bandeira, Nuno A. G.; Bo, Carles

    2016-01-01

    Abstract The synthesis of tetranuclear gold complexes, a structurally unprecedented octanuclear complex with a planar [AuI 8] core, and pentanuclear [AuI 4MI] (M=Cu, Ag) complexes is presented. The linear [AuI 4] complex undergoes C−H functionalization of carbonyl compounds under mild reaction conditions. In addition, [AuI 4AgI] catalyzes the carbonylation of primary amines to form ureas under homogeneous conditions with efficiencies higher than those achieved by gold nanoparticles. PMID:27167611

  12. Measuring the Optical Absorption Cross-sections of Au-Ag Nanocages and Au Nanorods by Photoacoustic Imaging

    PubMed Central

    Cho, Eun Chul; Kim, Chulhong; Zhou, Fei; Cobley, Claire M.; Song, Kwang Hyun; Chen, Jingyi; Li, Zhi-Yuhan; Wang, Lihong V.; Xia, Younan

    2009-01-01

    This paper presents a method for measuring the optical absorption cross-sections (σa) of Au-Ag nanocages and Au nanorods. The method is based on photoacoustic (PA) imaging, where the detected signal is directly proportional to the absorption coefficient (μa) of the nanostructure. For each type of nanostructure, we firstly obtained μa from the PA signal by benchmarking against a linear calibration curve (PA signal vs. μa) derived from a set of methylene blue solutions with different concentrations. We then calculated σa by dividing the μa by the corresponding concentration of the Au nanostructure. Additonally, we obtained the extinction cross-section (σe, sum of absorption and scattering) from the extinction spectrum recorded using a conventional UV-vis-NIR spectrometer. From the measurements of σa and σe, we were able to easily derive both the absorption and scattering cross-sections for each type of gold nanostructure. The ratios of absorption to extinction obtained from experimental and theoretical approaches agreed well, demonstrating the potential use of this method in determining the optical absorption and scattering properties of gold nanostructures and other types of nanomaterials. PMID:19680423

  13. 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

    Goto, Tomoyo; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

    2015-12-15

    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.

  14. 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.

  15. Electron Attachment in Low-Energy Electron Elastic Collisions with Au and Pt Atoms: Identification of Excited Anions

    NASA Astrophysics Data System (ADS)

    Msezane, A. Z.; Eure, A.; Felfli, Z.; Sokolovski, D.

    2009-11-01

    The recent Regge-pole methodology has been benchmarked [1] on the accurately measured binding energies of the excited Ge= and Sn= anions [2] through the binding energies (BEs) extracted from the Regge-pole calculated elastic total cross sections (TCSs). Here the methodology is applied together with a Thomas-Fermi type potential that incorporates the vital core polarization interaction to investigate the possibility of forming excited Au= and Pt= anions in low-energy electron elastic collisions with Au and Pt atoms. From the positions of the characteristic extremely narrow resonances in the total cross sections, we extract the binding energies of the excited Au= and Pt= anions formed as Regge resonances during the collisions. The angular life of the complexes thus formed is used to differentiate the stable excited bound states of the anions from the shape resonances [3]. The BEs for the excited Au= and Pt= anions are found to be 0.475eVand 0.543eV, respectively, challenging both theory and experiment to verify. [1] A. Msezane et al, Phys. Rev. A, Submitted (2009) [2] M. Scheer et al, Phys. Rev. A 58, 2844 (1998) [3] Z. Felfli et al, Phys. Rev. A 79, 012714 (2009)

  16. Near-threshold resonances in electron elastic scattering cross sections for Au and Pt atoms: identification of electron affinities

    NASA Astrophysics Data System (ADS)

    Msezane, A. Z.; Felfli, Z.; Sokolovski, D.

    2008-05-01

    The recent Regge-pole methodology has been employed together with a Thomas-Fermi type potential which incorporates the vital core-polarization interaction to investigate the near-threshold electron attachment in Au and Pt as Regge resonances. The resultant stable negative ion states are found to have the discernible characteristic of very small imaginary parts of the Regge poles, which translate into long-lived resonances. The near-threshold electron elastic total cross sections are characterized by multiple resonances from which we extract the electron affinity (EA) values through the scrutiny of the imaginary part of the relevant complex angular momentum. For the Au- and Pt- negative ions the extracted binding energies of 2.262 eV and 2.163 eV, respectively are in excellent agreement with the most recently measured EA values for Au and Pt. Ramsauer-Townsend minima, shape resonances and the Wigner threshold behaviour are identified in both Au- and Pt- ions.

  17. 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

  18. New isotopic evidence bearing on bonanza (Au-Ag) epithermal ore-forming processes

    NASA Astrophysics Data System (ADS)

    Saunders, James A.; Mathur, Ryan; Kamenov, George D.; Shimizu, Toru; Brueseke, Matthew E.

    2016-01-01

    New Cu, S, and Pb isotope data provide evidence for a magmatic source of metal(loid)s and sulfur in epithermal Au-Ag deposits even though their ore-forming solutions are composed primarily of heated meteoric (ground) waters. The apparent isotopic discrepancy between ore metals and ore-forming solutions, and even between the ore and associated gangue minerals, indicates two different sources of epithermal ore-forming constituents: (1) a shallow geothermal system that not only provides the bulk of water for the ore-forming solutions but also major chemical constituents leached from host rocks (silica, aluminum, potassium, sodium, calcium) to make gangue minerals and (2) metals and metalloids (As, Te, Sb, etc.) and sulfur (±Se) derived from deeper magma bodies. Isotopic data are consistent with either vapor-phase transport of metal(loids) and sulfur and their subsequent absorption by shallow geothermal waters or formation of metallic (Au, Ag, Cu phases) nanoparticles at depth from magmatic fluids prior to encountering the geothermal system. The latter is most consistent with ore textures that indicate physical transport and aggregation of nanoparticles were significant ore-forming processes. The recognition that epithermal Au-Ag ores form in tectonic settings that produce magmas capable of releasing metal-rich fluids necessary to form these deposits can refine exploration strategies that previously often have focused on locating fossil geothermal systems.

  19. Magnetic and electronic structure of Mn nanostructures on Ag(111) and Au(111)

    NASA Astrophysics Data System (ADS)

    Cardias, R.; Bezerra-Neto, M. M.; Ribeiro, M. S.; Bergman, A.; Szilva, A.; Eriksson, O.; Klautau, A. B.

    2016-01-01

    We present results of the electronic and magnetic structure of Mn nanowires adsorbed on Ag(111) and Au(111) surfaces. For finite Mn nanowires on Ag(111) and Au(111) surfaces, our ab initio results show that the large difference between the spin-orbit splitting of these two surfaces leads to completely different magnetic configurations. The magnetic ordering for Mn nanowires adsorbed on Ag(111) is governed by the strong exchange interaction between Mn adatoms. For Mn nano-chains on Au(111), the competition between Heisenberg and Dzyaloshinskii-Moriya interactions leads to a complex magnetic structure of the clusters considered here. Among the more conspicuous results we note a spin-spiral helical type for the nanowire with seven atoms, and a complex magnetic configuration incommensurate with the substrate lattice for a double-sized Mn wire. The effect of the structural relaxation is also investigated, showing sensitivity of the exchange interactions to the bond distance to the substrate. We also demonstrate that small changes in the band filling of these Mn chains results in drastically different changes of the interatomic exchange. Finally, we show that dispersion of the electronic energy spectrum is possible even in nanostructures with bounded spatial extension.

  20. Structural and electronic properties of graphene nanoflakes on Au(111) and Ag(111)

    PubMed Central

    Tesch, Julia; Leicht, Philipp; Blumenschein, Felix; Gragnaniello, Luca; Fonin, Mikhail; Marsoner Steinkasserer, Lukas Eugen; Paulus, Beate; Voloshina, Elena; Dedkov, Yuriy

    2016-01-01

    We investigate the electronic properties of graphene nanoflakes on Ag(111) and Au(111) surfaces by means of scanning tunneling microscopy and spectroscopy as well as density functional theory calculations. Quasiparticle interference mapping allows for the clear distinction of substrate-derived contributions in scattering and those originating from graphene nanoflakes. Our analysis shows that the parabolic dispersion of Au(111) and Ag(111) surface states remains unchanged with the band minimum shifted to higher energies for the regions of the metal surface covered by graphene, reflecting a rather weak interaction between graphene and the metal surface. The analysis of graphene-related scattering on single nanoflakes yields a linear dispersion relation E(k), with a slight p-doping for graphene/Au(111) and a larger n-doping for graphene/Ag(111). The obtained experimental data (doping level, band dispersions around EF, and Fermi velocity) are very well reproduced within DFT-D2/D3 approaches, which provide a detailed insight into the site-specific interaction between graphene and the underlying substrate. PMID:27002297

  1. Redox-Robust Pentamethylferrocene Polymers and Supramolecular Polymers, and Controlled Self-Assembly of Pentamethylferricenium Polymer-Embedded Ag, AgI, and Au Nanoparticles.

    PubMed

    Gu, Haibin; Ciganda, Roberto; Castel, Patricia; Vax, Amélie; Gregurec, Danijela; Irigoyen, Joseba; Moya, Sergio; Salmon, Lionel; Zhao, Pengxiang; Ruiz, Jaime; Hernández, Ricardo; Astruc, Didier

    2015-12-01

    We report the first pentamethylferrocene (PMF) polymers and the redox chemistry of their robust polycationic pentamethylferricenium (PMFium) analogues. The PMF polymers were synthesized by ring-opening metathesis polymerization (ROMP) of a PMF-containing norbornene derivative by using the third-generation Grubbs ruthenium metathesis catalyst. Cyclic voltammetry studies allowed us to determine confidently the number of monomer units in the polymers through the Bard-Anson method. Stoichiometric oxidation by using ferricenium hexafluorophosphate quantitatively and instantaneously provided fully stable (even in aerobic solutions) blue d(5) Fe(III) metallopolymers. Alternatively, oxidation of the PMF-containing polymers was conducted by reactions with Ag(I) or Au(III) , to give PMFium polymer-embedded Ag and Au nanoparticles (NPs). In the presence of I2 , oxidation by using Ag(I) gave polymer-embedded Ag/AgI NPs and AgNPs at the surface of AgI NPs. Oxidation by using Au(III) also produced an Au(I) intermediate that was trapped and characterized. Engineered single-electron transfer reactions of these redox-robust nanomaterial precursors appear to be a new way to control their formation, size, and environment in a supramolecular way.

  2. Redox-Robust Pentamethylferrocene Polymers and Supramolecular Polymers, and Controlled Self-Assembly of Pentamethylferricenium Polymer-Embedded Ag, AgI, and Au Nanoparticles.

    PubMed

    Gu, Haibin; Ciganda, Roberto; Castel, Patricia; Vax, Amélie; Gregurec, Danijela; Irigoyen, Joseba; Moya, Sergio; Salmon, Lionel; Zhao, Pengxiang; Ruiz, Jaime; Hernández, Ricardo; Astruc, Didier

    2015-12-01

    We report the first pentamethylferrocene (PMF) polymers and the redox chemistry of their robust polycationic pentamethylferricenium (PMFium) analogues. The PMF polymers were synthesized by ring-opening metathesis polymerization (ROMP) of a PMF-containing norbornene derivative by using the third-generation Grubbs ruthenium metathesis catalyst. Cyclic voltammetry studies allowed us to determine confidently the number of monomer units in the polymers through the Bard-Anson method. Stoichiometric oxidation by using ferricenium hexafluorophosphate quantitatively and instantaneously provided fully stable (even in aerobic solutions) blue d(5) Fe(III) metallopolymers. Alternatively, oxidation of the PMF-containing polymers was conducted by reactions with Ag(I) or Au(III) , to give PMFium polymer-embedded Ag and Au nanoparticles (NPs). In the presence of I2 , oxidation by using Ag(I) gave polymer-embedded Ag/AgI NPs and AgNPs at the surface of AgI NPs. Oxidation by using Au(III) also produced an Au(I) intermediate that was trapped and characterized. Engineered single-electron transfer reactions of these redox-robust nanomaterial precursors appear to be a new way to control their formation, size, and environment in a supramolecular way. PMID:26494439

  3. Raman scattering of 4-aminobenzenethiol sandwiched between Ag nanoparticle and macroscopically smooth Au substrate: effects of size of Ag nanoparticles and the excitation wavelength.

    PubMed

    Kim, Kwan; Choi, Jeong-Yong; Lee, Hyang Bong; Shin, Kuan Soo

    2011-09-28

    A nanogap formed by a metal nanoparticle and a flat metal substrate is one kind of "hot site" for surface-enhanced Raman scattering (SERS). Accordingly, although no Raman signal is observable when 4-aminobenzenethiol (4-ABT), for instance, is self-assembled on a flat Au substrate, a distinct spectrum is obtained when Ag or Au nanoparticles are adsorbed on the pendent amine groups of 4-ABT. This is definitely due to the electromagnetic coupling between the localized surface plasmon of Ag or Au nanoparticle with the surface plasmon polariton of the planar Au substrate, allowing an intense electric field to be induced in the gap even by visible light. To appreciate the Raman scattering enhancement and also to seek the optimal condition for SERS at the nanogap, we have thoroughly examined the size effect of Ag nanoparticles, along with the excitation wavelength dependence, by assembling 4-ABT between planar Au and a variable-size Ag nanoparticle (from 20- to 80-nm in diameter). Regarding the size dependence, a higher Raman signal was observed when larger Ag nanoparticles were attached onto 4-ABT, irrespective of the excitation wavelength. Regarding the excitation wavelength, the highest Raman signal was measured at 568 nm excitation, slightly larger than that at 632.8 nm excitation. The Raman signal measured at 514.5 and 488 nm excitation was an order of magnitude weaker than that at 568 nm excitation, in agreement with the finite-difference time domain simulation. It is noteworthy that placing an Au nanoparticle on 4-ABT, instead of an Ag nanoparticle, the enhancement at the 568 nm excitation was several tens of times weaker than that at the 632.8 nm excitation, suggesting the importance of the localized surface plasmon resonance of the Ag nanoparticles for an effective coupling with the surface plasmon polariton of the planar Au substrate to induce a very intense electric field at the nanogap.

  4. Synthesis of multifunctional Ag@Au@phenol formaldehyde resin particles loaded with folic acids for photothermal therapy.

    PubMed

    Yang, Ping; Xu, Qi-Zhi; Jin, Sheng-Yu; Lu, Yang; Zhao, Yang; Yu, Shu-Hong

    2012-07-23

    Multifunctional Ag@Au@ phenol formaldehyde resin (PFR) particles loaded with folic acids (FA) have been designed for killing tumor cells through photothermy conversion under the irradiation of near-infrared (NIR) light. Possessing the virtue of good fluorescence, low toxicity, and good targeting, the nanocomposite consists of an Ag core, an Au layer, a PFR shell, and folic acids on the PFR shell. The Ag@PFR core-shell structure can be prepared with a simple hydrothermal method after preheating. We then filled the PFR shell with a layer of Au by heating and modified the shell with polyelectrolyte to change its surface charge state. To capture tumor cells actively, FA molecules were attached onto the surface of the Ag@Au@PFR particles in the presence of 1-ethyl-3-(3-dimethly aminopropyl) carbodiimide (EDAC) and N-hydroxysuccinimide (NHS). Owing to the excellent property of Au NPs and Ag NPs as photothermal conversion agents, the Ag@Au@ PFR@FA particles can be utilized to kill tumor cells when exposed to NIR light.

  5. 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.

  6. Microwave Spectroscopy and Structure Determination of H_2S-MI (M=Cu,Ag,Au)

    NASA Astrophysics Data System (ADS)

    Medcraft, Chris; Legon, Anthony; Walker, Nick

    2016-06-01

    A series of hydrogen sulphide-metal iodide complexes (H_2S-MI, M=Cu, Ag and Au) have been measured via chirped pulse Fourier transform microwave spectroscopy between 7.5-18 GHz. The complexes were generated in a supersonic expansion via laser ablation of the metal and decomposition of CF_3I. Experimental structures were obtained by least squares fitting of structural parameters to the rotational constants of deuterium and metal (63Cu / 65Cu and 107Ag / 109Ag) isotopologues. Interestingly K-1=1 transitions were observed in the spectra containing D_2S, these were not observed in previous studies of similar molecules (H_2S-MCl). This allowed for the determination of an extra rotational constant and, consequently, extra structural information could be obtained. The structures are compared to high level coupled cluster theory calculations.

  7. Optical properties of Ag nanoparticle-polymer composite film based on two-dimensional Au nanoparticle array film

    PubMed Central

    2014-01-01

    The nanocomposite polyvinyl pyrrolidone (PVP) films containing Ag nanoparticles and Rhodamine 6G are prepared on the two-dimensional distinctive continuous ultrathin gold nanofilms. We investigate the optical properties and the fluorescence properties of silver nanoparticles-PVP polymer composite films influenced by Ag nanoparticles and Au nanoparticles. Absorption spectral analysis suggests that the prominently light absorption in Ag nanowire/PVP and Ag nanowire/PVP/Au film arises from the localized surface plasmon resonance of Ag nanowire and Au nanofilm. The enhanced fluorescence is observed in the presence of Ag nanowire and Au nanofilm, which is attributed to the excitation of surface plasmon polariton resonance of Ag nanowire and Au nanofilm. The gold nanofilm is proven to be very effective fluorescence resonance energy transfer donors. The fabricated novel structure, gold ultrathin continuous nanofilm, possesses high surface plasmon resonance properties and prominent fluorescence enhancement effect. Therefore, the ultrathin continuous gold nanofilm is an active substrate on nanoparticle-enhanced fluorescence. PMID:24685186

  8. Formation of a Pt-Decorated Au Nanoparticle Monolayer Floating on an Ionic Liquid by the Ionic Liquid/Metal Sputtering Method and Tunable Electrocatalytic Activities of the Resulting Monolayer.

    PubMed

    Sugioka, Daisuke; Kameyama, Tatsuya; Kuwabata, Susumu; Yamamoto, Takahisa; Torimoto, Tsukasa

    2016-05-01

    A novel strategy to prepare a bimetallic Au-Pt particle film was developed through sequential sputter deposition of Au and Pt on a room temperature ionic liquid (RTIL). Au sputter deposition onto an RTIL containing hydroxyl-functionalized cations produced a monolayer of Au particles 4.2 nm in size on the liquid surface. Subsequent Pt sputtering onto the original Au particle monolayer floating on the RTIL enabled decoration of individual Au particles with Pt metals, resulting in the formation of a bimetallic Au-Pt particle monolayer with a Pt-enriched particle surface. The particle size slightly increased to 4.8 nm with Pt deposition for 120 min. The shell layer of a bimetallic particle was composed of Au-Pt alloy, the composition of which was tunable by controlling the Pt sputter deposition time. The electrochemical surface area (ECSA) was determined by cyclic voltammetry of bimetallic Au-Pt particle monolayers transferred onto HOPG electrodes by a horizontal liftoff method. The Pt surface coverage, determined by ECSAs of Au and Pt, increased from 0 to 56 mol % with elapse of the Pt sputter deposition time up to 120 min. Thus-obtained Au-Pt particle films exhibited electrocatalytic activity for methanol oxidation reaction (MOR) superior to the activities of pure Au or Pt particles. Volcano-type dependence was observed between the MOR activity and Pt surface coverage on the particles. Maximum activity was obtained for Au-Pt particles with a Pt coverage of 49 mol %, being ca. 120 times higher than that of pure Pt particles. This method enables direct decoration of metal particles with different noble metal atoms, providing a novel strategy to develop highly efficient multinary particle catalysts. PMID:27074631

  9. Formation of a Pt-Decorated Au Nanoparticle Monolayer Floating on an Ionic Liquid by the Ionic Liquid/Metal Sputtering Method and Tunable Electrocatalytic Activities of the Resulting Monolayer.

    PubMed

    Sugioka, Daisuke; Kameyama, Tatsuya; Kuwabata, Susumu; Yamamoto, Takahisa; Torimoto, Tsukasa

    2016-05-01

    A novel strategy to prepare a bimetallic Au-Pt particle film was developed through sequential sputter deposition of Au and Pt on a room temperature ionic liquid (RTIL). Au sputter deposition onto an RTIL containing hydroxyl-functionalized cations produced a monolayer of Au particles 4.2 nm in size on the liquid surface. Subsequent Pt sputtering onto the original Au particle monolayer floating on the RTIL enabled decoration of individual Au particles with Pt metals, resulting in the formation of a bimetallic Au-Pt particle monolayer with a Pt-enriched particle surface. The particle size slightly increased to 4.8 nm with Pt deposition for 120 min. The shell layer of a bimetallic particle was composed of Au-Pt alloy, the composition of which was tunable by controlling the Pt sputter deposition time. The electrochemical surface area (ECSA) was determined by cyclic voltammetry of bimetallic Au-Pt particle monolayers transferred onto HOPG electrodes by a horizontal liftoff method. The Pt surface coverage, determined by ECSAs of Au and Pt, increased from 0 to 56 mol % with elapse of the Pt sputter deposition time up to 120 min. Thus-obtained Au-Pt particle films exhibited electrocatalytic activity for methanol oxidation reaction (MOR) superior to the activities of pure Au or Pt particles. Volcano-type dependence was observed between the MOR activity and Pt surface coverage on the particles. Maximum activity was obtained for Au-Pt particles with a Pt coverage of 49 mol %, being ca. 120 times higher than that of pure Pt particles. This method enables direct decoration of metal particles with different noble metal atoms, providing a novel strategy to develop highly efficient multinary particle catalysts.

  10. Scaling of pT distributions for p and p¯ produced in Au+Au collisions at sNN=200GeV

    NASA Astrophysics Data System (ADS)

    Zhang, W. C.; Zeng, Y.; Nie, W. X.; Zhu, L. L.; Yang, C. B.

    2007-10-01

    With the experimental data from STAR and PHENIX on the centrality dependence of the pT spectra of protons and antiprotons produced at midrapidity in Au+Au collisions at 200 GeV, we show that for protons and antiprotons there exists a scaling distribution independent of the colliding centrality. The scaling functions can also describe data from BRAHMS for both proton and antiproton spectra at y=2.2 and 3.2. The scaling behaviors are shown to be incompatible with the usual string fragmentation scenario for particle production.

  11. Formation of core-shell Au@Ag nanorods induced by catecholamines: A comparative study and an analytical application.

    PubMed

    Gorbunova, M V; Apyari, V V; Dmitrienko, S G; Garshev, A V

    2016-09-14

    Gold nanorods (AuNRs) stabilized by cetyltrimethylammonium bromide (CTAB) were synthesized and an interaction of catecholamines (CAs) with silver ions in the presence of the obtained AuNRs was studied. The reaction results into formation of core-shell Au@Ag nanorods (Au@AgNRs) and leads to a hypsochromic shift of the long-wave surface plasmon resonance (SPR) band in the absorption spectrum of AuNRs. The influence of a CA structure, excess of CTAB, interaction time, pH, concentration of AuNRs, silver ions and CAs on this interaction was studied. Based on correlation of the NRs spectral characteristics with the concentration of CAs, a method for spectrophotometric determination of dobutamine, epinephrine, norepinephrine and dopamine with detection limits 27, 18, 16 and 13 μg L(-1), respectively, has been developed. The method can be applied to the analysis of medicines. PMID:27566354

  12. Formation of core-shell Au@Ag nanorods induced by catecholamines: A comparative study and an analytical application.

    PubMed

    Gorbunova, M V; Apyari, V V; Dmitrienko, S G; Garshev, A V

    2016-09-14

    Gold nanorods (AuNRs) stabilized by cetyltrimethylammonium bromide (CTAB) were synthesized and an interaction of catecholamines (CAs) with silver ions in the presence of the obtained AuNRs was studied. The reaction results into formation of core-shell Au@Ag nanorods (Au@AgNRs) and leads to a hypsochromic shift of the long-wave surface plasmon resonance (SPR) band in the absorption spectrum of AuNRs. The influence of a CA structure, excess of CTAB, interaction time, pH, concentration of AuNRs, silver ions and CAs on this interaction was studied. Based on correlation of the NRs spectral characteristics with the concentration of CAs, a method for spectrophotometric determination of dobutamine, epinephrine, norepinephrine and dopamine with detection limits 27, 18, 16 and 13 μg L(-1), respectively, has been developed. The method can be applied to the analysis of medicines.

  13. All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures.

    PubMed

    Yang, Huayan; Wang, Yu; Huang, Huaqi; Gell, Lars; Lehtovaara, Lauri; Malola, Sami; Häkkinen, Hannu; Zheng, Nanfeng

    2013-01-01

    Noble metal nanoparticles stabilized by organic ligands are important for applications in assembly, site-specific bioconjugate labelling and sensing, drug delivery and medical therapy, molecular recognition and molecular electronics, and catalysis. Here we report crystal structures and theoretical analysis of three Ag44(SR)30 and three Au12Ag32(SR)30 intermetallic nanoclusters stabilized with fluorinated arylthiols (SR=SPhF, SPhF2 or SPhCF3). The nanocluster forms a Keplerate solid of concentric icosahedral and dodecahedral atom shells, protected by six Ag2(SR)5 units. Positive counterions in the crystal indicate a high negative charge of 4(-) per nanoparticle, and density functional theory calculations explain the stability as an 18-electron superatom shell closure in the metal core. Highly featured optical absorption spectra in the ultraviolet-visible region are analysed using time-dependent density functional perturbation theory. This work forms a basis for further understanding, engineering and controlling of stability as well as electronic and optical properties of these novel nanomaterials. PMID:24005600

  14. All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures.

    PubMed

    Yang, Huayan; Wang, Yu; Huang, Huaqi; Gell, Lars; Lehtovaara, Lauri; Malola, Sami; Häkkinen, Hannu; Zheng, Nanfeng

    2013-01-01

    Noble metal nanoparticles stabilized by organic ligands are important for applications in assembly, site-specific bioconjugate labelling and sensing, drug delivery and medical therapy, molecular recognition and molecular electronics, and catalysis. Here we report crystal structures and theoretical analysis of three Ag44(SR)30 and three Au12Ag32(SR)30 intermetallic nanoclusters stabilized with fluorinated arylthiols (SR=SPhF, SPhF2 or SPhCF3). The nanocluster forms a Keplerate solid of concentric icosahedral and dodecahedral atom shells, protected by six Ag2(SR)5 units. Positive counterions in the crystal indicate a high negative charge of 4(-) per nanoparticle, and density functional theory calculations explain the stability as an 18-electron superatom shell closure in the metal core. Highly featured optical absorption spectra in the ultraviolet-visible region are analysed using time-dependent density functional perturbation theory. This work forms a basis for further understanding, engineering and controlling of stability as well as electronic and optical properties of these novel nanomaterials.

  15. Determination of Anthracene on Ag-Au Alloy Nanoparticles/Overoxidized-Polypyrrole Composite Modified Glassy Carbon Electrodes

    PubMed Central

    Mailu, Stephen N.; Waryo, Tesfaye T.; Ndangili, Peter M.; Ngece, Fanelwa R.; Baleg, Abd A.; Baker, Priscilla G.; Iwuoha, Emmanuel I.

    2010-01-01

    A novel electrochemical sensor for the detection of anthracene was prepared by modifying a glassy carbon electrode (GCE) with over-oxidized polypyrrole (PPyox) and Ag-Au (1:3) bimetallic nanoparticles (Ag-AuNPs). The composite electrode (PPyox/Ag-AuNPs/GCE) was prepared by potentiodynamic polymerization of pyrrole on GCE followed by its overoxidation in 0.1 M NaOH. Ag-Au bimetallic nanoparticles were chemically prepared by the reduction of AgNO3 and HAuCl4 using C6H5O7Na3 as the reducing agent as well as the capping agent and then immobilized on the surface of the PPyox/GCE. The nanoparticles were characterized by UV-visible spectroscopy technique which confirmed the homogeneous formation of the bimetallic alloy nanoparticles. Transmission electron microscopy showed that the synthesized bimetallic nanoparticles were in the range of 20–50 nm. The electrochemical behaviour of anthracene at the PPyox/Ag-AuNPs/GCE with Ag: Au atomic ratio 25:75 (1:3) exhibited a higher electrocatalytic effect compared to that observed when GCE was modified with each constituent of the composite (i.e., PPyox, Ag-AuNPs) and bare GCE. A linear relationship between anodic current and anthracene concentration was attained over the range of 3.0 × 10−6 to 3.56 × 10−4 M with a detection limit of 1.69 × 10−7 M. The proposed method was simple, less time consuming and showed a high sensitivity. PMID:22163419

  16. 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.

  17. Cooperative effect of Au and Pt inside TiO2 matrix for optical hydrogen detection at room temperature using surface plasmon spectroscopy.

    PubMed

    Della Gaspera, Enrico; Bersani, Marco; Mattei, Giovanni; Nguyen, Tich-Lam; Mulvaney, Paul; Martucci, Alessandro

    2012-09-28

    Metal (Au, Pt, Au@Pt) and metal oxide (TiO(2)) nanoparticles are synthesized with colloidal techniques and subsequently used as nanocrystal inks for thin films deposition. The optical properties of Au colloids are strongly influenced by both Pt and TiO(2) interfaces: while platinum causes a damping and a blue-shift of the Au Surface Plasmon Resonance (SPR) peak as a consequence of the metal-metal interaction, the anatase matrix is responsible for the red shift of the plasmon frequency due to the increased refractive index. By a careful tailoring of the nanoparticles synthesis, high quality, scattering-free films composed of an anatase matrix embedding Au, Pt and Au@Pt colloids are deposited at room temperature and stabilized at 200 °C. Room temperature exposure of these films to hydrogen leads to optical changes. In the case of Au, there is a slow blue shift of the surface plasmon band, resulting in a wavelength dependent optical response. Much faster but smaller optical changes occur for titania films containing Pt. When both metals are present, the optical response of the gold is much faster. This is attributed to spillover of hydrogen atoms from platinum to gold. This synergy enables enhanced optical sensing of hydrogen at room temperature by combining the low temperature dissociation of H(2) on Pt with the intensive surface plasmon response of the gold nanocrystals. PMID:22907103

  18. Cooperative effect of Au and Pt inside TiO2 matrix for optical hydrogen detection at room temperature using surface plasmon spectroscopy.

    PubMed

    Della Gaspera, Enrico; Bersani, Marco; Mattei, Giovanni; Nguyen, Tich-Lam; Mulvaney, Paul; Martucci, Alessandro

    2012-09-28

    Metal (Au, Pt, Au@Pt) and metal oxide (TiO(2)) nanoparticles are synthesized with colloidal techniques and subsequently used as nanocrystal inks for thin films deposition. The optical properties of Au colloids are strongly influenced by both Pt and TiO(2) interfaces: while platinum causes a damping and a blue-shift of the Au Surface Plasmon Resonance (SPR) peak as a consequence of the metal-metal interaction, the anatase matrix is responsible for the red shift of the plasmon frequency due to the increased refractive index. By a careful tailoring of the nanoparticles synthesis, high quality, scattering-free films composed of an anatase matrix embedding Au, Pt and Au@Pt colloids are deposited at room temperature and stabilized at 200 °C. Room temperature exposure of these films to hydrogen leads to optical changes. In the case of Au, there is a slow blue shift of the surface plasmon band, resulting in a wavelength dependent optical response. Much faster but smaller optical changes occur for titania films containing Pt. When both metals are present, the optical response of the gold is much faster. This is attributed to spillover of hydrogen atoms from platinum to gold. This synergy enables enhanced optical sensing of hydrogen at room temperature by combining the low temperature dissociation of H(2) on Pt with the intensive surface plasmon response of the gold nanocrystals.

  19. Phonons, nature of bonding, and their relation to anomalous thermal expansion behavior of M2O (M = Au, Ag, Cu)

    NASA Astrophysics Data System (ADS)

    Gupta, M. K.; Mittal, R.; Chaplot, S. L.; Rols, S.

    2014-03-01

    We report a comparative study of the dynamics of Cu2O, Ag2O, and Au2O (i.e., M2O with M = Au, Ag, and Cu) using first principle calculations based on the density functional theory. Here, for the first time, we show that the nature of chemical bonding and open space in the unit cell are directly related to the magnitude of thermal expansion coefficient. A good match between the calculated phonon density of states and that derived from inelastic neutron scattering measurements is obtained for Cu2O and Ag2O. The calculated thermal expansions of Ag2O and Cu2O are negative, in agreement with available experimental data, while it is found to be positive for Au2O. We identify the low energy phonon modes responsible for this anomalous thermal expansion. We further calculate the charge density in the three compounds and find that the magnitude of the ionic character of the Ag2O, Cu2O, and Au2O crystals is in decreasing order, with an Au-O bond of covalent nature strongly rigidifying the Au4O tetrahedral units. The nature of the chemical bonding is also found to be an important ingredient to understand the large shift of the phonon frequencies of these solids with pressure and temperature. In particular, the quartic component of the anharmonic term in the crystal potential is able to account for the temperature dependence of the phonon modes.

  20. Pt L3,2-edge whiteline anomaly and its implications for the chemical behaviour of Pt 5d5/2 and 5d3/2 electronic states - a study of Pt-Au nanowires and nanoparticles

    SciTech Connect

    Sham, T. K.; Ward, M. J.; Murphy, M. W.; Liu, L. J.; Han, W. Q.

    2013-05-29

    We report the L3,2-edge whiteline anomaly observed in PtAu nanowire, PtAu and Pt nanoparticles deposited on Si nanowire, and their comparison with that of Pt metal. It is found that charge redistribution upon the formation of these materials can indeed be tracked with the L3,2 whiteline intensity. The implications of these findings are discussed.

  1. Lithogeochemistry and fluid inclusions of an Au-Ag vein deposit in a granodiorite intrusive

    SciTech Connect

    Hahn, R.; Ikramuddin, M.

    1985-01-01

    Forty-eight samples of altered and unaltered rocks and quartz veins from the Acme mine in northeast Washington, an Au-Ag vein deposit in a granodiorite intrusive, have been analyzed for SiO/sub 2/, Al/sub 2/O/sub 3/, Fe/sub 2/O/sub 3/, Feo, MgO, CaO, Na/sub 2/O, K/sub 2/O, TiO/sub 2/, MnO, P/sub 2/O/sub 5/, H/sub 2/O, CO/sub 2/, Ag, Au, Ba, Cu, Pb, Rb, Sr, Tl, and Zn. A comparison of major and trace elements shows that the altered granodiorite is enriched in SiO/sub 2/, Fe/sub 2/O/sub 3/, K/sub 2/O, Ag, Au, Ba, Cu, Pb, Rb, Tl, and Zn and depleted in Al/sub 2/O/sub 3/, FeO, MgO, CaO, Na/sub 2/O, TiO/sub 2/, MnO, P/sub 2/O/sub 5/, and Sr. The average contents of Au in unaltered and altered granodiorite and quartz veins are 9 ppb. 270 ppb and 1020 ppb respectively. The average Ba/Tl ratio in the altered samples decrease and average Rb/Sr and Tl/Sr ratios increase. K, Rb, and Tl are enriched in the altered granodiorite by factors of 1.5, 1.6, and 1.4 respectively. Tl is not enriched relative to Rb and K in the altered samples due to the high temperature of the deposit. The Ba/Tl, K/Tl and K/Rb ratios do not show complete separation of altered from unaltered samples. However, the Ba/Tl and K/Tl ratios in the quartz vein are significantly lower than the unaltered and altered granodiorite. This is due to the enrichment of Tl over K and Rb in the quartz veins. The Rb/Sr and Tl/Sr ratios are higher in the altered granodiorite and quartz veins compared to unaltered samples. The enrichment of Tl and presence of low Ba/Tl and high Rb/Sr and Tl/Sr ratios in a granodiorite indicate that the rocks are hydrothermally altered and represent a possible Au-Ag target.

  2. Analysis of d/p ratio in Au+Au collisions from the E866 experiment at the AGS

    SciTech Connect

    Shea, Y.; Garcia-Solis, E.J.; Stanskas, P.J.

    1996-02-01

    High energy nucleus-nucleus collisions are a great interest as a means of creating a new state of matter. The transition of nuclear matter to quark matter is expected to result in a strongly interacting region that lives for a long time and expands to a large volume. In order to understand the properties of the collision region, it is important to gather information experimentally on the lifetime and thermodynamic attributes such as temperature, volume, density, and entropy of the collision region. Deuteron production by phase space coalescence is particularly interesting because it can be used as a probe in studying the space-time structure of the heavy ion collisions. In the hot and dense participant region, a proton and a neutron coalesce when their relative momentum is small. The deuteron density in momentum space is proportional to the proton density squared in momentum space at equal momenta per nucleon, assuming proton and neutron density to be identical. The motivation here is to study the properties of the coalesced deuterons formed in the participant region of Au-Au collisions at 11.6 GeV/c. The d/p ratio as a function of centrality is studied in hopes of gaining information about any change in the size of the participant zone which could lead to the effort of searching for the Quark-Gluon-Plasma at the AGS. The results shown here is very preliminary and the work is in progress.

  3. Pseudorapidity and pt dependence of identified-particle azimuthal flow for √sNN=200 GeV Au+Au and Cu+Cu collisions

    NASA Astrophysics Data System (ADS)

    Zhukova, Victoria

    2008-10-01

    The observation of a strong azimuthal flow signature at RHIC suggests rapid system equilibration leading to an almost perfect fluid state. The longitudinal extent of the flow behavior depends on the formation dynamics for this state and can be studied by measuring the pseudorapidity dependence of the second Fourier component (v2) of the azimuthal angular distribution. We report on a measurement of identified-particle v2 as a function of pt (0.5-2.0 GeV/c), centrality (0-50%), and pseudorapidity (0<=η<3.2) for √sNN = 200 GeV Au+Au and Cu+Cu collisions. The results are obtained using the BRAHMS spectrometers for particle identification (π, K, p) and the BRAHMS global detectors to determine the corresponding reaction-plane angles. Preliminary results for the Au+Au system have been reported earlier. Here we compare the final Au+Au results to new results obtained for the Cu+Cu system.

  4. Physico-chemical and antimicrobial properties of co-sputtered Ag Au/PTFE nanocomposite coatings

    NASA Astrophysics Data System (ADS)

    Zaporojtchenko, V.; Podschun, R.; Schürmann, U.; Kulkarni, A.; Faupel, F.

    2006-10-01

    In this work, we used co-sputtering of noble metals together with polytetrafluorethylene (PTFE) as a method for producing antibacterial metal/polymer nanocomposite coatings, where the precious metals are only incorporated in a thin surface layer. Moreover, they are finely dispersed as nanoparticles, thus saving additional material and providing a very large effective surface for metal ion release. Nanocomposite films with thickness between 100 and 300 nm were prepared with a wide range of metal filling between 10 and 40%. The antimicrobial effect of the nanocomposite coatings was evaluated by means of two different assays. The bactericidal activity due to silver release from the surface was determined by a modification of conventional disc diffusion methods. Inhibition of bacterial growth on the coated surface was investigated through a modified proliferation assay. Staphylococcus aureus and S. epidermidis were used as test bacteria, as these species commonly cause infections associated with medical polymer devices. The antibacterial efficiency of the coatings against different bacteria was demonstrated at extremely small noble metal consumption: Au: ~1 mg m-2 and Ag: ~0.1 g m-2. The maximum ability for having an antibacterial effect was shown by the Ag-Au/PTFE nanocomposite, followed by the Ag/PTFE nanocomposite.

  5. Highly porous ZnS microspheres for superior photoactivity after Au and Pt deposition and thermal treatment

    SciTech Connect

    Singla, Shilpa; Pal, Bonamali

    2013-11-15

    Graphical abstract: Highly porous ZnS microsphere of size 2–5 μm having large surface area ca. 173.14 m{sup 2} g{sup −1} exhibits superior photocatalytic activity for the oxidation of 4-nitrophenol under UV light irradiation. The rate of photooxidation has been significantly improved by Au and Pt deposition and after sintering, respectively, due to rapid electron acceptance by metal from photoexcited ZnS and growth of crystalline ZnS phase. - Highlights: • Photoactive ZnS microsphere of size 2–5 μm was prepared by hydrothermal route. • Highly porous cubic spherical ZnS crystals possess a large surface area, 173 m{sup 2} g{sup −1}. • 1 wt% Au and Pt photodeposition highly quenched the photoluminescence at 437 nm. • Sintering and metal loading notably improve the photooxidation rate of 4-nitrophenol. • Pt co-catalyst always exhibits superior photoactivity of ZnS microsphere than Au. - Abstract: This work highlights the enhanced photocatalytic activity of porous ZnS microspheres after Au and Pt deposition and heat treatment at 500 °C for 2 h. Microporous ZnS particles of size 2–5 μm with large surface area 173.14 m{sup 2} g{sup −1} and pore volume 0.0212 cm{sup 3} g{sup −1} were prepared by refluxing under an alkaline medium. Photoluminescence of ZnS at 437 nm attributed to sulfur or zinc vacancies were quenched to 30% and 49%, respectively, after 1 wt% Au and Pt loading. SEM images revealed that each ZnS microparticle consist of several smaller ZnS spheres of size 2.13 nm as calculated by Scherrer's equation. The rate of photooxidation of 4-nitrophenol (10 μM) under UV (125 W Hg arc–10.4 mW/cm{sup 2}) irradiation has been significantly improved by Au and Pt deposition followed by sintering due to better electron capturing capacity of deposited metals and growth of crystalline ZnS phase with less surface defects.

  6. Luminescent Di and Polynuclear Organometallic Gold(I)-M (Au2, {Au2Ag}n and {Au2Cu}n) Compounds Containing Bidentate Phosphanes as Active Antimicrobial Agents

    PubMed Central

    Frik, Malgorzata; Jiménez, Josefina; Gracia, Ismael; Falvello, Larry R.; Abi-Habib, Sarya; Suriel, Karina; Muth, Theodore R.

    2012-01-01

    The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au2(mes)2(μ-LL)] (LL = dppe: 1,2-Bis(di-phenylphosphano)ethane 1a, and water-soluble dppy: 1,2-Bis(di-3-pyridylphosphano)ethane 1b) with Ag+ and Cu+ lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au2M(μ-mes)2(μ-LL)]A (M = Ag, A = ClO4−, L-L = dppe 2a, dppy 2b; M = Ag, A = SO3CF3−, L-L = dppe 3a, dppy 3b; M = Cu, A = PF6−, L-L = dppe 4a, dppy 4b). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au2(mes)2(μ-dppy)] 1b and [Au2Ag(μ-mes)2(μ-dppe)]SO3CF3 3a were determined by a single-crystal X-ray diffraction study. 3a in solid state is not a cyclic trinuclear Au2Ag derivative but it gives an open polymeric structure instead, with the {Au2(μ-dppe)} fragments “linked” by Ag(μ-mes)2 units. The very short distances of 2.7559(6) Å (Au-Ag) and 2.9229(8) Å (Au-Au) are indicative of gold-silver (metallophillic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self-aggregation of [Au2M(μ-mes)2(μ-LL)]+ units (M= Ag or Cu; LL= dppe or dppy) into an extended chain structure, through Au-Au and/or Au-M metallophylic interactions, as that observed for 3a. In solid state the heterometallic Au2M complexes with dppe (2a–4a) show a shift of emission maxima (from ca. 430 to the range of 520–540 nm) as compared to the parent dinuclear organometallic product 1a while the complexes with dppy (2b–4b) display a more moderate shift (505 for 1b to a max of 563 nm for 4b). More importantly, compound [Au2Ag(μ-mes)2(μ-dppy)]ClO4 2b resulted luminescent in diluted DMSO solution

  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. The IP6 micelle-stabilized small Ag cluster for synthesizing Ag-Au alloy nanoparticles and the tunable surface plasmon resonance effect

    NASA Astrophysics Data System (ADS)

    Wang, Na; Wen, Ying; Wang, Yao; Zhang, Rui; Chen, Xiyao; Ling, Bo; Huan, Shuangyan; Yang, Haifeng

    2012-04-01

    The stable small Ag seeds (size in diameter < 10 nm) were obtained in the presence of inositol hexakisphosphoric (IP6) micelles. Then Ag-Au bimetallic nanoparticles were synthesized through a replacement reaction with the rapid interdiffusion process between such small Ag seeds in nanoclusters and HAuCl4. Adjusting the dosage of HAuCl4 resulted in different products, which possessed unique surface plasmon resonances (SPR). The morphologies of the as-made nanoparticles were observed using transmission electron microscopy and field emission scanning electron microscopy and their compositions were determined by energy-dispersive x-ray spectroscopy. Among them, the Ag-Au alloy nanoparticles with the cauliflower-like structure had a suitable SPR for highly sensitive Raman detection application as a surface-enhanced Raman scattering (SERS) substrate with a long-term stability of six months.

  9. The alloying effect and AgCl-directing growth for synthesizing a trimetallic nanoring with improved SERS

    NASA Astrophysics Data System (ADS)

    Han, Shuhua; Zhou, Guangju; Fu, Yunzhi; Ma, Ying; Xu, Li; Zou, Chao; Chen, Wei; Yang, Yun; Huang, Shaoming

    2015-12-01

    We report the synthesis of high quality trimetallic Au/Ag/Pt nanorings (TAAPNs) by using Au/Ag alloy decahedra (AAAD) as templates. The alloying effect and AgCl-directing growth have been investigated in detail during the formation of TAAPN. It was found that the doping of Ag in AAAD changes the surrounding environment of Au atoms and decreases the oxidization reduction potential (ORP) of [AuCl2]-/Au because of the alloying effect, resulting in the dissolved O2 molecules that serve as an effective etchant for oxidizing Au to Au(i). Ascorbic acid (AA) and chloroplatinic acid (H2PtCl6) are weak acids which can accelerate the etching by increasing the concentration of H+. The AgCl selectively absorbs on {100} of the decahedra and induces the preferential deposition of H2PtCl6 here via their complexing interaction. AA reduces Pt(iv) and Ag(i) to atoms which grow on {100} facets. The formed Pt/Ag layer changes the etching direction from along [100] to [111] and generates the TAAPN. Besides, it has been noted that the TAAPNs exhibit good Surface Enhanced Raman Scattering (SERS) performance.We report the synthesis of high quality trimetallic Au/Ag/Pt nanorings (TAAPNs) by using Au/Ag alloy decahedra (AAAD) as templates. The alloying effect and AgCl-directing growth have been investigated in detail during the formation of TAAPN. It was found that the doping of Ag in AAAD changes the surrounding environment of Au atoms and decreases the oxidization reduction potential (ORP) of [AuCl2]-/Au because of the alloying effect, resulting in the dissolved O2 molecules that serve as an effective etchant for oxidizing Au to Au(i). Ascorbic acid (AA) and chloroplatinic acid (H2PtCl6) are weak acids which can accelerate the etching by increasing the concentration of H+. The AgCl selectively absorbs on {100} of the decahedra and induces the preferential deposition of H2PtCl6 here via their complexing interaction. AA reduces Pt(iv) and Ag(i) to atoms which grow on {100} facets. The formed

  10. Spontaneous formation of Au-Pt alloyed nanoparticles using pure nano-counterparts as starters: a ligand and size dependent process

    NASA Astrophysics Data System (ADS)

    Usón, Laura; Sebastian, Victor; Mayoral, Alvaro; Hueso, Jose L.; Eguizabal, Adela; Arruebo, Manuel; Santamaria, Jesus

    2015-05-01

    In this work we investigate the formation of PtAu monodisperse alloyed nanoparticles by ageing pure metallic Au and Pt small nanoparticles (sNPs), nanoparticle size <5 nm, under certain conditions. We demonstrate that those bimetallic entities can be obtained by controlling the size of the initial metallic sNPs separately prepared and by selecting their appropriate capping agents. The formation of this spontaneous phenomenon was studied using HR-STEM, EDS, ionic conductivity, UV-Vis spectroscopy and cyclic voltammetry. Depending on the type of capping agent used and the size of the initial Au sNPs, three different materials were obtained: (i) AuPt bimetallic sNPs showing a surface rich in Au atoms, (ii) segregated Au and Pt sNPs and (iii) a mixture of bimetallic nanoparticles as well as Pt sNPs and Au NPs. Surface segregation energies and the nature of the reaction environment are the driving forces to direct the distribution of atoms in the bimetallic sNPs. PtAu alloyed nanoparticles were obtained after 150 h of reaction at room temperature if a weak capping agent was used for the stabilization of the nanoparticles. It was also found that Au atoms diffuse towards Pt sNPs, producing a surface enriched in Au atoms. This study shows that even pure nanoparticles are prone to be modified by the surrounding nanoparticles to give rise to new nanomaterials if atomic diffusion is feasible.In this work we investigate the formation of PtAu monodisperse alloyed nanoparticles by ageing pure metallic Au and Pt small nanoparticles (sNPs), nanoparticle size <5 nm, under certain conditions. We demonstrate that those bimetallic entities can be obtained by controlling the size of the initial metallic sNPs separately prepared and by selecting their appropriate capping agents. The formation of this spontaneous phenomenon was studied using HR-STEM, EDS, ionic conductivity, UV-Vis spectroscopy and cyclic voltammetry. Depending on the type of capping agent used and the size of the

  11. Preparation of Ag/Au bimetallic nanostructures and their application in surface-enhanced fluorescence.

    PubMed

    Dong, Jun; Ye, Yanyan; Zhang, Wenhui; Ren, Zebin; Huo, Yiping; Zheng, Hairong

    2015-11-01

    An effective substrate for surface-enhanced fluorescence, which consists of cluster Ag/Au bimetallic nanostructures on a copper surface, was synthesized via a multi-stage galvanic replacement reaction of a Ag cluster in a chlorauric acid (HAuCl4) solution at room temperature. The fabricated silver/gold bimetallic cluster were found to yield large surface-enhanced fluorescence (SEF) enhancement factors for rhodamine 6G probe molecules deposited on the substrate, and also the fluorescence efficiency is critically dependent on the period of nanostructure growth. With the help of proper control reaction conditions, such as the reaction time, and concentration of reaction solutions, the maximum fluorescence enhanced effect was obtained. Therefore, the bimetallic nanostructure substrate also can be adapted to studies in SEF, which will expand the application of SEF.

  12. Hyperspectral reflected light microscopy of plasmonic Au/Ag alloy nanoparticles incubated as multiplex chromatic biomarkers with cancer cells.

    PubMed

    Patskovsky, Sergiy; Bergeron, Eric; Rioux, David; Simard, Mikaël; Meunier, Michel

    2014-10-21

    A hyperspectral microscopy system based on a reflected light method for plasmonic nanoparticle (NP) imaging was designed and compared with a conventional darkfield method for spatial localization and spectroscopic identification of single Au, Ag and Au/Ag alloy NPs incubated with fixed human cancer cell preparations. A new synthesis protocol based on co-reduction of Au and Ag salts combined with the seeded growth technique was used for the fabrication of monodispersed alloy NPs with sizes ranging from 30 to 100 nm in diameter. We validated theoretically and experimentally the performance of 60 nm Au, Ag and Au/Ag (50 : 50) NPs as multiplexed biological chromatic markers for biomedical diagnostics and optical biosensing. The advantages of the proposed reflected light microscopy method are presented for NP imaging in a complex and highly diffusing medium such as a cellular environment. The obtained information is essential for the development of a high throughput, selective and efficient strategy for cancer detection and treatment. PMID:25133743

  13. Structure and diffusion of small Ag and Au clusters on the regular MgO (100) surface

    NASA Astrophysics Data System (ADS)

    Barcaro, G.; Fortunelli, A.

    2007-02-01

    The lowest energy structures and the diffusion energy barriers of small MN (N = 1 4) Ag and Au clusters absorbed on the regular MgO (100) surface are investigated via density-functional (DF) calculations, using two different xc-functionals (PBE and LDA). In agreement with previous work, it is found that the lowest-energy structures of Ag and Au clusters in this size-range exhibit a strong 'metal-on-top' effect, by which the clusters are absorbed atop oxygen ions in a linear (dimer) or planar (trimer and tetramer) configuration perpendicular to the surface. The corresponding diffusion mechanisms range from monomer hopping, to dimer leapfrog (Ag2) or hopping (Au2), trimer walking, tetramer walking (Ag4) or rocking and rolling (Au4), exhibiting interesting differences between Ag and Au. An analysis of the corresponding energy barriers shows that trimers can diffuse at least as fast as monomers, while tetramers and (especially in the case of gold) dimers present somewhat higher barriers, but are anyway expected to be mobile on the surface at the temperatures of molecular beam epitaxy (MBE) experiments. The calculated PBE diffusion energy barriers compare reasonably well with the values extracted from the analysis of recent MBE experimental data, with the LDA predicting slightly higher barriers in the case of gold.

  14. Synthesis of (Au)Ag core-shell nanocomposite in the water- ethanol mixture and its optical properties

    NASA Astrophysics Data System (ADS)

    Abakshonok, A. V.; Panarin, A. Yu; Agabekov, V. E.; Eryomin, A. N.; Terekhov, S. N.

    2014-08-01

    The technique of synthesis of (Au)Ag core-shell bimetallic nanocomposite was developed. Gold seed nanoparticles (NPs) were obtained by HAuCl4 reduction with sodium citrate at ultrasonic treatment during 3 hours in a mixture of water - ethanol (1:1). Then, the surface of gold NPs was modified by silver. In the presence of polyvinylpyrrolidone (PVP) K30 (Mw ~ 24000) and K90 (Mw ~ 360000) the coreshell (Au)Ag NPs of spherical shape were formed. They are characterized by aggregate stability and well-defined absorption maximum at 400-514 nm. Composite (Au)Ag, prepared in the solution without a polymer or in the presence of carboxymethylcellulose (CMC), sodium polystyrene sulfonate (PSS), dextran T100 and T500, had a broad band plasmon resonance in the whole range of visible spectrum. The ability to use the (Au)Ag core-shell nanoparticles in absorption nanospectroscopy based on the phenomenon of plasmon resonance energy transfer (PRET) was evaluated. In the presence of 0,1-2,0 μM of water-soluble cationic Cu (II) -5,10,15,20-tetrakis (4-N-methyl pyridinium) porphyrin (CuTMPyP4) distinct dips due to plasmon quenching matched the absorption maximum of CuTMPyP4 were detected in the resonant scattering spectrum of (Au)Ag solution.

  15. A general and high-yield galvanic displacement approach to Au-M (M = Au, Pd, and Pt) core-shell nanostructures with porous shells and enhanced electrocatalytic performances.

    PubMed

    Kuai, Long; Geng, Baoyou; Wang, Shaozhen; Sang, Yan

    2012-07-23

    In this work, we utilize the galvanic displacement synthesis and make it a general and efficient method for the preparation of Au-M (M = Au, Pd, and Pt) core-shell nanostructures with porous shells, which consist of multilayer nanoparticles. The method is generally applicable to the preparation of Au-Au, Au-Pd, and Au-Pt core-shell nanostructures with typical porous shells. Moreover, the Au-Au isomeric core-shell nanostructure is reported for the first time. The lower oxidation states of Au(I), Pd(II), and Pt(II) are supposed to contribute to the formation of porous core-shell nanostructures instead of yolk-shell nanostructures. The electrocatalytic ethanol oxidation and oxygen reduction reaction (ORR) performance of porous Au-Pd core-shell nanostructures are assessed as a typical example for the investigation of the advantages of the obtained core-shell nanostructures. As expected, the Au-Pd core-shell nanostructure indeed exhibits a significantly reduced overpotential (the peak potential is shifted in the positive direction by 44 mV and 32 mV), a much improved CO tolerance (I(f)/I(b) is 3.6 and 1.63 times higher), and an enhanced catalytic stability in comparison with Pd nanoparticles and Pt/C catalysts. Thus, porous Au-M (M = Au, Pd, and Pt) core-shell nanostructures may provide many opportunities in the fields of organic catalysis, direct alcohol fuel cells, surface-enhanced Raman scattering, and so forth.

  16. Holey Au-Ag alloy nanoplates with built-in hotspots for surface-enhanced Raman scattering.

    PubMed

    Wei, Xinyu; Fan, Qikui; Liu, Hongpo; Bai, Yaocai; Zhang, Lei; Zheng, Haoquan; Yin, Yadong; Gao, Chuanbo

    2016-08-25

    Plasmonic noble metal nanocrystals with interior nanogaps have attracted great attention in surface-enhanced Raman scattering (SERS) applications due to the presence of built-in hotspots. Herein, we report a synthesis route to holey Au-Ag alloy nanoplates by controlled galvanic replacement with Ag nanoplates as the sacrificial template, a sulfite-coordinated Au(i) salt as the Au source, and polyvinylpyrrolidone (PVP) as the capping agent. PVP helps regulate the anisotropic growth of nanopores on the Ag nanoplates to afford a highly holey nanostructure, and the monovalent Au(i) salt plays a critical role in stabilizing these holey nanoplates by rapidly enriching Au in the alloy nanostructures. Numerical simulations and experimental results suggest that these holey Au-Ag alloy nanoplates possess enormous internal hotspots for high sensitivity in the SERS analysis, and high stability for excellent reliability of the analysis under many harsh conditions. We believe that this strategy is potentially applicable to the synthesis of many other types of plasmonic nanostructures with inherent nanogaps for many sensing and imaging applications. PMID:27524663

  17. Localized surface plasmon resonance-based hybrid Au-Ag nanoparticles for detection of Staphylococcus aureus enterotoxin B

    NASA Astrophysics Data System (ADS)

    Zhu, Shaoli; Du, ChunLei; Fu, Yongqi

    2009-09-01

    A triangular hybrid Au-Ag nanoparticles array was proposed for the purpose of biosensing in this paper. Constructing the hybrid nanoparticles, an Au thin film is capped on the Ag nanoparticles which are attached on glass substrate. The hybrid nanoparticles array was designed by means of finite-difference and time-domain (FDTD) algorithm-based computational numerical calculation and optimization. Sensitivity of refractive index of the hybrid nanoparticles array was obtained by the computational calculation and experimental detection. Moreover, the hybrid nanoparticles array can prevent oxidation of the pure Ag nanoparticles from atmosphere environment because the Au protective layer was deposited on top of the Ag nanoparticles so as to isolate the Ag particles from the atmosphere. We presented a novel surface covalent link method between the localized surface plasmon resonance (LSPR) effect-based biosensors with hybrid nanoparticles array and the detected target molecules. The generated surface plasmon wave from the array carries the biological interaction message into the corresponding spectra. Staphylococcus aureus enterotoxin B (SEB), a small protein toxin was directly detected at nanogramme per milliliter level using the triangular hybrid Au-Ag nanoparticles. Hence one more option for the SEB detection is provided by this way.

  18. Magnetic properties of self-organized L1 0 FePtAg nanoparticle arrays

    NASA Astrophysics Data System (ADS)

    Wang, S.; Kang, S. S.; Nikles, D. E.; Harrell, J. W.; Wu, X. W.

    2003-10-01

    The magnetic properties of chemically synthesized high anisotropy L1 0 [Fe 49Pt 51] 88Ag 12 nanoparticle arrays have been studied as a function of annealing temperature. Particles were prepared by the simultaneous polyol reduction of platinum acetylacetonate and silver acetate and the thermal decomposition of iron carbonyl, yielding monodispersed particles of diameter ˜3.5 nm. Addition of Ag lowers the ordering temperature of self-assembled arrays by ˜150°C. After annealing at Ta=500°C for 30 min in an Ar/H 2 atmosphere, the coercivity was 13,800 Oe. TEM and delta- M measurements indicate weak particle aggregation up to Ta=400°C, with evidence of sintering at higher temperatures. Large ratios of remanent to hysteresis coercivity indicate a large distribution in anisotropy energies. Anomalously large thermal stability constants, KV/ kBT, and switching volumes were measured, even in samples with very little evidence of sintering. Zero field viscosity versus remanence curves show evidence of exchange interactions.

  19. Heteroepitaxial growth of Pt and Au thin films on MgO single crystals by bias-assisted sputtering.

    PubMed

    Tolstova, Yulia; Omelchenko, Stefan T; Shing, Amanda M; Atwater, Harry A

    2016-03-17

    The crystallographic orientation of a metal affects its surface energy and structure, and has profound implications for surface chemical reactions and interface engineering, which are important in areas ranging from optoelectronic device fabrication to catalysis. However, it can be very difficult and expensive to manufacture, orient, and cut single crystal metals along different crystallographic orientations, especially in the case of precious metals. One approach is to grow thin metal films epitaxially on dielectric substrates. In this work, we report on growth of Pt and Au films on MgO single crystal substrates of (100) and (110) surface orientation for use as epitaxial templates for thin film photovoltaic devices. We develop bias-assisted sputtering for deposition of oriented Pt and Au films with sub-nanometer roughness. We show that biasing the substrate decreases the substrate temperature necessary to achieve epitaxial orientation, with temperature reduction from 600 to 350 °C for Au, and from 750 to 550 °C for Pt, without use of transition metal seed layers. In addition, this temperature can be further reduced by reducing the growth rate. Biased deposition with varying substrate bias power and working pressure also enables control of the film morphology and surface roughness.

  20. Heteroepitaxial growth of Pt and Au thin films on MgO single crystals by bias-assisted sputtering

    DOE PAGES

    Tolstova, Yulia; Omelchenko, Stefan T.; Shing, Amanda M.; Atwater, Harry A.

    2016-03-17

    The crystallographic orientation of a metal affects its surface energy and structure, and has profound implications for surface chemical reactions and interface engineering, which are important in areas ranging from optoelectronic device fabrication to catalysis. However, it can be very difficult and expensive to manufacture, orient, and cut single crystal metals along different crystallographic orientations, especially in the case of precious metals. One approach is to grow thin metal films epitaxially on dielectric substrates. In this work, we report on growth of Pt and Au films on MgO single crystal substrates of (100) and (110) surface orientation for use asmore » epitaxial templates for thin film photovoltaic devices. We develop bias-assisted sputtering for deposition of oriented Pt and Au films with sub-nanometer roughness. We show that biasing the substrate decreases the substrate temperature necessary to achieve epitaxial orientation, with temperature reduction from 600 to 350 °C for Au, and from 750 to 550 °C for Pt, without use of transition metal seed layers. Additionally, this temperature can be further reduced by reducing the growth rate. Biased deposition with varying substrate bias power and working pressure also enables control of the film morphology and surface roughness.« less

  1. Electrical parameters and series resistance analysis of Au/Y/p-InP/Pt Schottky barrier diode at room temperature

    NASA Astrophysics Data System (ADS)

    Rao, L. Dasaradha; Reddy, V. Rajagopal

    2016-05-01

    The current-voltage (I-V) characteristics of Au/Y/p-InP/Pt Schottky barrier diode (SBD) are analyzed at room temperature. The Au/Y/p-InP/Pt SBD shows a good rectification behavior. The ideality factor (n), barrier height (Φb), series resistance (Rs) and shunt resistance (Rsh) are determined from the I-V measurements. The n and Φb values of Au/Y/p-InP/Pt SBD are found to be 1.32 and 0.62 eV respectively. The value of barrier height (BH) obtained from Norde function is compared with those calculated from Cheung's functions. The series resistance (Rs) is calculated from Cheung's and modified Norde functions. Additionally, it is found that n, Φb, Rs, and Rsh have strong correlation with the applied bias. Furthermore, at low and high voltage regions, ohmic and space-charge-limited conduction mechanisms are found to govern the current flow in the diode.

  2. Effect of pretreatment conditions on particle size of bimetallic pt-au catalysts supported on ZnO/Al2O3 and its activity for toluene oxidation.

    PubMed

    Kim, Ki-Joong; Kang, Sang-Jun; Chung, Min-Chul; Jung, Sang-Chul; Jeong, Woon-Jo; Park, Gye-Choon; Kim, Sang-Chai; Boo, Su-Il; Jeong, Seung-Won; Ahn, Ho-Geun

    2010-09-01

    Bimetallic Pt-Au catalysts supported on ZnO/Al2O3 were prepared by incipient wetness impregnation (IW-IMP) method with different pretreatment conditions such as flow velocity, calcination temperature, and heating rate under H2 during the calcination procedure, and characterized by X-ray diffraction (XRD), CO chemisorption, and scanning transmission electron microscopy (STEM) equipped energy dispersive spectroscopy (EDS). Furthermore, catalytic activity for complete oxidation of toluene was measured using a flow reactor under atmospheric pressure. Finally, relationship between the particle sizes with pretreatment conditions and catalytic activity for toluene on the bimetallic Pt-Au catalysts was discussed. In these results, nanosized bimetallic Pt-Au particles on ZnO/Al2O3 could be prepared by IW-IMP method. Relationship between the Pt and Au particle size and activity for toluene oxidation was clearly observed. PMID:21133118

  3. Molecular dynamics simulation of joining process of Ag-Au nanowires and mechanical properties of the hybrid nanojoint

    SciTech Connect

    Ding, Su; Tian, Yanhong Jiang, Zhi; He, Xiaobin

    2015-05-15

    The nanojoining process of Ag-Au hybrid nanowires at 800K was comprehensively studied by virtue of molecular dynamics (MD) simulation. Three kinds of configurations including end-to-end, T-like and X-like were built in the simulation aiming to understand the nanojoining mechanism. The detailed dynamic evolution of atoms, crystal structure transformation and defects development during the nanojoining processes were performed. The results indicate that there are two stages in the nanojoining process of Ag-Au nanowires which are atom diffusion and new bonds formation. Temperature is a key parameter affecting both stages ascribed to the energy supply and the optimum temperature for Ag-Au nanojoint with diameter of 4.08 nm has been discussed. The mechanical properties of the nanojoint were examined with simulation of tensile test on the end-to-end joint. It was revealed that the nanojoint was strong enough to resist fracture at the joining area.

  4. Hexagonal core-shell and alloy Au/Ag nanodisks on ZnO nanorods and their optical enhancement effect

    PubMed Central

    2014-01-01

    Au and Ag hybrid hexagonal nanodisks were synthesized on ZnO nanorods' (0002) surface via a new two-step deposition-annealing method. The structural, compositional, as well as optical investigations were carried out systematically to find out the nanodisks' formation mechanism and optical enhancement effect. It was shown that the core-shell Au/Ag nanodisk can be formed under rapid annealing temperature of 500°C, while Au/Ag alloy nanodisks are formed if higher temperatures (>550°C) are applied. The optical effect from these nanodisks was studied through photoluminescence and absorption spectroscopy. It was found that the carrier-plasmon coupling together and carrier transfer between metal and ZnO contribute to the emission enhancement. Furthermore, the results suggest that the composition of nanodisk on the vicinity of metal/ZnO interface plays an important role in terms of the enhancement factors. PMID:24936157

  5. Interatomic interactions and thermodynamic parameters in dilute solid solutions of the Ag-Au system

    NASA Astrophysics Data System (ADS)

    Bogdanov, V. I.; Bol'shov, L. A.; Korneichuk, E. A.; Popov, V. A.; Korneichuk, S. K.; Badanin, D. A.

    2015-07-01

    The thermodynamic parameters of interaction and the enthalpy parameters are of fundamental importance in the theory of solutions, i.e., the coefficients of the expansion of partial excess thermodynamic functions into series in terms of the concentrations of the dissolved components. In the approximation of pairwise interactions between the impurity atoms in the solution, the above parameters can be computed using the methods of the density-functional theory in the electron theory of alloys. As an example, the substitutional solid solutions of Au in Ag have been chosen, which are formed by atoms of the components with close chemical properties, in which the deformation interactions should be small, and in which there is no need to take into account the complex magnetic contributions to the pair potentials. The total energy of the dilute solution of Au in Ag and the contributions from the chemical and strain-induced interactions to the potentials of pairwise interactions are calculated up to the seventh coordination shell. Quite satisfactory agreement with the thermodynamic parameters obtained from the experimental data has been obtained.

  6. Selective oxidation of ethane using the Au|YSZ|Ag electrochemical membrane system

    SciTech Connect

    Hamakawa, Satoshi; Sato, Koichi; Hayakawa, Takashi; York, A.P.E.; Tsunoda, Tatsuo; Suzuki, Kunio; Shimizu, Masao; Takehira, Katsuomi

    1997-01-01

    The catalytic conversion of ethane to acetaldehyde on an inert gold electrode has been studied using the electrochemical membrane reactor with yttria-stabilized zirconia (YSZ) solid electrolyte at 475 C. On applying a direct current to the reaction cell, 5% ethane in N{sub 2}, Au|YSZ|Ag, 100% O{sub 2}, acetaldehyde was formed and the formation rate increased linearly with increasing current. Selectivities to acetaldehyde and carbon dioxide were 45 and 55%, respectively. The addition of oxygen to the ethane-mixed gas in the anode space did not affect the acetaldehyde formation. The use of YSZ powder as a fixed bed catalyst under the mixed gas flow of ethane and oxygen at 450 to 600 C resulted in the formation of carbon monoxide, carbon dioxide, and ethene. Even the use of N{sub 2}O instead of oxygen resulted in no formation of acetaldehyde. Hence, it is likely that partial oxidation of ethane to acetaldehyde was carried out by the oxygen species transferred electrochemically through the YSZ which appeared at the gold-YSZ-gas triple-phase boundary. From the results of ethanol oxidation over the Au|YSZ|Ag system, the following mechanism was proposed: ethane is dehydrogenated to an ethyl radical, then converted to ethoxide, and finally to acetaldehyde by the oxygen species transferred through the YSZ.

  7. Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

    SciTech Connect

    Ji, Jianlong; Li, Pengwei; Sang, Shengbo Zhang, Wendong Li, Gang; Hu, Jie; Zhou, Zhaoying Yang, Xing; Dong, Hualai

    2014-03-15

    Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and UV–vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA) models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electric field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO) flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS) activity, using 4-mercaptopyridine (4-MP) as model molecules.

  8. Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

    NASA Astrophysics Data System (ADS)

    Ji, Jianlong; Li, Pengwei; Sang, Shengbo; Zhang, Wendong; Zhou, Zhaoying; Yang, Xing; Dong, Hualai; Li, Gang; Hu, Jie

    2014-03-01

    Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and UV-vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA) models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electric field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO) flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS) activity, using 4-mercaptopyridine (4-MP) as model molecules.

  9. Hybrid microfluidic fuel cell based on Laccase/C and AuAg/C electrodes.

    PubMed

    López-González, B; Dector, A; Cuevas-Muñiz, F M; Arjona, N; Cruz-Madrid, C; Arana-Cuenca, A; Guerra-Balcázar, M; Arriaga, L G; Ledesma-García, J

    2014-12-15

    A hybrid glucose microfluidic fuel cell composed of an enzymatic cathode (Laccase/ABTS/C) and an inorganic anode (AuAg/C) was developed and tested. The enzymatic cathode was prepared by adsorption of 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and Laccase on Vulcan XC-72, which act as a redox mediator, enzymatic catalyst and support, respectively. The Laccase/ABTS/C composite was characterised by Fourier Transform Infrared (FTIR) Spectroscopy, streaming current measurements (Zeta potential) and cyclic voltammetry. The AuAg/C anode catalyst was characterised by Transmission electron microscopy (TEM) and cyclic voltammetry. The hybrid microfluidic fuel cell exhibited excellent performance with a maximum power density value (i.e., 0.45 mW cm(-2)) that is the highest reported to date. The cell also exhibited acceptable stability over the course of several days. In addition, a Mexican endemic Laccase was used as the biocathode electrode and evaluated in the hybrid microfluidic fuel cell generating 0.5 mW cm(-2) of maximum power density. PMID:25016252

  10. Au@Ag/Au nanoparticles assembled with activatable aptamer probes as smart ``nano-doctors'' for image-guided cancer thermotherapy

    NASA Astrophysics Data System (ADS)

    Shi, Hui; Ye, Xiaosheng; He, Xiaoxiao; Wang, Kemin; Cui, Wensi; He, Dinggeng; Li, Duo; Jia, Xuekun

    2014-07-01

    Although nanomaterial-based theranostics have increased positive expectations from cancer treatment, it remains challenging to develop in vivo ``nano-doctors'' that provide high-contrast image-guided site-specific therapy. Here we designed an activatable theranostic nanoprobe (ATNP) via self-assembly of activatable aptamer probes (AAPs) on Au@Ag/Au nanoparticles (NPs). As both quenchers and heaters, novel Au@Ag/Au NPs were prepared, showing excellent fluorescence quenching and more effective near-infrared photothermal therapy than Au nanorods. The AAP comprised a thiolated aptamer and a fluorophore-labeled complementary DNA; thus, the ATNP with quenched fluorescence in the free state could realize signal activation through target binding-induced conformational change of the AAP, and then achieve on-demand treatment under image-guided irradiation. By using S6 aptamer as the model, in vitro and in vivo studies of A549 lung cancer verified that the ATNP greatly improved imaging contrast and specific destruction, suggesting a robust and versatile theranostic strategy for personalized medicine in future.Although nanomaterial-based theranostics have increased positive expectations from cancer treatment, it remains challenging to develop in vivo ``nano-doctors'' that provide high-contrast image-guided site-specific therapy. Here we designed an activatable theranostic nanoprobe (ATNP) via self-assembly of activatable aptamer probes (AAPs) on Au@Ag/Au nanoparticles (NPs). As both quenchers and heaters, novel Au@Ag/Au NPs were prepared, showing excellent fluorescence quenching and more effective near-infrared photothermal therapy than Au nanorods. The AAP comprised a thiolated aptamer and a fluorophore-labeled complementary DNA; thus, the ATNP with quenched fluorescence in the free state could realize signal activation through target binding-induced conformational change of the AAP, and then achieve on-demand treatment under image-guided irradiation. By using S6 aptamer as

  11. Investigation of oxygen reduction and methanol oxidation reaction activity of PtAu nano-alloy on surface modified porous hybrid nanocarbon supports

    NASA Astrophysics Data System (ADS)

    Parambath Vinayan, Bhaghavathi; Nagar, Rupali; Ramaprabhu, Sundara

    2016-09-01

    We investigate the electrocatalytic activity of PtAu alloy nanoparticles supported on various chemically modified carbon morphologies towards oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). The surface-modification of graphene nanosheets (f-G), multi-walled carbon nanotubes (f-MWNTs) and (graphene nanosheets-carbon nanotubes) hybrid support (f-G-MWNTs) were carried out by soft functionalization method using a cationic polyelectrolyte poly-(diallyldimethyl ammonium chloride). The Pt and PtAu alloy nanoparticles were dispersed over chemically modified carbon supports by sodium-borohydride assisted modified polyol reduction method. The electrochemical performance of all electrocatalysts were studied by half- and full-cell proton exchange membrane fuel cell (PEMFC) measurements and PtAu/f-G-MWNTs catalyst comparatively yielded the best catalytic performance. PEMFC full cell measurements of PtAu/f-G-MWNTs cathode electrocatalyst yield a maximum power density of 319 mW cm-2 at 60 °C without any back pressure,which is 2.1 times higher than that of cathode electrocatalyst Pt on graphene support. The high ORR and MOR activity of PtAu/f-G-MWNTs electrocatalyst is due to the alloying effect and inherent beneficial properties of porous hybrid nanocarbon support.

  12. Folic acid bio-inspired route for facile synthesis of AuPt nanodendrites as enhanced electrocatalysts for methanol and ethanol oxidation reactions

    NASA Astrophysics Data System (ADS)

    Wang, Ai-Jun; Ju, Ke-Jian; Zhang, Qian-Li; Song, Pei; Wei, Jie; Feng, Jiu-Ju

    2016-09-01

    Folic acid (FA), as an important biomolecule in cell division and growth, is firstly employed as the structure director and stabilizing agent for controlled synthesis of uniform Au65Pt35 nanodendrites (NDs) by a one-pot wet-chemical bio-inspired route at room temperature. No pre-seed, template, organic solvent, polymer, surfactant or complex instrument is involved. The products are mainly characterized by transmission electron microscopy (TEM), high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray diffraction (XRD), and X-Ray photoelectron spectroscopy (XPS). The architectures have enlarged electrochemically active surface area (60.6 m2 gPt-1), enhanced catalytic activity and durability for methanol and ethanol oxidation in contrast with commercial Pt black and the other AuPt alloys by tuning the molar ratios of Au to Pt (e.g., Au31Pt69 and Au82Pt18 nanoparticles). This strategy would be applied to fabricate other bimetallic nanocatalysts in fuel cells.

  13. Low-temperature formation of the FePt phase in the presence of an intermediate Au layer in Pt /Au /Fe thin films

    NASA Astrophysics Data System (ADS)

    Vladymyrskyi, I. A.; Gafarov, A. E.; Burmak, A. P.; Sidorenko, S. I.; Katona, G. L.; Safanova, N. Y.; Ganss, F.; Beddies, G.; Albrecht, M.; Makogon, Yu N.; Beke, D. L.

    2016-01-01

    Pt /Fe and Pt /Au /Fe layered films were deposited at room temperature by dc magnetron sputtering on Al2O3(0 0 0 1) single crystalline substrates and heat treated in vacuum at 330 °C with different durations (up to 62 h). It is shown by secondary neutral mass spectrometry depth profiling and x-ray diffraction that the introduction of an additional Au layer between Pt /Fe layers leads to enhanced intermixing and formation of the partially chemically ordered L10 FePt phase. The underlying diffusion processes can be explained by the grain boundary diffusion induced reaction layer formation mechanism. During the solid state reaction between Pt and Fe, the Au layer moves towards the substrate interface replacing the Fe layer. This was explained by the much faster diffusion of Fe, as compared to Pt, along the grain boundaries in Au. Enhancement of the process and formation of the ordered FePt phase in the presence of the Au intermediate layer were interpreted by the effect of stress accumulation during the grain boundary reactions: the disordered FePt phase formed initially at different Au and Pt grain boundaries can experience appropriate compressive stress along the {1 0 0} directions, which can initiate the formation of the chemically ordered L10 FePt phase.

  14. Au-Ag Alloy Static High Pressure EOS measurements: FY09 summary of results

    SciTech Connect

    Evans, W J; Jenei, Z

    2009-09-17

    Static high-pressure measurements of the equation of state of a Gold-Silver alloy (23.5 wt-% Ag) at room temperature were performed up to a pressure of approximately 100 GPA (1 megabar). Measurements were made using an energy-dispersive x-ray diffraction method. The data was analyzed, yielding crystal structure lattice constants and volume/density as a function of pressure. The results are extremely precise yielding accuracy of better than 1%. The experiments were carried out at the HPCAT 16BM-D beamline at the Advanced Photon Source. Two experiments on separate samples were carried out using conventional membrane diamond anvil cells. To achieve hydrostatic conditions, we loaded a 50-100 micron piece of the Au-Ag alloy into the cell and surrounded it with neon and mineral oil pressure media in the respective experiments. The differing pressure media demonstrated no measurable difference on the resultant crystal structures, lattice constants or pressure-volume curves. Results of our work are shown in the figures below. Up to the maximum pressure of 100 GPa the sample remained in the face-centered cubic structure, e.g., we observed no change in crystal structure. EOS curves of silver and gold, taken from the literature, are shown for comparison. We fit our data to a Vinet EOS functional form, and the parameters for this EOS were found to be, Reference (ambient pressure) volume, V{sub 0} = 16.965435 {angstrom}{sup 3}; Reference (ambient pressure) density, {rho}{sub 0} = 16.14584 g/cm{sup 3}; Bulk Modulus, K{sub 0} = 144 GPa; and Bulk Mod Derivative, K{prime}{sub 0} = 5.66. As one might expect the Au-Ag alloy lies between the gold and silver EOS curves, and tracks more closely to the gold EOS. These data are useful in validating and developing predictive EOS models of the pressure-dependent behavior of Au-Ag alloys.

  15. An ab-initio study of silicon adsorption on metallic surfaces (Au/Ag): Novel perspective to explore chemical bonding

    NASA Astrophysics Data System (ADS)

    Chakraborty, S.; Ghaisas, S. V.; Majumder, C.

    2012-07-01

    We report a first-principle investigation of the structure and electronic properties of small Sin (n = 1-6,9) clusters deposited on the Au(111) and Ag(111) surfaces. The calculations were performed using a plane wave based pseudopotential method under the framework of density functional theory. The results reveal the preference of Si atom to be adsorbed on the h.c.p. site of the metal (111) surfaces with strong binding energy. We study monolayer (ML) deposition as well as the cluster deposition on both the surfaces. The clusters introduce interlayer forces in the adsorbate. Based on PDOS (projected density of states) analysis it is found that Si atoms acquire charges from the Au/Ag surface. The binding energies are consistent with the known cohesive energy of Ag and Au silicides. The planar Sin cluster deposition on metal surfaces show that Au provides an adjustable surface with relatively strong Au-Si interaction while Ag-Si relatively weak interaction leading to dimerization of Si. The strong bonding with the surface atoms is a result of p-d hybridization. Some of the 3-D clusters show shape distortions after deposition on metal surfaces. This leads to internal stresses after deposition. A statistical parameter is defined over PDOS. It helps to measure the state delocalization in energy. Implications of the Si-Metal interaction on the initial stages of growth are discussed.

  16. Activity of calcined Ag,Cu,Au/TiO2 catalysts in the dehydrogenation/dehydration of ethanol

    NASA Astrophysics Data System (ADS)

    Mai, Do Tkhyui; Pylinina, A. I.; Mikhailenko, I. I.

    2015-07-01

    The catalytic activity of the anatase TiO2 and M z+/TiO2 with supported ions M z+ = Ag+, Cu2+, Au3+ in vapor phase conversions of ethanol is investigated at temperatures of 100-400°C. It is shown that the yields of acetaldehyde and ethylene decline for the most active catalyst Cu2+/TiO2 but increase for TiO2 and Ag/TiO2. The drop in the activation energy of the dehydrogenation reaction over calcined samples is linearly correlated with the one in the reduction potential of M z+ to Cu+, Au+, Ag0 and the ionic radius of M z+ in the crystal. The energies of activation for ethylene formation change in the series TiO2 > Au3+ > Cu2+ >Ag+ and TiO2 ≈ Cu2+ ≈ Ag+ > Au3+ for the calcined samples. The rate of pyridine adsorption, considered as an indicator of the activity of acid sites, is a linear function of ion charge + z = 1, 2, 3, and slows by two-thirds after calcination.

  17. A colorimetric assay for measuring iodide using Au@Ag core-shell nanoparticles coupled with Cu(2+).

    PubMed

    Zeng, Jingbin; Cao, Yingying; Lu, Chun-Hua; Wang, Xu-Dong; Wang, Qianru; Wen, Cong-Ying; Qu, Jian-Bo; Yuan, Cunguang; Yan, Zi-Feng; Chen, Xi

    2015-09-01

    Au@Ag core-shell nanoparticles (NPs) were synthesized and coupled with copper ion (Cu(2+)) for the colorimetric sensing of iodide ion (I(-)). This assay relies on the fact that the absorption spectra and the color of metallic core-shell NPs are sensitive to their chemical ingredient and dimensional core-to-shell ratio. When I(-) was added to the Au@Ag core-shell NPs-Cu(2+) system/solution, Cu(2+) can oxidize I(-) into iodine (I2), which can further oxidize silver shells to form silver iodide (AgI). The generated Au@AgI core-shell NPs led to color changes from yellow to purple, which was utilized for the colorimetric sensing of I(-). The assay only took 10 min with a lowest detectable concentration of 0.5 μM, and it exhibited excellent selectivity for I(-) over other common anions tested. Furthermore, Au@Ag core-shell NPs-Cu(2+) was embedded into agarose gels as inexpensive and portable "test strips", which were successfully used for the semi-quantitation of I(-) in dried kelps. PMID:26388386

  18. A colorimetric assay for measuring iodide using Au@Ag core-shell nanoparticles coupled with Cu(2+).

    PubMed

    Zeng, Jingbin; Cao, Yingying; Lu, Chun-Hua; Wang, Xu-Dong; Wang, Qianru; Wen, Cong-Ying; Qu, Jian-Bo; Yuan, Cunguang; Yan, Zi-Feng; Chen, Xi

    2015-09-01

    Au@Ag core-shell nanoparticles (NPs) were synthesized and coupled with copper ion (Cu(2+)) for the colorimetric sensing of iodide ion (I(-)). This assay relies on the fact that the absorption spectra and the color of metallic core-shell NPs are sensitive to their chemical ingredient and dimensional core-to-shell ratio. When I(-) was added to the Au@Ag core-shell NPs-Cu(2+) system/solution, Cu(2+) can oxidize I(-) into iodine (I2), which can further oxidize silver shells to form silver iodide (AgI). The generated Au@AgI core-shell NPs led to color changes from yellow to purple, which was utilized for the colorimetric sensing of I(-). The assay only took 10 min with a lowest detectable concentration of 0.5 μM, and it exhibited excellent selectivity for I(-) over other common anions tested. Furthermore, Au@Ag core-shell NPs-Cu(2+) was embedded into agarose gels as inexpensive and portable "test strips", which were successfully used for the semi-quantitation of I(-) in dried kelps.

  19. Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles

    NASA Astrophysics Data System (ADS)

    Kim, Chang-Eun; Lim, Dong-Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo; Hong, Seong-Ahn; Soon, Aloysius; Ham, Hyung Chul

    2015-01-01

    The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

  20. Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt{sub 3}M (where M = 3d transition metals) alloy catalyst from first-principles

    SciTech Connect

    Kim, Chang-Eun; Lim, Dong-Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo; Hong, Seong-Ahn; Soon, Aloysius E-mail: hchahm@kist.re.kr; Ham, Hyung Chul E-mail: hchahm@kist.re.kr

    2015-01-21

    The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt{sub 3}M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt{sub 3}M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt{sub 3}M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt{sub 3}M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

  1. Controlled protein embedment onto Au/Ag core-shell nanoparticles for immuno-labeling of nanosilver surface.

    PubMed

    Lee, In Hwan; Lee, Jeong Min; Jung, Yongwon

    2014-05-28

    Difficulties in stable conjugation of biomolecules to nanosilver surfaces have severely limited the use of silver nanostructures in biological applications. Here, we report a facile antibody conjugation onto gold/silver (Au/Ag) core-shell nanoparticles by stable and uniform embedment of an antibody binding protein, protein G, in silver nanoshells. A rigid helical peptide linker with a terminal cysteine residue was fused to protein G. A mixture of the peptide-fused protein G and space-filling free peptide was reacted with gold nanoparticles (AuNPs) to form a protein G-linked peptide layer on the particle surface. Uniform silver nanoshells were successfully formed on these protein G-AuNPs, while stably embedding protein G-linked peptide layers. Protein G specifically targets the Fc region of an antibody and thus affords properly orientated antibodies on the particle surface. Compared to Au nanoparticles of similar size with randomly adsorbed antibodies, the present immuno-labeled Au/Ag core-shell nanoparticles offered nearly 10-fold higher sensitivities for naked-eye detection of surface bound antigens. In addition, small dye molecules that were bonded to the peptide layer on Au nanoparticles exhibited highly enhanced surface-enhanced Raman scattering (SERS) signals upon Ag shell formation. The present strategy provides a simple but efficient way to conjugate antibodies to nanosilver surfaces, which will greatly facilitate wider use of the superior optical properties of silver nanostructures in biological applications. PMID:24801432

  2. Facile synthesis and intraparticle self-catalytic oxidation of dextran-coated hollow Au-Ag nanoshell and its application for chemo-thermotherapy.

    PubMed

    Jang, Hongje; Kim, Young-Kwan; Huh, Hyun; Min, Dal-Hee

    2014-01-28

    Galvanic replacement reaction is a useful method to prepare various hollow nanostructures. We developed fast and facile preparation of biocompatible and structurally robust hollow Au-Ag nanostructures by using dextran-coated Ag nanoparticles. Oxidation of the surface dextran alcohols was enabled by catalytic activity of the core Au-Ag nanostructure, introducing carbonyl groups that are useful for further bioconjugation. Subsequent doxorubicin (Dox) conjugation via Schiff base formation was achieved, giving high payload of approximately 35 000 Dox per particle. Near-infrared-mediated photothermal conversion showed high efficacy of the Dox-loaded Au-Ag nanoshell as a combinational chemo-thermotherapy to treat cancer cells.

  3. Surface Grafted Hyper-Branched Polyglycerol Stabilized Ag and AuNPs Heterogeneous Catalysts for Efficient Reduction of Congo Red.

    PubMed

    Murugan, Eagambaram; Shanmugam, Paramasivam

    2016-01-01

    Six types of insoluble polymer-supported beads immobilized with Ag and AuNPs nanoparticle catalysts were synthesized using newly prepared three different types of polymer-supported poly(styrene)-co-poly(vinyl benzene chloride) matrix (PS-PVBC), surface grafted with (i) triethanolamine (TEA), (ii) glycidyl trimethyl ammonium chloride (GTMAC) and (iii) hyper-branched polyglycerol (HPG) and Ag and AuNPs as a catalytic moiety and thus yield polymer-supported nanoparticle catalysts viz., PS-PVBC-TEA-AgNPs and AuNPs, PS-PVBC-g-GTMAC-AgNPs and AuNPs and PS-PVBC-g-GTMAC-AgNPs and AuNPs catalyst respectively. These bead-shaped heterogonous nanoparticle catalysts were characterized by UV-Vis, FTIR, FESEM, HRTEM and TGA techniques. The efficiency for stabilization/loading of metal nanoparticles with respect to varied intensities of hyper-branched chain grafted onto their matrix was screened by determining their comparative catalytic activity. The catalytic potential of these catalysts was inspected through reduction of Congo Red (CR) keeping pseudo first order identical reaction condition. The observed k(obs) values reveal that irrespective of metal the catalyst derived from hyper-branched polyglycerol as stabilizing agent viz., PS-PVBC-g-HPG-AgNPs and PS-PVBC-g-HPG-AuNPs shows (k(obs) = 3.98 x 10⁻² min⁻¹ and k(obs) = 4.54 x 10⁻² min⁻¹) four and two times greater activity than the catalyst derived from TEA and GTMAC hyper-branched chain. Further, for the same reaction PS-PVBC-g-HPG-AuNPs showed more efficiency than the PS-PVBC-g-HPG AgNPs catalyst. The stability and reusability of the superior catalyst viz., PS-PVBC-g-HPG-AuNPs catalyst was observed to be good even at the sixth cycle. This catalyst can be continuously used to conduct the reduction of various dyes in continuous mode operation in industrial scale. PMID:27398471

  4. 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.

  5. Thermodynamic properties and equations of state for Ag, Al, Au, Cu and MgO using a lattice vibrational method

    NASA Astrophysics Data System (ADS)

    Jacobs, M.; Schmid-Fetzer, R.

    2012-04-01

    A prerequisite for the determination of pressure in static high pressure measurements, such as in diamond anvil cells is the availability of accurate equations of state for reference materials. These materials serve as luminescence gauges or as X-ray gauges and equations of state for these materials serve as secondary pressure scales. Recently, successful progress has been made in the development of consistency between static, dynamic shock-wave and ultrasonic measurements of equations of state (e.g. Dewaele et al. Phys. Rev. B70, 094112, 2004, Dorogokupets and Oganov, Doklady Earth Sciences, 410, 1091-1095, 2006, Holzapfel, High Pressure Research 30, 372-394, 2010) allowing testing models to arrive at consistent thermodynamic descriptions for X-ray gauges. Apart from applications of metallic elements in high-pressure work, thermodynamic properties of metallic elements are also of mandatory interest in the field of metallurgy for studying phase equilibria of alloys, kinetics of phase transformation and diffusion related problems, requiring accurate thermodynamic properties in the low pressure regime. Our aim is to develop a thermodynamic data base for metallic alloy systems containing Ag, Al, Au, Cu, Fe, Ni, Pt, from which volume properties in P-T space can be predicted when it is coupled to vibrational models. This mandates the description of metallic elements as a first step aiming not only at consistency in the pressure scales for the elements, but also at accurate representations of thermodynamic properties in the low pressure regime commonly addressed in metallurgical applications. In previous works (e.g. Jacobs and de Jong, Geochim. Cosmochim. Acta, 71, 3630-3655, 2007, Jacobs and van den Berg, Phys. Earth Planet. Inter., 186, 36-48, 2011) it was demonstrated that a lattice vibrational framework based on Kieffer's model for the vibrational density of states, is suitable to construct a thermodynamic database for Earth mantle materials. Such a database aims at

  6. Au@Ag/Au nanoparticles assembled with activatable aptamer probes as smart "nano-doctors" for image-guided cancer thermotherapy.

    PubMed

    Shi, Hui; Ye, Xiaosheng; He, Xiaoxiao; Wang, Kemin; Cui, Wensi; He, Dinggeng; Li, Duo; Jia, Xuekun

    2014-08-01

    Although nanomaterial-based theranostics have increased positive expectations from cancer treatment, it remains challenging to develop in vivo "nano-doctors" that provide high-contrast image-guided site-specific therapy. Here we designed an activatable theranostic nanoprobe (ATNP) via self-assembly of activatable aptamer probes (AAPs) on Au@Ag/Au nanoparticles (NPs). As both quenchers and heaters, novel Au@Ag/Au NPs were prepared, showing excellent fluorescence quenching and more effective near-infrared photothermal therapy than Au nanorods. The AAP comprised a thiolated aptamer and a fluorophore-labeled complementary DNA; thus, the ATNP with quenched fluorescence in the free state could realize signal activation through target binding-induced conformational change of the AAP, and then achieve on-demand treatment under image-guided irradiation. By using S6 aptamer as the model, in vitro and in vivo studies of A549 lung cancer verified that the ATNP greatly improved imaging contrast and specific destruction, suggesting a robust and versatile theranostic strategy for personalized medicine in future.

  7. Sintered Cr/Pt and Ni/Au ohmic contacts to B{sub 12}P{sub 2}

    SciTech Connect

    Frye, Clint D.; Kucheyev, Sergei O.; Voss, Lars F.; Conway, Adam M.; Shao, Qinghui; Nikolić, Rebecca J.; Edgar, James H.

    2015-05-15

    Icosahedral boron phosphide (B{sub 12}P{sub 2}) is a wide-bandgap semiconductor possessing interesting properties such as high hardness, chemical inertness, and the reported ability to self-heal from irradiation by high energy electrons. Here, the authors developed Cr/Pt and Ni/Au ohmic contacts to epitaxially grown B{sub 12}P{sub 2} for materials characterization and electronic device development. Cr/Pt contacts became ohmic after annealing at 700 °C for 30 s with a specific contact resistance of 2 × 10{sup −4} Ω cm{sup 2}, as measured by the linear transfer length method. Ni/Au contacts were ohmic prior to any annealing, and their minimum specific contact resistance was ∼l–4 × 10{sup −4} Ω cm{sup 2} after annealing over the temperature range of 500–800 °C. Rutherford backscattering spectrometry revealed a strong reaction and intermixing between Cr/Pt and B{sub 12}P{sub 2} at 700 °C and a reaction layer between Ni and B{sub 12}P{sub 2} thinner than ∼25 nm at 500 °C.

  8. Growth of periodic nano-layers of nano-crystals of Au, Ag, Cu by ion beam

    NASA Technical Reports Server (NTRS)

    Smith, Cydale C.; Zheng, B.; Muntele, C. I.; Muntele, I. C.; Ila, D.

    2005-01-01

    Multilayered thin films of SiO2/AU+ SiO2/, SiO2/Ag+ SiO2/, and SiO2/Cu+ SiO2/, were grown by deposition. We have previously shown that MeV ion Bombardment of multi-nano-layers of SiO2/AU+ SiO2/ produces Au nanocrystals in the AU+ SiO2 layers. An increased number of nano-layers followed by MeV ion bombardment produces a wide optical absorption band, of which its FWHM depends on the number of nano-layers of SiO2/AU+ SiO2/. We have successfully repeated this process for nano-layers of SiO2/Ag+ SiO2/, and SiO2/Cu+ SiO2/. In this work we used 5 MeV Si as the post deposition bombardment ion and monitored the location as well as the optical absorption's FWHM for each layered structure using Optical Absorption Photospectrometry. The concentration and location of the metal nano-crystals were measured by Rutherford Backscattering Spectrometry. We will report on the results obtained for nano-layered structures produced by post deposition bombardment of SiO2/AU+ SiO2/, SiO2/Ag+ SiO2/, and SiO2/Cu+ SiO2/ layered systems as well as the results obtained from a system containing a periodic combination of SiO2/AU+ SiO2/, SiO2/Ag+ SiO2/, and SiO2/Cu+ SiO2/.

  9. Charge-induced dipole vs. relativistically enhanced covalent interactions in Ar-tagged Au-Ag tetramers and pentamers.

    PubMed

    Shayeghi, A; Schäfer, R; Rayner, D M; Johnston, R L; Fielicke, A

    2015-07-14

    Vibrational spectra of Au(n)Ag(m)(+)⋅Ar(k) (n + m = 4, 5; k = 1-4) clusters are determined by far-infrared resonant multiple photon dissociation spectroscopy in the range ν̃=100-250 cm(-1). The experimental spectra are assigned using density functional theory for geometries obtained by the Birmingham cluster genetic algorithm. Putative global minimum candidates of the Ar complexes are generated by adding Ar atoms to the Au(n)Ag(m)(+) low energy isomers and subsequent local optimization. Differential Ar binding energies indicate exceptionally strong Au-Ar bonds in Au-rich clusters, leading to fundamental changes to the IR spectra. The stronger Ar binding is attributed to a relativistically enhanced covalent character of the Au-Ar bond, while in Au-rich species charge-induced dipole interactions overcompensate the relativistic affinity to Au. Moreover, not only the absolute composition but also the topologies are essential in the description of Ar binding to a certain cluster.

  10. The effect of Au and Ni doping on the heavy fermion state of the Kondo lattice antiferromagnet CePtZn

    SciTech Connect

    Dhar, S. K.; Aoki, Y.; Suemitsu, B.; Miyazaki, R.; Provino, A.; Manfrinetti, P.

    2014-05-07

    We have probed the effect of doping CePtZn with Au and Ni and also investigated in detail the magnetic behavior of the iso-structural CeAuZn. A magnetic ground state is observed in both CePt{sub 0.9}Au{sub 0.1}Zn and CePt{sub 0.9}Ni{sub 0.1}Zn with T{sub N} = 2.1 and 1.1 K and the coefficient of the linear term of electronic heat capacity γ = 0.34 and 0.9 J/mol K{sup 2}, respectively. The corresponding values for CePtZn are 1.7 K and 0.6 J/mol K{sup 2}. The altered values of T{sub N} and γ show that the electronic correlations in CePtZn are affected by doping with Au and Ni. CeAuZn orders magnetically near 1.7 K and its electrical resistivity shows a normal metallic behavior. Together with a γ of 0.022 J/mol K{sup 2} the data indicate a weak 4f-conduction electron hybridization in CeAuZn characteristic of normal trivalent cerium based systems.

  11. Highly sensitive electrochemical label-free aptasensor based on dual electrocatalytic amplification of Pt-AuNPs and HRP.

    PubMed

    Bai, Lijuan; Yuan, Ruo; Chai, Yaqin; Yuan, Yali; Mao, Li; Zhuo, Ying

    2011-05-01

    In this work, a label-free electrochemical aptamer-based sensor (aptasensor) was constructed on account of the direct immobilization of redox probes on an electrode surface. For this proposed aptasensor, a gold nanoparticles (AuNPs)-coated electrode was firstly modified with redox probes-nickel hexacyanoferrates nanoparticles (NiHCFNPs) through chemisorption and electrostatic adsorption. Then, platinum-gold alloy nanoparticles (Pt-AuNPs) and horseradish peroxidase (HRP) were respectively assembled onto the modified electrode surface, which formed the multilayer films for amplifying the electrochemical signal of NiHCFNPs and immobilizing thiolated thrombin aptamers (TBAs). In the presence of target thrombin, the TBA on the multilayer could catch the thrombin onto the electrode surface, which resulted in a barrier for electro-transfer, leading to the decrease of the electrochemical signal of NiHCFNPs amplified by the Pt-AuNPs and HRP toward H(2)O(2). The proposed method avoided the redox probes labeling process, increased the amount of redox probes, and further amplified the electrochemical signal. Thus, the approach showed a high sensitivity and a wider linearity to thrombin in the range between 0.01 nM and 50 nM with a detection limit of 6.3 pM.

  12. Direct Cross-Linking of Au/Ag Alloy Nanoparticles into Monolithic Aerogels for Application in Surface-Enhanced Raman Scattering.

    PubMed

    Gao, Xiaonan; Esteves, Richard J Alan; Nahar, Lamia; Nowaczyk, Jordan; Arachchige, Indika U

    2016-05-25

    The direct cross-linking of Au/Ag alloy nanoparticles (NPs) into high surface area, mesoporous Au/Ag aerogels via chemical oxidation of the surface ligands is reported. The precursor alloy NPs with composition-tunable morphologies were produced by galvanic replacement of the preformed Ag hollow NPs. The effect of Au:Ag molar ratio on the NP morphology and surface plasmon resonance has been thoroughly investigated and resulted in smaller Au/Ag alloy NPs (4-8 nm), larger Au/Ag alloy hollow NPs (40-45 nm), and Au/Ag alloy hollow particles decorated with smaller Au NPs (2-5 nm). The oxidative removal of surfactant ligands, followed by supercritical drying, is utilized to construct large (centimeter to millimeter) self-supported Au/Ag alloy aerogels. The resultant assemblies exhibit high surface areas (67-73 m(2)/g), extremely low densities (0.051-0.055 g/cm(3)), and interconnected mesoporous (2-50 nm) networks, making them of great interest for a number of new technologies. The influence of mesoporous gel morphology on surface-enhanced Raman scattering (SERS) has been studied using Rhodamine 101 (Rd 101) as the probe molecule. The alloy aerogels exhibit SERS signal intensities that are 10-42 times higher than those achieved from the precursor Au/Ag alloy NPs. The Au/Ag alloy aerogel III exhibits SERS sensing capability down to 1 nM level. The increased signal intensities attained for alloy aerogels are attributed to highly porous gel morphology and enhanced surface roughness that can potentially generate a large number of plasmonic hot spots, creating efficient SERS substrates for future applications. PMID:27142886

  13. Band bending at Al, In, Ag, and Pt interfaces with CdTe and ZnTe (110)

    SciTech Connect

    Wahi, A.K.; Miyano, K.; Carey, G.P.; Chiang, T.T.; Lindau, I.; Spicer, W.E. )

    1990-05-01

    Band bending behavior and interfacial chemistry for Al, In, Ag, and Pt overlayers on vacuum-cleaved {ital p}-CdTe and {ital p}-ZnTe (110) have been studied using ultraviolet photoelectron spectroscopy (UPS) and x-ray photoelectron spectroscopy (XPS). These metals provide a range of metal--substrate reactivities: Al reacts strongly with Te, Ag moderately, and In minimally, with no evidence seen for In reaction on ZnTe. Pt exhibits strong alloying behavior with both Cd and Zn. All four metals are found to yield Schottky barriers on CdTe and ZnTe, with a narrow range of final Fermi level positions, {ital E}{sub {ital fi}}={ital E}{sub {ital f}}{minus}{ital E}{sub VBM}, observed on CdTe, from 0.9 to 1.05{plus minus}0.1 eV, and on ZnTe from 0.65 to 1.0{plus minus}0.1 eV. The prediction of the MIGS model that a difference in barrier height exists for two semiconductors dependent upon their band lineup (valence band offset) is examined and found to agree with experiment for Ag, Pt, and Al, but not for In. For the highly reactive Al, no evidence for the overlayer metallicity required for metal-induced gap states (MIGS) to operate is seen on CdTe or ZnTe until after band bending has stabilized. Reaction and intermixing for Al, Ag, and Pt overlayers on CdTe and ZnTe indicate these interfaces are not ideal. The possible role of defects at these four metal/CdTe and metal/ZnTe interfaces is considered, and provides a consistent explanation for the final Fermi level positions observed.

  14. Binding of Trivalent Arsenic onto the Tetrahedral Au20 and Au19Pt Clusters: Implications in Adsorption and Sensing.

    PubMed

    Cortés-Arriagada, Diego; Oyarzún, María Paz; Sanhueza, Luis; Toro-Labbé, Alejandro

    2015-07-01

    The interaction of arsenic(III) onto the tetrahedral Au20 cluster was studied computationally to get insights into the interaction of arsenic traces (presented in polluted waters) onto embedded electrodes with gold nanostructures. Pollutant interactions onto the vertex, edge, or inner gold atoms of Au20 were observed to have a covalent character by forming metal-arsenic or metal-oxygen bonding, with adsorption energies ranging from 0.5 to 0.8 eV, even with a stable physisorption; however, in aqueous media, the Au-vertex-pollutant interaction was found to be disadvantageous. The substituent effect of a platinum atom onto the Au20 cluster was evaluated to get insights into the changes in the adsorption and electronic properties of the adsorbent-adsorbate systems due to chemical doping. It was found that the dopant atom increases both the metal-pollutant adsorption energy and stability onto the support in a water media for all interaction modes; adsorption energies were found to be in a range of 0.6 to 1.8 eV. All interactions were determined to be accompanied by electron transfer as well as changes in the local reactivity that determine the amount of transferred charge and a decrease in the HOMO-LUMO energy gap with respect to the isolated substrate.

  15. Binding of Trivalent Arsenic onto the Tetrahedral Au20 and Au19Pt Clusters: Implications in Adsorption and Sensing.

    PubMed

    Cortés-Arriagada, Diego; Oyarzún, María Paz; Sanhueza, Luis; Toro-Labbé, Alejandro

    2015-07-01

    The interaction of arsenic(III) onto the tetrahedral Au20 cluster was studied computationally to get insights into the interaction of arsenic traces (presented in polluted waters) onto embedded electrodes with gold nanostructures. Pollutant interactions onto the vertex, edge, or inner gold atoms of Au20 were observed to have a covalent character by forming metal-arsenic or metal-oxygen bonding, with adsorption energies ranging from 0.5 to 0.8 eV, even with a stable physisorption; however, in aqueous media, the Au-vertex-pollutant interaction was found to be disadvantageous. The substituent effect of a platinum atom onto the Au20 cluster was evaluated to get insights into the changes in the adsorption and electronic properties of the adsorbent-adsorbate systems due to chemical doping. It was found that the dopant atom increases both the metal-pollutant adsorption energy and stability onto the support in a water media for all interaction modes; adsorption energies were found to be in a range of 0.6 to 1.8 eV. All interactions were determined to be accompanied by electron transfer as well as changes in the local reactivity that determine the amount of transferred charge and a decrease in the HOMO-LUMO energy gap with respect to the isolated substrate. PMID:26061641

  16. Differences in intermediate structures and electronic states associated with oxygen adsorption onto Pt, Cu, and Au clusters as oxygen reduction catalysts

    NASA Astrophysics Data System (ADS)

    Morishita, Tetsunori; Ueno, Tomonaga; Panomsuwan, Gasidit; Hieda, Junko; Bratescu, Maria Antoaneta; Saito, Nagahiro

    2016-10-01

    We used ab initio molecular orbital (MO) calculations to study the differences in the intermediate structures and the electronic states involved in the adsorption of O2 onto 13-atom metal clusters of Pt, Cu, and Au. Additionally, the conditions required for the electrocatalytic oxygen reduction reaction (ORR) on the Pt, Cu, and Au clusters were investigated and discussed. The intermediates involved in O2 adsorption onto Pt, Cu, and Au were found to be (Pt-O)-(Pt-O), Cu-O, and Au-O2, respectively. The differences in the O2 adsorption intermediates is explained on the basis of our analysis of the projected density of state (PDOS) area of the new MOs produced from a mixture of the 2pπ * orbitals of O2 and the d orbitals of the metal clusters. The formation of the (Pt-O)-(Pt-O) intermediate after the adsorption of O2 onto the Pt cluster is attributed to the emergence of an antibonding orbital above the Fermi level. Thus, this electronic state can lead to the decomposition and desorption of O2 molecules, thereby promoting the high-activity level of ORR. For the Cu cluster, a new antibonding orbital was observed below the Fermi level. Moreover, the Cu cluster surface can only promote O2 decomposition and not O2 desorption due to the formation of copper oxides. For the Au cluster, no new MOs related to 2pπ * orbitals of O2 appeared because O2 was molecularly adsorbed, implying that the Au cluster is an inefficient ORR catalyst.

  17. Chitosan nanocomposite films based on Ag-NP and Au-NP biosynthesis by Bacillus Subtilis as packaging materials.

    PubMed

    Youssef, Ahmed M; Abdel-Aziz, Mohamed S; El-Sayed, Samah M

    2014-08-01

    Chitosan-silver (CS-Ag) and Chitosan-gold (CS-Au) nanocomposites films were synthesized by a simple chemical method. A local bacterial isolate identified as Bacillus subtilis ss subtilis was found to be capable to synthesize both silver nanoparticles (Ag-NP) and gold nanoparticles (Au-NP) from silver nitrate (AgNO3) and chloroauric acid (AuCl(4-)) solutions, respectively. The biosynthesis of both Ag-NP and Au-NP characterize using UV/vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD), and then added to chitosan by different ratios (0.5, 1 and 2%). The prepared chitosan nanocomposites films were characterize using UV, XRD, SEM and TEM. Moreover, the antibacterial activity of the prepared films was evaluated against gram positive (Staphylococcus aureus) and gram negative bacteria (Pseudomonas aerugenosa), fungi (Aspergillus niger) and yeast (Candida albicans). Therefore, these materials can be potential used as antimicrobial agents in packaging applications.

  18. β-Cyclodextrin coated SiO₂@Au@Ag core-shell nanoparticles for SERS detection of PCBs.

    PubMed

    Lu, Yilin; Yao, Guohua; Sun, Kexi; Huang, Qing

    2015-09-01

    A new type of surface-enhanced Raman scattering (SERS) substrate consisting of β-cyclodextrin (β-CD) coated SiO2@Au@Ag nanoparticles (SiO2@Au@Ag@CD NPs) has been achieved. Our protocol was a simplified approach as the fabrication and modification of the silver shell were realized in a single-step reaction by taking advantage of β-CD as both the reducing and stabilizing agents. The as-synthesized SiO2@Au@Ag@CD NPs were uniform in size and demonstrated high SERS activity and reproducibility. The substrates consisting of the SiO2@Au@Ag@CD NPs were employed for SERS detection of polychlorinated biphenyls (PCBs) including PCB-3, PCB-29 and PCB-77. The SERS detection sensitivity was significantly improved due to enrichment of more PCB molecules captured by β-CD on the substrate surface, as confirmed by the appearance of the new Raman bands which are attributed to the complexes between β-CD and PCBs according to the theoretical simulation. Therefore, this work presents a novel approach to the fabrication of effective SERS substrates that can be employed for rapid determination of trace amounts of PCBs in the environment with high detection sensitivity and recognition selectivity. PMID:25478906

  19. Different Mechanisms Govern the Two-Phase Brust–Schiffrin Dialkylditelluride Syntheses of Ag and Au Nanoparticles

    SciTech Connect

    Li, Ying; Zaluzhna, Oksana; Zangmeister, Christopher D.; Allison, Thomas C.; Tong, YuYe J.

    2012-02-01

    Here we report the first unambiguous identification of the chemical structures of the precursor species involving metal (Au and Ag) ions and Te containing ligands in the Brust-Schiffrin syntheses of the respective metal nanoparticles, through which the different reaction pathways involved are delineated.

  20. Enzyme-free hydrogen peroxide sensor based on Au@Ag@C core-double shell nanocomposites

    NASA Astrophysics Data System (ADS)

    Li, Yancai; Zhang, Yayun; Zhong, Yanmei; Li, Shunxing

    2015-08-01

    The well-designed Au@Ag@C core-double shell nanocomposites were synthesized via a facile method, and were used to fabricate an enzyme-free amperometric hydrogen peroxide (H2O2) sensor. The size, shape, elementary composition and structure of the nanocomposites were characterized by transmission electron microscope (TEM), energy-dispersed spectrum (EDS) and X-ray diffraction (XRD). The outermost layer of the nanocomposites was amorphous carbon, the second layer was Ag and the core was Au. The Au@Ag@C core-double shell nanocomposites exhibit attractive activity for electrocatalytic reduction of H2O2 according to the electrochemical experiments. It also demonstrates the H2O2 sensor possess well performance with a wide linear range of 5.0 μM to 4.75 mM and a limit of detection (LOD) as low as 0.14 μM (S/N = 3). Furthermore, the interference from the common interfering species, such as glucose, ascorbic acid, dopamine and uric acid can be effectively avoided. In a word, the Au@Ag@C nanocomposites are promising candidates for enzyme-free H2O2 sensor.

  1. Porous Au-Ag Nanospheres with High-Density and Highly Accessible Hotspots for SERS Analysis.

    PubMed

    Liu, Kai; Bai, Yaocai; Zhang, Lei; Yang, Zhongbo; Fan, Qikui; Zheng, Haoquan; Yin, Yadong; Gao, Chuanbo

    2016-06-01

    Colloidal plasmonic metal nanoparticles have enabled surface-enhanced Raman scattering (SERS) for a variety of analytical applications. While great efforts have been made to create hotspots for amplifying Raman signals, it remains a great challenge to ensure their high density and accessibility for improved sensitivity of the analysis. Here we report a dealloying process for the fabrication of porous Au-Ag alloy nanoparticles containing abundant inherent hotspots, which were encased in ultrathin hollow silica shells so that the need of conventional organic capping ligands for stabilization is eliminated, producing colloidal plasmonic nanoparticles with clean surface and thus high accessibility of the hotspots. As a result, these novel nanostructures show excellent SERS activity with an enhancement factor of ∼1.3 × 10(7) on a single particle basis (off-resonant condition), promising high applicability in many SERS-based analytical and biomedical applications. PMID:27192436

  2. Tunable Au-Ag nanobowl arrays for size-selective plasmonic biosensing.

    PubMed

    Jana, Debrina; Lehnhoff, Emily; Bruzas, Ian; Robinson, Jendai; Lum, William; Sagle, Laura

    2016-08-01

    Selectivity is often a major obstacle for localized surface plasmon resonance-based biosensing in complex biological solutions. An additional degree of selectivity can be achieved through the incorporation of shape complementarity on the nanoparticle surface. Here, we report the versatile fabrication of substrate-bound Au-Ag nanobowl arrays through the galvanic ion replacement of silver nanodisk arrays. Both localized surface plasmon resonance (LSPR) and surface enhanced Raman spectroscopy (SERS) were carried out to detect the binding of analytes of varying size to the nanobowl arrays. Large increases in the LSPR and SERS response were measured for analytes that were small enough to enter the nanobowls, compared to those too large to come into contact with the interior of the nanobowls. This size-selective sensing should prove useful in both size determination and differentiation of large analytes in biological solutions, such as viruses, fungi, and bacterial cells.

  3. AuPt Alloy on TiO2: A Selective and Durable Catalyst for L-Sorbose Oxidation to 2-Keto-Gulonic Acid.

    PubMed

    Chan-Thaw, Carine E; Chinchilla, Lidia E; Campisi, Sebastian; Botton, Gianluigi A; Prati, Laura; Dimitratos, Nikolaos; Villa, Alberto

    2015-12-21

    Pt nanoparticles were prepared by a sol immobilization route, deposited on supports with different acid/base properties (MgO, activated carbon, TiO2 , Al2O3, H-Mordenite), and tested in the selective oxidation of sorbose to 2-keto-gulonic acid (2-KGUA), an important precursor for vitamin C. In general, as the basicity of the support increased, a higher catalytic activity occurred. However, in most cases, a strong deactivation was observed. The best selectivity to 2-KGUA was observed with acidic supports (TiO2 and H-Mordenite) that were able to minimize the formation of C1/C2 products. We also demonstrated that, by alloying Pt to Au, it is possible to enhance significantly the selectivity of Pt-based catalysts. Moreover, the AuPt catalyst, unlike monometallic Pt, showed good stability in recycling because of the prevention of metal leaching during the reaction. PMID:26611807

  4. AuPt Alloy on TiO2: A Selective and Durable Catalyst for L-Sorbose Oxidation to 2-Keto-Gulonic Acid.

    PubMed

    Chan-Thaw, Carine E; Chinchilla, Lidia E; Campisi, Sebastian; Botton, Gianluigi A; Prati, Laura; Dimitratos, Nikolaos; Villa, Alberto

    2015-12-21

    Pt nanoparticles were prepared by a sol immobilization route, deposited on supports with different acid/base properties (MgO, activated carbon, TiO2 , Al2O3, H-Mordenite), and tested in the selective oxidation of sorbose to 2-keto-gulonic acid (2-KGUA), an important precursor for vitamin C. In general, as the basicity of the support increased, a higher catalytic activity occurred. However, in most cases, a strong deactivation was observed. The best selectivity to 2-KGUA was observed with acidic supports (TiO2 and H-Mordenite) that were able to minimize the formation of C1/C2 products. We also demonstrated that, by alloying Pt to Au, it is possible to enhance significantly the selectivity of Pt-based catalysts. Moreover, the AuPt catalyst, unlike monometallic Pt, showed good stability in recycling because of the prevention of metal leaching during the reaction.

  5. One-Pot Fabrication of Mesoporous Core-Shell Au@PtNi Ternary Metallic Nanoparticles and Their Enhanced Efficiency for Oxygen Reduction Reaction.

    PubMed

    Shi, Qiurong; Zhu, Chengzhou; Fu, Shaofang; Du, Dan; Lin, Yuehe

    2016-02-01

    Currently, Pt-based nanomaterials with tailorable shapes, structures, and morphologies are the most popular electrocatalysts for oxygen reduction reaction, which is a significant cathode reaction in fuel cells for renewable energy applications. We have successfully synthesized mesoporous core-shell Au@PtNi ternary metallic nanoparticles through a one-pot reduction method for cathodic materials used as oxygen reduction reaction catalysts. The as-synthesized nanoparticles exhibited superior catalytic activities and long-term stabilities compared with mesoporous core-shell Au@Pt nanoparticles and commercial Pt/C. The unique mesoporous core-shell structures as well as the alloy shells enable the enhanced electrochemical oxygen reduction reaction performances of the Pt-based materials via the electronic effect and geometric effect, holding great promise in fuel cell application.

  6. Ultrafine Au and Ag Nanoparticles Synthesized from Self-Assembled Peptide Fibers and Their Excellent Catalytic Activity.

    PubMed

    Xu, Wenlong; Hong, Yue; Hu, Yuanyuan; Hao, Jingcheng; Song, Aixin

    2016-07-18

    The self-assembly of an amphiphilic peptide molecule to form nanofibers facilitated by Ag(+) ions was investigated. Ultrafine AgNPs (NPs=nanoparticles) with an average size of 1.67 nm were synthesized in situ along the fibers due to the weak reducibility of the -SH group on the peptide molecule. By adding NaBH4 to the peptide solution, ultrafine AgNPs and AuNPs were synthesized with an average size of 1.35 and 1.18 nm, respectively. The AuNPs, AgNPs, and AgNPs/nanofibers all exhibited excellent catalytic activity toward the reduction of 4-nitrophenol, with turnover frequency (TOF) values of 720, 188, and 96 h(-1) , respectively. Three dyes were selected for catalytic degradation by the prepared nanoparticles and the nanoparticles showed selective catalysis activity toward the different dyes. It was a surprising discovery that the ultrafine AuNPs in this work had an extremely high catalytic activity toward methylene blue, with a reaction rate constant of 0.21 s(-1) and a TOF value of 1899 h(-1) .

  7. Intensification of surface enhanced Raman scattering of thiol-containing molecules using Ag@Au core@shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Singh, Prerna; Thuy, Nguyen T. B.; Aoki, Yoshiya; Mott, Derrick; Maenosono, Shinya

    2011-05-01

    In this paper, we study the relationship between nanoparticles' structure/composition and the chemical nature of the molecules to be identified in surface enhanced Raman scattering (SERS) spectroscopy. Three types of nanoparticles (NPs) were synthesized, including Ag, Au, and silver coated by gold (Ag@Au), in order to study the resulting enhancement effects. When a rhodamine 6G dye molecule was used to assemble the NPs, it was found that Ag NPs exhibited the highest enhancement activity. However, when a thiol containing 3-amino-1,2,4-triazole-5-thiol molecule was used to assemble the NPs, it was found that the Ag@Au NPs exhibited high Raman activity as well as the Ag NPs. The results give insight into how the chemical properties of the molecules to be analyzed play an important role in the SERS detection. An additional parameter of the analysis reveals the relative stability of the three types of NP probes synthesized with regard to oxidation in the presence of different mediating molecules and varying salt concentrations. The results are of interest in designing and employing NP probes to detect biological molecules using colorimetric and SERS based approaches.

  8. 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.

  9. 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.

  10. 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

  11. Contact property of Ni(Ti)/Pt/Au on p-In0.52Al 0.48As

    NASA Astrophysics Data System (ADS)

    Wei, P.; Deng, H. H.; Tang, H. J.; Li, X.; Zhu, Y. M.; Gong, H. M.

    2012-10-01

    The annealing effects of rapid thermal processing in N2 from 350 °C to 500 °C for 60 s on Ni/Pt/Au contacts to p-InAlAs have been investigated. The result indicated that the contacts were all Schottky contacts and lowest barrier height(0.67eV) was achieved at about 450 °C. Then we used evacuated sealed-ampoule Zn diffusion method to form a heavily doped layer on p-InAlAs layer of the same sample. The diffusion conditions were 530 °C -4 min and 530 °C -8 min, respectively. Also Ni/Pt/Au contacts were deposited on the two samples and annealed at 450 °C -60 s. Although I-V characteristics which were measured indicated that a heavily doped layer is beneficial for the cantacts properties, the contacts were still Schottky contacts and the barrier heights were reduced to 0.54 eV and 0.57 eV for the two samples. Finally, we investigated contacts property of Ti/Pt/Au on p-In0.52Al0.48As of the sample which is Zn-diffused at 530 °C for 4 min. The sample was annealed at 450 °C for 60 s and the contact resistivity of the contacts was determined using the transfer line model measurements. Low resistance ohmic contacts (ρc=8.88×10-4 Ωcm2) were achieved. The results indicated that the contacts property is controlled by chemical and metallurgical reaction between the contact metal and the InAlAs layer, and a heavily doped layer is beneficial to contact properties.

  12. Pt@AuNPs integrated quantitative capillary-based biosensors for point-of-care testing application.

    PubMed

    Wu, Ze; Fu, Qiangqiang; Yu, Shiting; Sheng, Liangrong; Xu, Meng; Yao, Cuize; Xiao, Wei; Li, Xiuqing; Tang, Yong

    2016-11-15

    Current diagnostic technologies primarily rely on bulky and costly analytical instruments. Therefore, cost-effective and portable diagnosis tools that can be used for point-of-care tests (POCT) are highly desirable. In this study, we report a cost-effective, portable capillary-based biosensor for quantitative detection of biomarkers by the naked eye. This capillary-based biosensor was tested by measuring the distance of blue ink movement, which was directly correlated with the oxygen (O2) produced by efficient core-shell Pt@Au nanoparticles (Pt@AuNPs) catalysts decomposed hydrogen peroxide (H2O2). By linking the Pt@AuNPs with antibodies, capillary-based biosensor sandwich immunoassays were constructed. The concentrations of the target proteins were positively correlated with the distances of ink movement. To demonstrate their performance, the biosensors were used to detect the cancer biomarker sprostate-specific antigen (PSA) and carcinoembryonic antigen (CEA). The linear detection range (LDR) of the capillary-based biosensor for detecting PSA was from 0.02 to 2.5ng/mL, and the limit of detection (LOD) was 0.017ng/mL. LDR of the biosensor for detecting CEA was from 0.063 to 16ng/mL, and the LOD was 0.044ng/mL. For detection of PSA and CEA in clinical serum samples, the detection results of the capillary-based biosensor were well correlate with the results from of chemiluminescence immunoassays (CLIAs). Thus, the capillary-based biosensor may potentially be a useful strategy for point-of-care testing, in addition to being portable and cost effective. PMID:27240013

  13. Sensitive detection of Escherichia coli O157:H7 using Pt-Au bimetal nanoparticles with peroxidase-like amplification.

    PubMed

    Jiang, Tao; Song, Yang; Wei, Tianxiang; Li, He; Du, Dan; Zhu, Mei-Jun; Lin, Yuehe

    2016-03-15

    Escherichia coli O157:H7 is one of the most notorious foodborne pathogens causing serious disease at low infectious dose. To protect consumers from deadly foodborne E. coli O157:H7 infection, it is vital to develop a simple, reliable, sensitive and rapid method which can detect low level E. coli O157:H7 in foods at real-time. We have successfully developed a novel immunochromatographic assay (ICA) with enhanced sensitivity for the visual and quantitative detection of E. coli O157:H7. Sandwich-type immunoreactions were performed on the ICA, and Pt-Au bimetal nanoparticles (NPs) were accumulated on the test zone. The signal amplification is based on Pt-Au bimetal NPs possessing high peroxidase activity toward 3,3',5,5'-tetramethylbenzidine, which can produce characteristic colored bands and thus, enable visual detection of E. coli O157:H7 without instrumentation. The innovative aspect of this approach lies in the visualization and quantification of target pathogen through the detection of color intensity. Due to the excellent peroxidase activity of Pt-Au NPs, they emit strong visible color intensity in less than 1 min for visual observation even in low concentration range of E. coli O157:H7. Quantification was performed using a commercial assay meter. The sensitivity was improved more than 1000-folds compared to the conventional test strip based on colored gold-colloids. Although the feasibility was demonstrated using E. coli O157:H7 as a model analyte, this approach could be easily developed to be a universal signal amplification technique and applied to detection of a wide variety of foodborne pathogens and protein biomarkers.

  14. Sensitive detection of Escherichia coli O157:H7 using Pt-Au bimetal nanoparticles with peroxidase-like amplification.

    PubMed

    Jiang, Tao; Song, Yang; Wei, Tianxiang; Li, He; Du, Dan; Zhu, Mei-Jun; Lin, Yuehe

    2016-03-15

    Escherichia coli O157:H7 is one of the most notorious foodborne pathogens causing serious disease at low infectious dose. To protect consumers from deadly foodborne E. coli O157:H7 infection, it is vital to develop a simple, reliable, sensitive and rapid method which can detect low level E. coli O157:H7 in foods at real-time. We have successfully developed a novel immunochromatographic assay (ICA) with enhanced sensitivity for the visual and quantitative detection of E. coli O157:H7. Sandwich-type immunoreactions were performed on the ICA, and Pt-Au bimetal nanoparticles (NPs) were accumulated on the test zone. The signal amplification is based on Pt-Au bimetal NPs possessing high peroxidase activity toward 3,3',5,5'-tetramethylbenzidine, which can produce characteristic colored bands and thus, enable visual detection of E. coli O157:H7 without instrumentation. The innovative aspect of this approach lies in the visualization and quantification of target pathogen through the detection of color intensity. Due to the excellent peroxidase activity of Pt-Au NPs, they emit strong visible color intensity in less than 1 min for visual observation even in low concentration range of E. coli O157:H7. Quantification was performed using a commercial assay meter. The sensitivity was improved more than 1000-folds compared to the conventional test strip based on colored gold-colloids. Although the feasibility was demonstrated using E. coli O157:H7 as a model analyte, this approach could be easily developed to be a universal signal amplification technique and applied to detection of a wide variety of foodborne pathogens and protein biomarkers. PMID:26496223

  15. Theoretical study on intramolecular allene-diene cycloadditions catalyzed by PtCl2 and Au(I) complexes.

    PubMed

    Montserrat, Sergi; Alonso, Isaac; López, Fernando; Mascareñas, José L; Lledós, Agustí; Ujaque, Gregori

    2011-11-14

    The intramolecular [4C+3C] cycloaddition reaction of allenedienes catalysed by PtCl(2) and several Au(I) complexes has been studied by means of DFT calculations. Overall, the reaction mechanism comprises three main steps: (i) the formation of a metal allyl cation intermediate, (ii) a [4C(4π)+3C(2π)] cycloaddition that produces a seven-membered ring and (iii) a 1,2-hydrogen migration process on these intermediates. The reaction proceeds with complete diastereochemical control resulting from a favoured exo-like cycloaddition. Allene substituents have a critical influence in the reaction outcome and mechanism. The experimental observation of [4C+2C] cycloadducts in the reaction of substrates lacking substituents at the allene terminus can be explained through a mechanism involving Pt(IV)-metallacycles. With gold catalysts it is also possible to obtain [4C+2C] cycloaddition products, but only with substrates featuring terminally disubstituted allenes, and employing π-acceptor ligands at gold. However the mechanism for the formation of these adducts is completely different to that proposed with PtCl(2), and consists of the formation of a metal allyl cation, subsequent [4C+3C] cycloaddition and a 1,2-alkyl shift (ring contraction). Electronic analysis indicates that the divergent pathways are mainly controlled by the electronic properties of the gold heptacyclic species (L-Au-C(2)), in particular, the backdonation capacity of the metal center to the unoccupied C(2) (pπ-orbital) of the intermediate resulting from the [4C+3C] cycloaddition. The less backdonation, (i.e. using P(OR)(3)Au(+) complexes), the more favoured is the 1,2-alkyl shift.

  16. Multilevel unipolar resistive switching with negative differential resistance effect in Ag/SiO2/Pt device

    NASA Astrophysics Data System (ADS)

    Sun, Haitao; Liu, Qi; Long, Shibing; Lv, Hangbing; Banerjee, Writam; Liu, Ming

    2014-10-01

    In this paper, we report a multilevel unipolar resistive switching (RS) phenomenon with negative differential resistance (NDR) effect in Ag/SiO2/Pt sandwich structure. After positive electroforming process with low compliance current (ICC, 10 nA), a conductive filament consisting of isolated Ag nanocrystals is formed inside SiO2 layer. Then, an abnormal unipolar resistive switching (RESET voltage is larger than SET voltage) with NDR effect is obtained under negative voltage sweep without ICC. Based on I-V fitting and temperature dependence of the resistance results, we suggest that the abnormal unipolar RS is dominated by the charging/discharging of carriers in Ag nanocrystals. In addition, we demonstrate that the unipolar RS exhibits good performances, including large Roff/Ron ratio, high uniformity, long retention time, and multilevel storage potential.

  17. Real-Time Ab Initio KMC Simulation of the Self-Assembly and Sintering of Bimetallic Epitaxial Nanoclusters: Au + Ag on Ag(100)

    SciTech Connect

    Han, Yong; Liu, Da-Jiang; Evans, James W

    2014-08-13

    Far-from-equilibrium shape and structure evolution during formation and post-assembly sintering of bimetallic nanoclusters is extremely sensitive to the periphery diffusion and intermixing kinetics. Precise characterization of the many distinct local-environment-dependent diffusion barriers is achieved for epitaxial nanoclusters using density functional theory to assess interaction energies both with atoms at adsorption sites and at transition states. Kinetic Monte Carlo simulation incorporating these barriers then captures structure evolution on the appropriate time scale for two-dimensional core-ring and intermixed Au-Ag nanoclusters on Ag(100).

  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. Chemical noise produced by equilibrium adsorption/desorption of surface pyridine at Au-Ag-Au bimetallic atom-scale junctions studied by fluctuation spectroscopy.

    PubMed

    Hwang, Tai-Wei; Branagan, Sean P; Bohn, Paul W

    2013-03-20

    The chemical noise contained in conductance fluctuations resulting from adsorption and desorption of pyridine at Au-Ag-Au bimetallic atom-scale junctions (ASJs) exhibiting ballistic electron transport is studied using fluctuation spectroscopy. ASJs are fabricated by electrochemical Ag deposition in a Au nanogap to produce a high-conductance Ag quantum wire, followed by electromigration-induced thinning in pyridine solution to create stable ASJs. The conductance behavior of the resulting ASJs is analyzed by sequential autocorrelation and Fourier transform of the current-time data to yield the power spectral density (PSD). In these experiments the PSDs from Ag ASJs in pyridine exhibit two main frequency regions: 1/f noise originating from resistance fluctuations of the junction itself at low frequencies, and a Lorentzian noise component arising from molecular adsorption/desorption fluctuations at higher frequencies. The characteristic cutoff frequency of the Lorentzian noise component determines the relaxation time of molecular fluctuations, which, in turn, is sensitive to the kinetics of the adsorption/desorption process. The kinetics are found to depend on concentration and on the adsorption binding energy. The junction size (<5G0), on the other hand, does not affect the kinetics, as the cutoff frequency remains unchanged. Concentration-dependent adsorption free energies are interpreted as arising from a distribution of binding energies, N(E(b)), on the Ag ASJ. Other observations, such as long lifetime ASJs and two-level fluctuations in conductance, provide additional evidence for the integral role of the adsorbate in determining ASJ reorganization dynamics.

  20. Unusual Rh nanocrystal morphology control by hetero-epitaxially growing Rh on Au@Pt nanowires with numerous vertical twinning boundaries

    NASA Astrophysics Data System (ADS)

    An, Hyohyun; Khi, Nguyen Tien; Yoon, Jisun; Lee, Hyunkyung; Baik, Hionsuck; Sohn, Jeong-Hun; Lee, Kwangyeol

    2015-04-01

    Simultaneously growing multiple nanocrystallites in a crowded space can cause a shortage of precursors, and this can lead to a vertical growth of nanocrystallites on a given substrate. The presence of surfactant-surfactant interactions among adjacent nanocrystals can also place a unique structural constraint on the growing nanocrystallites, resulting in novel nanocrystal facet control. Herein, we report the growth of Rh on Au@Pt nanowires with multiple twinning boundaries, which are found along the entire nanowire length. The Au@Pt nanowires exhibit numerous bead-like structures, resulting from the preferred Pt deposition on the twinning boundaries, which can serve as nucleation sites for Rh. The heteroepitaxial growth of Rh on the Au@Pt nanowires results in unusual crystal growth behaviours. First, novel morphologies of Rh nanorods, nanoplates, and tangled manes are obtained temperature-dependently, which are not obtained in the absence of the Au@Pt nanowire substrate. Secondly, the thickness of vertically grown nanorods and nanoplates is tightly controlled. We also report the structure-catalytic activity relationship on the catalytic hydrogenation of phthalimides by the new Rh nanostructures.Simultaneously growing multiple nanocrystallites in a crowded space can cause a shortage of precursors, and this can lead to a vertical growth of nanocrystallites on a given substrate. The presence of surfactant-surfactant interactions among adjacent nanocrystals can also place a unique structural constraint on the growing nanocrystallites, resulting in novel nanocrystal facet control. Herein, we report the growth of Rh on Au@Pt nanowires with multiple twinning boundaries, which are found along the entire nanowire length. The Au@Pt nanowires exhibit numerous bead-like structures, resulting from the preferred Pt deposition on the twinning boundaries, which can serve as nucleation sites for Rh. The heteroepitaxial growth of Rh on the Au@Pt nanowires results in unusual crystal

  1. 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.

  2. Electrochemical Co-Reduction Synthesis of AuPt Bimetallic Nanoparticles-Graphene Nanocomposites for Selective Detection of Dopamine in the Presence of Ascorbic Acid and Uric Acid.

    PubMed

    Zhao, Zongya; Zhang, Mingming; Chen, Xiang; Li, Youjun; Wang, Jue

    2015-07-09

    In this paper, AuPt bimetallic nanoparticles-graphene nanocomposites were obtained by electrochemical co-reduction of graphene oxide (GO), HAuCl4 and H2PtCl6. The as-prepared AuPt bimetallic nanoparticles-graphene nanocomposites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and other electrochemical methods. The morphology and composition of the nanocomposite could be easily controlled by adjusting the HAuCl4/H2PtCl6 concentration ratio. The electrochemical experiments showed that when the concentration ratio of HAuCl4/H2PtCl6 was 1:1, the obtained AuPt bimetallic nanoparticles-graphene nanocomposite (denoted as Au1Pt1NPs-GR) possessed the highest electrocatalytic activity toward dopamine (DA). As such, Au1Pt1NPs-GR nanocomposites were used to detect DA in the presence of ascorbic acid (AA) and uric acid (UA) using the differential pulse voltammetry (DPV) technique and on the modified electrode, there were three separate DPV oxidation peaks with the peak potential separations of 177 mV, 130 mV and 307 mV for DA and AA, DA and UA, AA and UA, respectively. The linear range of the constructed DA sensor was from 1.6 μM to 39.7 μM with a detection limit of 0.1 μM (S/N = 3). The obtained DA sensor with good stability, high reproducibility and excellent selectivity made it possible to detect DA in human urine samples.

  3. Electrochemical Co-Reduction Synthesis of AuPt Bimetallic Nanoparticles-Graphene Nanocomposites for Selective Detection of Dopamine in the Presence of Ascorbic Acid and Uric Acid

    PubMed Central

    Zhao, Zongya; Zhang, Mingming; Chen, Xiang; Li, Youjun; Wang, Jue

    2015-01-01

    In this paper, AuPt bimetallic nanoparticles-graphene nanocomposites were obtained by electrochemical co-reduction of graphene oxide (GO), HAuCl4 and H2PtCl6. The as-prepared AuPt bimetallic nanoparticles-graphene nanocomposites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and other electrochemical methods. The morphology and composition of the nanocomposite could be easily controlled by adjusting the HAuCl4/H2PtCl6 concentration ratio. The electrochemical experiments showed that when the concentration ratio of HAuCl4/H2PtCl6 was 1:1, the obtained AuPt bimetallic nanoparticles-graphene nanocomposite (denoted as Au1Pt1NPs-GR) possessed the highest electrocatalytic activity toward dopamine (DA). As such, Au1Pt1NPs-GR nanocomposites were used to detect DA in the presence of ascorbic acid (AA) and uric acid (UA) using the differential pulse voltammetry (DPV) technique and on the modified electrode, there were three separate DPV oxidation peaks with the peak potential separations of 177 mV, 130 mV and 307 mV for DA and AA, DA and UA, AA and UA, respectively. The linear range of the constructed DA sensor was from 1.6 μM to 39.7 μM with a detection limit of 0.1 μM (S/N = 3). The obtained DA sensor with good stability, high reproducibility and excellent selectivity made it possible to detect DA in human urine samples. PMID:26184200

  4. Organic-inorganic hybrid nanoparticles for bacterial inhibition: synthesis and characterization of doped and undoped ONPs with Ag/Au NPs.

    PubMed

    Aguilar, Carlos Alberto Huerta; Jiménez, Adriana Berenice Pérez; Silva, Antonio Romero; Kaur, Navneet; Thangarasu, Pandiyan; Ramos, Jorge Manuel Vázquez; Singh, Narinder

    2015-01-01

    Organic nanoparticles (ONPs) of lipoic acid and its doped derivatives ONPs/Ag and ONPs/Au were prepared and characterized by UV-Visible, EDS, and TEM analysis. The antibacterial properties of the ONPs ONPs/Ag and ONPs/Au were tested against bacterial strains (Staphylococcus aureus, Bacillus cereus, Escherichia coli and Salmonella typhi). Minimal Inhibitory Concentration (MIC) and bacterial growth inhibition tests show that ONPs/Ag are more effective in limiting bacterial growth than other NPs, particularly, for Gram positive than for Gram-negative ones. The order of bacterial cell growth inhibition was ONPs/Ag > ONPs > ONPs/Au. The morphology of the cell membrane for the treated bacteria was analyzed by SEM. The nature of bond formation of LA with Ag or Au was analyzed by molecular orbital and density of state (DOS) using DFT. PMID:25853317

  5. Au-loaded TiO2 and Ag-loaded TiO2 synthesized by modified sol-gel/impregnation method as photocatalysts

    NASA Astrophysics Data System (ADS)

    Ninsonti, Hathaithip; Sriwichai, Saengrawee; Wetchakun, Natda; Kangwansupamonkon, Wiyong; Phanichphant, Sukon

    2016-02-01

    In this work, Au-loaded TiO2 and Ag-loaded TiO2 nanoparticles were synthesized by modified sol-gel method together with impregnation method. The samples were characterized by their physicochemical properties using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy in order to obtain the correlation between structure and photocatalytic properties. XRD results indicated unloaded TiO2, Au-loaded TiO2 and Ag-loaded TiO2 nanoparticles were all in the anatase phase with average crystallite size in the range of 10-13 nm. In addition, XPS analysis confirmed the presence of Au and Ag elements in Au-loaded TiO2 and Ag-loaded TiO2 nanoparticles, respectively. The photocatalytic activities of TiO2, Au-loaded TiO2 and Ag-loaded TiO2 nanoparticles were evaluated through the mineralization of formic acid under UV-light illumination. The results showed that Au-loading and Ag-loading could effectively improve the photocatalytic activities of TiO2. Furthermore, Au-loaded TiO2 exhibited a higher photocatalytic activity than Ag-loaded TiO2.

  6. Reduction of Ag(I), Au(III), Cu(II), and Hg(II) by Fe(II)/Fe(III) hydroxysulfate green rust.

    PubMed

    O'Loughlin, Edward J; Kelly, Shelly D; Kemner, Kenneth M; Csencsits, Roseann; Cook, Russell E

    2003-11-01

    Green rusts are mixed Fe(II)/Fe(III) hydroxides that are found in many suboxic environments where they are believed to play a central role in the biogeochemical cycling of iron. X-ray absorption fine structure analysis of hydroxysulfate green rust suspensions spiked with aqueous solutions of AgCH(3)COO, AuCl(n)(OH)(4-n), CuCl(2), or HgCl(2) showed that Ag(I), Au(III), Cu(II), and Hg(II) were readily reduced to Ag(0), Au(0), Cu(0), and Hg(0). Imaging of the resulting solids from the Ag(I)-, Au(III)-, and Cu(II)-amended green rust suspensions by transmission electron microscopy indicated the formation of submicron-sized particles of Ag(0), Au(0), and Cu(0). The facile reduction of Ag(I), Au(III), Cu(II), and Hg(II) to Ag(0), Au(0), Cu(0), and Hg(0), respectively, by green rust suggests that the presence of green rusts in suboxic soils and sediments can have a significant impact on the biogeochemistry of silver, gold, copper, and mercury, particularly with respect to their mobility.

  7. Tunable thermodynamic stability of Au-CuPt core-shell trimetallic nanoparticles by controlling the alloy composition: insights from atomistic simulations.

    PubMed

    Huang, Rao; Shao, Gui-Fang; Wen, Yu-Hua; Sun, Shi-Gang

    2014-11-01

    A microscopic understanding of the thermal stability of metallic core-shell nanoparticles is of importance for their synthesis and ultimately application in catalysis. In this article, molecular dynamics simulations have been employed to investigate the thermodynamic evolution of Au-CuPt core-shell trimetallic nanoparticles with various Cu/Pt ratios during heating processes. Our results show that the thermodynamic stability of these nanoparticles is remarkably enhanced upon rising Pt compositions in the CuPt shell. The melting of all the nanoparticles initiates at surface and gradually spreads into the core. Due to the lattice mismatch among Au, Cu and Pt, stacking faults have been observed in the shell and their numbers are associated with the Cu/Pt ratios. With the increasing temperature, they have reduced continuously for the Cu-dominated shell while more stacking faults have been produced for the Pt-dominated shell because of the significantly different thermal expansion coefficients of the three metals. Beyond the overall melting, all nanoparticles transform into a trimetallic mixing alloy coated by an Au-dominated surface. This work provides a fundamental perspective on the thermodynamic behaviors of trimetallic, even multimetallic, nanoparticles at the atomistic level, indicating that controlling the alloy composition is an effective strategy to realize tunable thermal stability of metallic nanocatalysts. PMID:25234428

  8. 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

  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. Ultrasensitive electrochemical sensor for Hg(2+) by using hybridization chain reaction coupled with Ag@Au core-shell nanoparticles.

    PubMed

    Li, Zongbing; Miao, Xiangmin; Xing, Ke; Peng, Xue; Zhu, Aihua; Ling, Liansheng

    2016-06-15

    A novel electrochemical biosensor for Hg(2+) detection was reported by using DNA-based hybridization chain reaction (HCR) coupled with positively charged Ag@Au core-shell nanoparticles ((+)Ag@Au CSNPs) amplification. To construct the sensor, capture probe (CP ) was firstly immobilized onto the surface of glass carbon electrode (GCE). In the presence of Hg(2+), the sandwiched complex can be formed between the immobilized CP on the electrode surface and the detection probe (DP) modified on the gold nanoparticles (AuNPs) based on T-Hg(2+)-T coordination chemistry. The carried DP then opened two ferrocene (Fc) modified hairpin DNA (H1 and H2) in sequence and propagated the happen of HCR to form a nicked double-helix. Numerous Fc molecules were formed on the neighboring probe and produced an obvious electrochemical signal. Moreover, (+)Ag@Au CSNPs were assembly onto such dsDNA polymers as electrochemical signal enhancer. Under optimal conditions, such sensor presents good electrochemical responses for Hg(2+) detection with a detection limit of 3.6 pM. Importantly, the methodology has high selectivity for Hg(2+) detection. PMID:26852203

  11. Ultrasensitive electrochemical sensor for Hg(2+) by using hybridization chain reaction coupled with Ag@Au core-shell nanoparticles.

    PubMed

    Li, Zongbing; Miao, Xiangmin; Xing, Ke; Peng, Xue; Zhu, Aihua; Ling, Liansheng

    2016-06-15

    A novel electrochemical biosensor for Hg(2+) detection was reported by using DNA-based hybridization chain reaction (HCR) coupled with positively charged Ag@Au core-shell nanoparticles ((+)Ag@Au CSNPs) amplification. To construct the sensor, capture probe (CP ) was firstly immobilized onto the surface of glass carbon electrode (GCE). In the presence of Hg(2+), the sandwiched complex can be formed between the immobilized CP on the electrode surface and the detection probe (DP) modified on the gold nanoparticles (AuNPs) based on T-Hg(2+)-T coordination chemistry. The carried DP then opened two ferrocene (Fc) modified hairpin DNA (H1 and H2) in sequence and propagated the happen of HCR to form a nicked double-helix. Numerous Fc molecules were formed on the neighboring probe and produced an obvious electrochemical signal. Moreover, (+)Ag@Au CSNPs were assembly onto such dsDNA polymers as electrochemical signal enhancer. Under optimal conditions, such sensor presents good electrochemical responses for Hg(2+) detection with a detection limit of 3.6 pM. Importantly, the methodology has high selectivity for Hg(2+) detection.

  12. Au-Ag polymetallic mineralization within tectonically weak zones along the southwestern edge of the Colorado Plateau

    SciTech Connect

    Wenrich, K.J.; Silberman, M.L. )

    1993-04-01

    The Music Mountain mining district lies at the base of the Grand Wash Cliffs, a major fault-line scarp along the Grand Wash fault, which marks the SW margin of the Colorado Plateau. Nearly vertical Au-Ag polymetallic quartz veins parallel, and are in contact with, altered diabase and granite porphyry dikes that cut Proterozoic granite, schist, and gneiss. The gold-bearing veins range in thickness from an inch to several feet and contain significant amounts of sulfide minerals. Diabase dikes and quartz veins in the district and to the north consistently strike N42[degree]W to N57[degree]W, which is one of the most prevalent fracture orientation throughout NW Arizona. In the Gold Basin-Lost Basin districts to the north, the Au occurs in such pegmatite-quartz veins that strike NE. Thirty miles east along Diamond Creek, quartz veins and diabase dikes strike N45[degree]E and are associated with Au and Ag anomalies in stream-sediments and panned concentrates. To the west major Au-Ag polymetallic quartz veins of the Wallapai mining district show consistent strikes from N30[degree] to 60[degree]W. K-Ar ages of hydrothermal alterations of 4 NW oriented diabase dikes that have quartz veins along them, range from 935 [+-] 35 to 755 [+-] 21 Ma. Sericite from altered granite porphyry, adjacent to a mineralized vein, gave a K-Ar age of 72 [+-]2 Ma. All geochemical sites (within a 1,000 mi[sup 2] area) determined to be anomalous in Au lie within 2 mi of either the Grand Wash or Hurricane faults. The Hurricane and Grand Wash faults, major Precambrian fault zones that were reactivated in the Phanerozoic, appear to be good exploration targets for Au-rich quartz veins associated with pegmatite or diabase dikes, many of which may be buried beneath the thick alluvium of Hualapai Valley.

  13. Photophysics and non-linear absorption of Au(I) and Pt(II) acetylide complexes of a thienyl-carbazole chromophore.

    PubMed

    Goswami, Subhadip; Wicks, Geoffrey; Rebane, Aleksander; Schanze, Kirk S

    2014-12-21

    In order to understand the photophysics and non-linear optical properties of carbazole containing π-conjugated oligomers of the type ET-Cbz-TE (E = ethynylene, T = 2,5-thienylene, Cbz = 3,6-carbazole), a detailed investigation was carried out on a series of oligomers that feature Au(i) or Pt(ii) acetylide "end groups", as well as a Pt(ii)-acetylide linked polymer (CBZ-Au-1 and CBZ-Pt-1, CBZ-Poly-Pt). These organometallic chromophores were characterized by UV-visible absorption and variable temperature photoluminescence spectroscopy, nanosecond transient absorption spectroscopy, open aperture nanosecond z-scan and two photon absorption (2PA) spectroscopy. The Au(i) and Pt(ii) oligomers and polymer exhibit weak fluorescence in fluid solution at room temperature. Efficient phosphorescence is observed from the Pt(ii) systems below 150 K in a solvent glass; however, the Au(i) oligomer exhibits only weak phosphorescence at 77 K. Taken together, the emission results indicate that the intersystem crossing efficiency for the Pt(ii) chromophores is greater than for the Au(i) oligomer. Nonetheless, nanosecond transient absorption indicates that direct excitation affords moderately long-lived triplet states for all of the chromophores. Open aperture z-scan measurement shows effective optical attenuation can be achieved by using these materials. The 2PA cross section in the degenerate S0→S1 transition region was in the range 10-100 GM, and increased monotonically toward shorter wavelengths, reaching 800-1000 GM at 550 nm.

  14. Thermodynamic guidelines for the design of bimetallic catalysts for oxygen electroreduction and rapid screening by scanning electrochemical microscopy. M-co (M: Pd, Ag, Au).

    PubMed

    Fernández, José L; Walsh, Darren A; Bard, Allen J

    2005-01-12

    We propose guidelines for the design of improved bimetallic (and related) electrocatalysts for the oxygen reduction reaction (ORR) in acidic media. This guide is based on simple thermodynamic principles assuming a simple mechanism where one metal breaks the oxygen-oxygen bond of molecular O(2) and the other metal acts to reduce the resulting adsorbed atomic oxygen. Analysis of the Gibbs free energies of these two reactions guides the selection of combinations of metals that can produce alloy surfaces with enhanced activity for the ORR when compared to the constituent metals. Selected systems have been tested by fabricating arrays of metallic catalysts consisting of various binary and ternary combinations of Pd, Au, Ag, and Co deposited on glassy carbon (GC) substrates. The electrocatalytic activity of these materials for the ORR in acidic medium was examined using scanning electrochemical microscopy (SECM) in a new rapid-imaging mode. This was used to rapidly screen arrays covering a wide range of catalyst compositions for their activity for the ORR in 0.5 M H(2)SO(4). Using the SECM technique, we have identified combinations of metals with enhanced electrocatalytic activities when compared with the constituent, pure metals. Addition of Co to Pd, Au, and Ag clearly decreases the ORR overpotential, in agreement with the proposed model. Catalyst spots that exhibited enhanced electrocatalytic activity in the SECM screening technique were then examined using classical rotating disk electrode (RDE) experiments. The activity of carbon black supported catalyst mixtures on a GC RDE and the electrocatalytic activity determined using the SECM screening technique showed excellent agreement. C/Pd-Co electrodes (10-30% Co) exhibited remarkable activity for ORR catalysis, close to that of carbon-supported Pt.

  15. 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.

  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. Hotspots engineering by grafting Au@Ag core-shell nanoparticles on the Au film over slightly etched nanoparticles substrate for on-site paraquat sensing.

    PubMed

    Wang, Chaoguang; Wu, Xuezhong; Dong, Peitao; Chen, Jian; Xiao, Rui

    2016-12-15

    Paraquat (PQ) pollutions are ultra-toxic to human beings and hard to be decomposed in the environment, thus requiring an on-site detection strategy. Herein, we developed a robust and rapid PQ sensing strategy based on the surface-enhanced Raman scattering (SERS) technique. A hybrid SERS substrate was prepared by grafting the Au@Ag core-shell nanoparticles (NPs) on the Au film over slightly etched nanoparticles (Au FOSEN). Hotspots were engineered at the junctions as indicated by the finite difference time domain calculation. SERS performance of the hybrid substrate was explored using p-ATP as the Raman probe. The hybrid substrate gives higher enhancement factor comparing to either the Au FOSEN substrate or the Au@Ag core-shell NPs, and exhibits excellent reproducibility, homogeneity and stability. The proposed SERS substrates were prepared in batches for the practical PQ sensing. The total analysis time for a single sample, including the pre-treatment and measurement, was less than 5min with a PQ detection limit of 10nM. Peak intensities of the SERS signal were plotted as a function of the PQ concentrations to calibrate the sensitivity by fitting the Hill's equation. The plotted calibration curve showed a good log-log linearity with the coefficient of determination of 0.98. The selectivity of the sensing proposal was based on the "finger print" Raman spectra of the analyte. The proposed substrate exhibited good recovery when it applied to real water samples, including lab tap water, bottled water, and commercially obtained apple juice and grape juice. This SERS-based PQ detection method is simple, rapid, sensitive and selective, which shows great potential in pesticide residue and additives abuse monitoring. PMID:27498319

  18. Hardening behavior after high-temperature solution treatment of Ag-20Pd-12Au-xCu alloys with different Cu contents for dental prosthetic restorations.

    PubMed

    Kim, Yonghwan; Niinomi, Mitsuo; Hieda, Junko; Nakai, Masaaki; Cho, Ken; Fukui, Hisao

    2014-07-01

    Ag-Pd-Au-Cu alloys have been used widely for dental prosthetic applications. Significant enhancement of the mechanical properties of the Ag-20Pd-12Au-14.5Cu alloy as a result of the precipitation of the β' phase through high-temperature solution treatment (ST), which is different from conventional aging treatment in these alloys, has been reported. The relationship between the unique hardening behavior and precipitation of the β' phase in Ag-20Pd-12Au-xCu alloys (x=6.5, 13, 14.5, 17, and 20mass%) subjected to the high-temperature ST at 1123K for 3.6ks was investigated in this study. Unique hardening behavior after the high-temperature ST also occurs in Ag-20Pd-12Au-xCu alloys (x=13, 17, and 20) with precipitation of the β' phase. However, hardening is not observed and the β' phase does not precipitate in the Ag-20Pd-12Au-6.5Cu alloy after the same ST. The tensile strength and 0.2% proof stress also increase in Ag-20Pd-12Au-xCu alloys (x=13, 14.5, 17, and 20) after the high-temperature ST. In addition, these values after the high-temperature ST increase with increasing Cu content in Ag-20Pd-12Au-xCu alloys (x=14.5, 17, and 20). The formation process of the β' phase can be explained in terms of diffusion of Ag and Cu atoms and precipitation of the β' phase. Clarification of the relationship between hardening and precipitation of the β' phase via high-temperature ST is expected to help the development of more effective heat treatments for hardening in Ag-20Pd-12Au-xCu alloys.

  19. Integrated logic gate for fluorescence turn-on detection of histidine and cysteine based on Ag/Au bimetallic nanoclusters-Cu²⁺ ensemble.

    PubMed

    Sun, Jian; Yang, Fan; Zhao, Dan; Chen, Chuanxia; Yang, Xiurong

    2015-04-01

    By means of employing 11-mercaptoundecanoic acid (11-MUA) as a reducing agent and protecting ligand, we present straightforward one-pot preparation of fluorescent Ag/Au bimetallic nanoclusters (namely AgAuNCs@11-MUA) from AgNO3 and HAuCl4 in alkaline aqueous solution at room temperature. It is found that the fluorescence of AgAuNCs@11-MUA has been selectively quenched by Cu(2+) ions, and the nonfluorescence off-state of the as-prepared AgAuNCs@11-MUA-Cu(2+) ensemble can be effectively switched on upon the addition of histidine and cysteine. By incorporating Ni(2+) ions and N-ethylmaleimide, this phenomenon is further exploited as an integrated logic gate and a specific fluorescence turn-on assay for selectively and sensitively sensing histidine and cysteine has been designed and established based on the original noncovalent AgAuNCs@11-MUA-Cu(2+) ensemble. Under the optimal conditions, histidine and cysteine can be detected in the concentration ranges of 0.25-9 and 0.25-7 μM; besides, the detection limits are found to be 87 and 111 nM (S/N = 3), respectively. Furthermore, we demonstrate that the proposed AgAuNCs@11-MUA-based fluorescent assay can be successfully utilized for biological fluids sample analysis.

  20. Integrated logic gate for fluorescence turn-on detection of histidine and cysteine based on Ag/Au bimetallic nanoclusters-Cu²⁺ ensemble.

    PubMed

    Sun, Jian; Yang, Fan; Zhao, Dan; Chen, Chuanxia; Yang, Xiurong

    2015-04-01

    By means of employing 11-mercaptoundecanoic acid (11-MUA) as a reducing agent and protecting ligand, we present straightforward one-pot preparation of fluorescent Ag/Au bimetallic nanoclusters (namely AgAuNCs@11-MUA) from AgNO3 and HAuCl4 in alkaline aqueous solution at room temperature. It is found that the fluorescence of AgAuNCs@11-MUA has been selectively quenched by Cu(2+) ions, and the nonfluorescence off-state of the as-prepared AgAuNCs@11-MUA-Cu(2+) ensemble can be effectively switched on upon the addition of histidine and cysteine. By incorporating Ni(2+) ions and N-ethylmaleimide, this phenomenon is further exploited as an integrated logic gate and a specific fluorescence turn-on assay for selectively and sensitively sensing histidine and cysteine has been designed and established based on the original noncovalent AgAuNCs@11-MUA-Cu(2+) ensemble. Under the optimal conditions, histidine and cysteine can be detected in the concentration ranges of 0.25-9 and 0.25-7 μM; besides, the detection limits are found to be 87 and 111 nM (S/N = 3), respectively. Furthermore, we demonstrate that the proposed AgAuNCs@11-MUA-based fluorescent assay can be successfully utilized for biological fluids sample analysis. PMID:25761537

  1. DNA origami based Au-Ag-core-shell nanoparticle dimers with single-molecule SERS sensitivity

    NASA Astrophysics Data System (ADS)

    Prinz, J.; Heck, C.; Ellerik, L.; Merk, V.; Bald, I.

    2016-03-01

    DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled.DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled. Electronic supplementary information (ESI) available: Additional information about materials and methods, designs of DNA origami templates, height profiles, additional SERS spectra, assignment of DNA

  2. High-spin states in {sup 191,193}Au and {sup 192}Pt: Evidence for oblate deformation and triaxial shapes

    SciTech Connect

    Oktem, Y.; Akkus, B.; Bostan, M.; Cakirli, R. B.; Erduran, M. N.; Balabanski, D. L.; Beausang, C. W.; Casten, R. F.; Kruecken, R.; Novak, J. R.; Danchev, M.; Djongolov, M.; Riedinger, L. L.; Zeidan, O.; Erturk, S.; Gladniski, K. A.; Rainovski, G.; Guerdal, G.; Goon, J. Tm.; Hartley, D. J.

    2007-10-15

    High-spin states of {sup 191,193}Au and {sup 192}Pt have been populated in the {sup 186}W({sup 11}B, xn) and {sup 186}W({sup 11}B, p4n) reactions, respectively, at a beam energy of 68 MeV and their {gamma} decay was studied using the YRAST Ball detector array at the Wright Nuclear Structure Laboratory at Yale University. The level scheme of {sup 193}Au has been extended up to I{sup {pi}}=55/2{sup +}. New transitions were observed also in {sup 191}Au and {sup 192}Pt. Particle-plus-Triaxial-Rotor (PTR) and Total Routhian Surface (TRS) calculations were performed to determine the equilibrium deformations of the Au isotopes. The predictions for oblate deformations in these nuclei are in agreement with the experimental data. Development of nonaxial shapes is discussed within the framework of the PTR model.

  3. 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.

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

    SciTech Connect

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

    2004-10-01

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

  5. Surface plasmon dispersion engineering via double-metallic AU/AG layers for nitride light-emitting diodes

    DOEpatents

    Tansu, Nelson; Zhao, Hongping; Zhang, Jing; Liu, Guangyu

    2014-04-01

    A double-metallic deposition process is used whereby adjacent layers of different metals are deposited on a substrate. The surface plasmon frequency of a base layer of a first metal is tuned by the surface plasmon frequency of a second layer of a second metal formed thereon. The amount of tuning is dependent upon the thickness of the metallic layers, and thus tuning can be achieved by varying the thicknesses of one or both of the metallic layers. In a preferred embodiment directed to enhanced LED technology in the green spectrum regime, a double-metallic Au/Ag layer comprising a base layer of gold (Au) followed by a second layer of silver (Ag) formed thereon is deposited on top of InGaN/GaN quantum wells (QWs) on a sapphire/GaN substrate.

  6. Broadband light absorption enhancement in dye-sensitized solar cells with Au-Ag alloy popcorn nanoparticles

    NASA Astrophysics Data System (ADS)

    Xu, Qi; Liu, Fang; Liu, Yuxiang; Cui, Kaiyu; Feng, Xue; Zhang, Wei; Huang, Yidong

    2013-07-01

    In this paper, we present an investigation on the use of Au-Ag alloy popcorn-shaped nanoparticles (NPs) to realise the broadband optical absorption enhancement of dye-sensitized solar cells (DSCs). Both simulation and experimental results indicate that compared with regular plasmonic NPs, such as nano-spheres, irregular popcorn-shaped alloy NPs exhibit absorption enhancement over a broad wavelength range due to the excitation of localized surface plasmons (LSPs) at different wavelengths. The power conversion efficiency (PCE) of DSCs is enhanced by 16% from 5.26% to 6.09% by incorporating 2.38 wt% Au-Ag alloy popcorn NPs. Moreover, by adding a scattering layer on the exterior of the counter electrode, the popcorn NPs demonstrate an even stronger ability to increase the PCE by 32% from 5.94% to 7.85%, which results from the more efficient excitation of the LSP mode on the popcorn NPs.

  7. 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

  8. Generation of Localized Surface Plasmon Resonance Using Hybrid Au-Ag Nanoparticle Arrays as a Sensor of Polychlorinated Biphenyls Detection.

    PubMed

    Liu, Jing; Cai, Haoyuan; Chen, Chaoyang; Yang, Guangsong; Yang, Cheng-Fu

    2016-01-01

    In this study, the hybrid Au-Ag hexagonal lattice of triangular and square lattice of quadrate periodic nanoparticle arrays (PNAs) were designed to investigate their extinction spectra of the localized surface plasmon resonances (LSPRs). First, their simulating extinction spectra were calculated by discrete dipole approximation (DDA) numerical method by changing the media refractive index. Simulation results showed that as the media refractive index was changed from 1.0 to 1.2, the maximum peak intensity of LSPRs spectra had no apparent change and the wavelength to reveal the maximum peak intensity of LSPRs spectra was shifted lower value. Polystyrene (PS) nanospheres with two differently arranged structures were used as the templates to deposit the hybrid Au-Ag hexagonal lattice of triangular and square lattice of quadrate periodic PNAs by evaporation method. The hybrid Au-Ag hexagonal lattice of triangular and square lattice of quadrate PNAs were grown on single crystal silicon (c-Si) substrates, and their measured extinction spectra were compared with the calculated results. Finally, the fabricated hexagonal lattices of triangular PNAs were investigated as a sensor of polychlorinated biphenyl solution (PCB-77) by observing the wavelength to reveal the maximum extinction efficiency (λmax). We show that the adhesion of β-cyclodextrins (SH-β-CD) on the hybrid Au-Ag hexagonal lattice of triangular PNAs could be used to increase the variation of λmax. We also demonstrate that the adhesion of SH-β-CD increases the sensitivity and detection effect of PCB-77 in hexagonal lattice of triangular PNAs. PMID:27527188

  9. Enzymatic plasmonic engineering of Ag/Au bimetallic nanoshells and their use for sensitive optical glucose sensing.

    PubMed

    He, Haili; Xu, Xiaolong; Wu, Haoxi; Jin, Yongdong

    2012-04-01

    Enzyme works for plasmonic nanostructure: an interesting enzyme-responsive hybrid Ag/Au-GOx bimetallic nanoshell (NS) system is reported, in which control over the enzyme reaction of glucose oxidase (GOx) can automatically fine-tune the morphology (from complete NS to porous NS) and optical properties of the hybrid nanostructure. The phenomenon is further exploited as a new platform for sensitive optical glucose sensing. PMID:22388952

  10. Electronic structure and conductivity of nanocomposite metal (Au,Ag,Cu,Mo)-containing amorphous carbon films

    SciTech Connect

    Endrino, Jose L.; Horwat, David; Gago, Raul; Andersson, Joakim; Liu, Y.S.; Guo, Jinghua; Anders, Andre

    2008-05-14

    In this work, we study the influence of the incorporation of different metals (Me = Au, Ag, Cu, Mo) on the electronic structure of amorphous carbon (a-C:Me) films. The films were produced at room temperature using a novel pulsed dual-cathode arc deposition technique. Compositional analysis was performed with secondary neutral mass spectroscopy whereas X-ray diffraction was used to identify the formation of metal nanoclusters in the carbon matrix. The metal content incorporated in the nanocomposite films induces a drastic increase in the conductivity, in parallel with a decrease in the band gap corrected from Urbach energy. The electronic structure as a function of the Me content has been monitored by x-ray absorption near edge structure (XANES) at the C K-edge. XANES showed that the C host matrix has a dominant graphitic character and that it is not affected significantly by the incorporation of metal impurities, except for the case of Mo, where the modifications in the lineshape spectra indicated the formation of a carbide phase. Subtle modifications of the spectral lineshape are discussed in terms of nanocomposite formation.

  11. Formation of recent Pb-Ag-Au mineralization by potential sub-surface microbial activity.

    PubMed

    Tornos, Fernando; Velasco, Francisco; Menor-Salván, César; Delgado, Antonio; Slack, John F; Escobar, Juan Manuel

    2014-08-06

    Las Cruces is a base-metal deposit in the Iberian Pyrite Belt, one of the world's best-known ore provinces. Here we report the occurrence of major Pb-Ag-Au mineralization resulting from recent sub-surface replacement of supergene oxyhydroxides by carbonate and sulphide minerals. This is probably the largest documented occurrence of recent microbial activity producing an ore assemblage previously unknown in supergene mineralizing environments. The presence of microbial features in the sulphides suggests that these may be the first-described natural bacteriomorphs of galena. The low δ(13)C values of the carbonate minerals indicate formation by deep anaerobic microbial processes. Sulphur isotope values of sulphides are interpreted here as reflecting microbial reduction in a system impoverished in sulphate. We suggest that biogenic activity has produced around 3.1 × 10(9) moles of reduced sulphur and 10(10) moles of CO2, promoting the formation of ca. 1.19 Mt of carbonates, 114,000 t of galena, 638 t of silver sulphides and 6.5 t of gold.

  12. Dihydrogen bond interactions as a result of H2 cleavage at Cu, Ag and Au centres.

    PubMed

    Grabowski, Sławomir J; Ruipérez, Fernando

    2016-05-14

    A quantum chemical study of H2 activation at fluorides of coinage metals, MF (M = Cu, Ag and Au), and its splitting was performed. The following reaction path was analyzed: FMH2→ FHHM → HMFH, where both the molecular complexes and the corresponding transition states have been characterized at the CCSD(T)/aug-cc-pVQZ//MP2/aug-cc-pVQZ level of theory. Further single-point CASSCF/CASPT2 calculations, including spin-orbit coupling effects, were also performed to analyze the role of non-dynamic correlation. The scalar relativistic effects are included via aug-cc-pVQZ-PP basis sets used for the metals. The dihydrogen-bonded copper (FHHCu) and silver (FHHAg) complexes are observed as a result of H2 cleavage, while the corresponding FHHAu gold complex is not found but the HAuHF arrangement is observed, instead. The energetic and geometrical parameters of the complexes have been analyzed and both the Quantum Theory of Atoms in Molecules approach and the Natural Bond Orbitals method were additionally applied to analyze the intermolecular interactions. PMID:27101741

  13. Formation of recent Pb-Ag-Au mineralization by potential sub-surface microbial activity

    NASA Astrophysics Data System (ADS)

    Tornos, Fernando; Velasco, Francisco; Menor-Salván, César; Delgado, Antonio; Slack, John F.; Escobar, Juan Manuel

    2014-08-01

    Las Cruces is a base-metal deposit in the Iberian Pyrite Belt, one of the world’s best-known ore provinces. Here we report the occurrence of major Pb-Ag-Au mineralization resulting from recent sub-surface replacement of supergene oxyhydroxides by carbonate and sulphide minerals. This is probably the largest documented occurrence of recent microbial activity producing an ore assemblage previously unknown in supergene mineralizing environments. The presence of microbial features in the sulphides suggests that these may be the first-described natural bacteriomorphs of galena. The low δ13C values of the carbonate minerals indicate formation by deep anaerobic microbial processes. Sulphur isotope values of sulphides are interpreted here as reflecting microbial reduction in a system impoverished in sulphate. We suggest that biogenic activity has produced around 3.1 × 109 moles of reduced sulphur and 1010 moles of CO2, promoting the formation of ca. 1.19 Mt of carbonates, 114,000 t of galena, 638 t of silver sulphides and 6.5 t of gold.

  14. 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.

  15. Faceting of Nanoscale Pt and Au Particles for Applications in Catalysis

    SciTech Connect

    Richards, R. M.; Leong, J.; Dinh, H.; Pivovar, B.

    2012-01-01

    In an effort to reduce the world's dependence on fossil fuels as well as lower green house gas emissions, proton exchange membrane fuel cells (PEMFC) have been considered by many as a prime candidate for both mobile and stationary alternative energy sources. The principal limiting factor for efficiency in fuel cells is the oxygen reduction reaction (ORR) which is driven by platinum based catalyst materials. Numerous methods have been developed to synthesize particles that make more efficient use of the active surfaces by tuning shapes, sizes and facets. For example, it was recently demonstrated that selectivity can be tuned by controlling particle shape in the case of promoting trans olefin isomerization to their cis counterparts using close-packed Pt (111), Pt (557) and Pt (100) surfaces as opposed to a more open Pt (110), which favored the trans-counterparts. Furthermore, it has been reported that certain facets exhibit improved ORR activity while others may decrease activity at the bulk phase single crystal level. Here, we will present a study of various wet chemical reduction methods targeting specific morphologies and the resulting electrochemical activity. Determining the effects of synthetic parameters on the final product via transmission electron microscopy (TEM), small angle x-ray scattering (SAXS) and wide angle x-ray scattering (WAXS) provides mechanistic insight on growth kinetics, while electrochemical studies correlate physical properties to performance. Understanding structure and activity relationships will allow us to intuitively design next generation materials with enhanced properties.

  16. Particle size dependence of the surface-enhanced Raman scattering properties of densely arranged two-dimensional assemblies of Au(core)-Ag(shell) nanospheres.

    PubMed

    Sugawa, Kosuke; Akiyama, Tsuyoshi; Tanoue, Yoshimasa; Harumoto, Takashi; Yanagida, Sayaka; Yasumori, Atsuo; Tomita, Shohei; Otsuki, Joe

    2015-09-01

    We investigated the dependence of the surface-enhanced Raman scattering (SERS) activity of densely arranged two-dimensional assemblies of spherical Au(core)-Ag(shell) nanoparticles (Au/AgNSs) on the nanoparticle diameter. The size-controlled Au/AgNSs were synthesized using the Au nanosphere seed-mediated growth method without any bulky stabilizers. The diameters of the Au/AgNSs were 38, 53, and 90 nm and the ratio of the total diameter to the Au core diameter was adjusted to ca. 2.0. Extinction spectra of the colloidal solutions of these nanoparticles exhibited the prominent peak of the localized surface plasmon resonance (LSPR) of Ag and therefore the Au/AgNSs exhibited LSPR properties almost the same as Ag nanospheres. It was confirmed from SEM observation that the organic solvent-mediated liquid-liquid interface assembly technique easily generated densely arranged two-dimensional assemblies of the nanospheres. The extinction spectra of all the assemblies exhibited a prominent broad peak ranging from 500 nm to the near-infrared region, which is assigned to the longitudinal LSPR mode of the coupling nanospheres. The extinction intensity increased with increasing nanosphere diameter. The SERS activities of these assemblies were investigated using p-aminothiophenol as a probe molecule. The result revealed that the enhancement factor (EF) of the Raman signal dramatically increased upon increasing the particle diameter. The maximum EF obtained with a laser excitation wavelength of 785 nm was 1.90 × 10(6) for a nanosphere diameter of 90 nm. This renders the two-dimensional assemblies of the plasmonic Au/AgNSs promising for the development of highly sensitive SERS sensor platforms due to their strong electromagnetic effect.

  17. The enhancing of Au-Ag-Te content in tellurium-bearing ore mineral by bio-oxidation-leaching

    NASA Astrophysics Data System (ADS)

    Kim, PyeongMan; Kim, HyunSoo; Myung, EunJi; Kim, YoonJung; Lee, YongBum; Park*, CheonYoung

    2015-04-01

    The purpose of this study is to enhance the content of valuable metals such as Au-Ag-Te in tellurium-bearing minerals by bio-oxidation-leaching. It was confirmed that pyrite, chalcopyrite, sphalerite and galena were produced together with tellurium-bearing minerals including hessite, sylvanite and tellurobismuthite from ore minerals and concentrates through microscopic observation and SEM/EDS analysis. In a bio-oxidation-leaching experiment, with regard to Au, Ag, Te, Cu and Fe, the changes in the amount of leaching and the content of leaching residues were compared and analyzed with each other depending on the adaptation of an indigenous microbe identified as Acidithiobacillus ferrooxidans. As a result of the experiment, the Au-Ag-Te content in tellurium-bearing ore mineral was enhanced in the order of physical oxidation leaching, physical/non-adaptive bio-oxidation-leaching and physical/adaptive biological leaching. It suggests that the bio-oxidation-leaching using microbes adapted in tellurium-bearing ore mineral can be used as a pre-treatment and a main process in a recovery process of valuable metals. "This research was supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education(NRF-2013R1A1A2004898)"

  18. Probing the mechanism of plasma protein adsorption on Au and Ag nanoparticles with FT-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Mengmeng; Fu, Cuiping; Liu, Xingang; Lin, Zhipeng; Yang, Ning; Yu, Shaoning

    2015-09-01

    Protein-nanoparticle interactions are important in biomedical applications of nanoparticles and for growing biosafety concerns about nanomaterials. In this study, the interactions of four plasma proteins, human serum albumin (HSA), myoglobin (MB), hemoglobin (HB), and trypsin (TRP), with Au and Ag nanoparticles were investigated by FT-IR spectroscopy. The secondary structure of thio-proteins changed with time during incubation with Au and Ag nanoparticles, but the secondary structures of non-thio-proteins remained unchanged. The incubation time for structural changes depended on the sulfur-metal bond energy; the stronger the sulfur-metal energy, the less the time needed. H/D exchange experiments revealed that protein-NP complexes with thio-proteins were less dynamic than free proteins. No measurable dynamic differences were found between free non-thio-proteins and the protein-Au (or Ag) nanoparticle complex. Therefore, the impact of covalent bonds on the protein structure is greater than that of the electrostatic force.

  19. The effect of Zn, Ag and Au substitution for Cu in Finemet on the crystallization and magnetic properties

    NASA Astrophysics Data System (ADS)

    Chau, N.; Hoa, N. Q.; The, N. D.; Vu, L. V.

    2006-08-01

    Soft magnetic ribbons of Finemet compound with Zn, Ag and Au substituted for Cu: Fe 73.5Si 13.5B 9Nb 3Cu 1-xM x (M=Zn, Ag, Au; x=0.5, 1.0) have been fabricated by rapid quenching technique with wheel speeds of 10, 25 and 30 m/s, respectively. The crystallization evolution of samples examined by DSC measurements showed that the high cooling rates make the ribbons in amorphous state whereas the samples with M=Zn; x=0.5, 1.0 showed to be partly crystallized when they fabricated by the wheel speed of 10 m/s. In the case of Zn ( x=0.5, 1.0) and Ag ( x=1.0) substitution there is a sharp peak in the DSC curve corresponding to crystallization of α-Fe(Si) phase. However, the role of Au is similar to that of Cu. Hysteresis loops of as-cast samples exhibited square form which relates to the pinning centers in domain wall displacement. After appropriate annealing, the ultrasoft magnetic properties of studied ribbons are obtained.

  20. Effect of thione primers on adhesive bonding between an indirect composite material and Ag-Pd-Cu-Au alloy.

    PubMed

    Imai, Hideyuki; Koizumi, Hiroyasu; Shimoe, Saiji; Hirata, Isao; Matsumura, Hideo; Nikawa, Hiroki

    2014-01-01

    The current study evaluated the effect of primers on the shear bond strength of an indirect composite material joined to a silverpalladium-copper-gold (Ag-Pd-Cu-Au) alloy (Castwell). Disk specimens were cast from the alloy and were air-abraded with alumina. Eight metal primers were applied to the alloy surface. A light-polymerized indirect composite material (Solidex) was bonded to the alloy. Shear bond strength was determined both before and after the application of thermocycling. Two groups primed with Metaltite (thione) and M. L. Primer (sulfide) showed the greatest post-thermocycling bond strength (8.8 and 6.5 MPa). The results of the X-ray photoelectron spectroscopic (XPS) analysis suggested that the thione monomer (MTU-6) in the Metaltite primer was strongly adsorbed onto the Ag-Pd-Cu-Au alloy surface even after repeated cleaning with acetone. The application of either the thione (MTU-6) or sulfide primer is effective for enhancing the bonding between a composite material and Ag-Pd-Cu-Au alloy.

  1. Ab initio study of MXe{sub n}{sup +} (M=Cu, Ag, and Au; n=1,2)

    SciTech Connect

    Li Xinying; Cao Xue

    2008-02-15

    The equilibrium geometries, vibrational frequencies, dissociation energies, and populations of the title species were studied at Hartree-Fock (HF), second-order Moeller-Plesset (MP2), and coupled-cluster singles-doubles (triples) [CCSD(T)] levels. The electron correlation effects and relativistic effects on the geometry and stability were investigated at the CCSD(T) level. Both effects stabilize title species. The populations analyses show that M-Xe bonding is dominated by electrostatic interactions and the best theoretical estimate of the dissociation energies are 1.104 and 2.260 eV for AuXe{sup +} and AuXe{sub 2}{sup +}, respectively. The Cu and Ag are weakly bonded to Xe compared to Au.

  2. Tuning Interior Nanogaps of Double-shelled Au/Ag Nanoboxes for Surface-Enhanced Raman Scattering

    PubMed Central

    Zhang, Weiqing; Rahmani, Mohsen; Niu, Wenxin; Ravaine, Serge; Hong, Minghui; Lu, Xianmao

    2015-01-01

    Double-shelled Au/Ag hollow nanoboxes with precisely controlled interior nanogaps (1 to 16 nm) were synthesized for gap-tunable surface-enhanced Raman scattering (SERS). The double-shelled nanoboxes were prepared via a two-step galvanic replacement reaction approach using Ag nanocubes as the templates, while 4-aminothiolphenol (4-ATP) as SERS probe molecules were loaded between the two shells. More than 10-fold enhancement of SERS is observed from the double-shelled nanoboxes than Ag nanocubes. In addition, the SERS of the double-shelled nanoboxes increase significantly with the decrease of gap size, consistent with the theoretical prediction that smaller gap size induces larger localized electromagnetic enhancement. PMID:25670352

  3. Tuning interior nanogaps of double-shelled Au/Ag nanoboxes for surface-enhanced Raman scattering.

    PubMed

    Zhang, Weiqing; Rahmani, Mohsen; Niu, Wenxin; Ravaine, Serge; Hong, Minghui; Lu, Xianmao

    2015-02-11

    Double-shelled Au/Ag hollow nanoboxes with precisely controlled interior nanogaps (1 to 16 nm) were synthesized for gap-tunable surface-enhanced Raman scattering (SERS). The double-shelled nanoboxes were prepared via a two-step galvanic replacement reaction approach using Ag nanocubes as the templates, while 4-aminothiolphenol (4-ATP) as SERS probe molecules were loaded between the two shells. More than 10-fold enhancement of SERS is observed from the double-shelled nanoboxes than Ag nanocubes. In addition, the SERS of the double-shelled nanoboxes increase significantly with the decrease of gap size, consistent with the theoretical prediction that smaller gap size induces larger localized electromagnetic enhancement.

  4. Current transport mechanisms in lattice-matched Pt/Au-InAlN/GaN Schottky diodes

    SciTech Connect

    Ren, Jian; Yan, Dawei Yang, Guofeng; Wang, Fuxue; Xiao, Shaoqing; Gu, Xiaofeng

    2015-04-21

    Lattice-matched Pt/Au-In{sub 0.17}Al{sub 0.83}N/GaN hetreojunction Schottky diodes with circular planar structure have been fabricated and investigated by temperature dependent electrical measurements. The forward and reverse current transport mechanisms are analyzed by fitting the experimental current-voltage characteristics of the devices with various models. The results show that (1) the forward-low-bias current is mainly due to the multiple trap-assisted tunneling, while the forward-high-bias current is governed by the thermionic emission mechanism with a significant series resistance effect; (2) the reverse leakage current under low electric fields (<6 MV/cm) is mainly carried by the Frenkel-Poole emission electrons, while at higher fields the Fowler-Nordheim tunneling mechanism dominates due to the formation of a triangular barrier.

  5. 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

  6. 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.

  7. Increasing Stability and Activity of Core-Shell Catalysts by Preferential Segregation of Oxide on Edges and Vertexes: Oxygen Reduction on Ti-Au@Pt/C

    DOE PAGES

    Hu, J.; Wu, L.; Kuttiyiel, K.; Goodman, K. R.; Zhang, C.; Zhu, Y.; Vukmirovic, M. B.; White, M. G.; Sasaki, K.; Adzic, R. R.

    2016-06-30

    We describe a new class of core-shell nanoparticle catalysts having edges and vertexes covered by refractory metal oxide that preferentially segregates onto these catalyst sites. The monolayer shell is deposited on the oxidefree core atoms. The oxide on edges and vertexes induces high catalyst’s stability and activity. The catalyst and synthesis are exemplified by fabrication of Au nanoparticles doped by Ti atoms that segregate as oxide onto low–coordination sites of edges and vertexes. Pt monolayer shell deposited on Au sites has the mass and specific activities for the oxygen reduction reaction about 13 and 5 times higher than those ofmore » commercial Pt/C catalysts. The durability tests show no activity loss after 10000 potential cycles from 0.6 to 1.0V. The superior activity and durability of the Ti-Au@Pt catalyst originate from protective Ti oxide located at the most dissolution-prone edge and vertex sites, and Au-supported active and stable Pt shell.« less

  8. The synthesis of Au@C@Pt core-double shell nanocomposite and its application in enzyme-free hydrogen peroxide sensing

    NASA Astrophysics Data System (ADS)

    Zhang, Yayun; Li, Yuhui; Jiang, Yingying; Li, Yancai; Li, Shunxing

    2016-08-01

    A novel Au@C@Pt core-double shell nanocomposite was synthesized and used to fabricate enzyme-free electrochemical sensor for rapid and sensitive detection of hydrogen peroxide (H2O2). The well-designed Au@C@Pt core-double shell nanocomposite was characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM) and energy-dispersed spectrum (EDS). The Au@C@Pt core-double shell nanocomposite modified glassy carbon electrode (Au@C@Pt/GCE) exhibits good electrocatalytic activity towards H2O2 reduction at 0.0 V and can be used as H2O2 sensor. The sensor displays two wide linear ranges towards H2O2 detection. The one is 9.0 μM-1.86 mM with high sensitivity of 144.7 μA mM-1 cm-2, and the other is 1.86 mM-7.11 mM with sensitivity of 80.1 μA mM-1 cm-2. When signal to noise (S/N) is 3, the calculated detection limit (LOD) is 0.13 μM. Furthermore, the interference from the common interfering species such as glucose, ascorbic acid, dopamine and uric acid can be effectively avoided to H2O2 detection. Additionally, the H2O2 sensor also displays good stability and reproducibility.

  9. Fabrication of electrodes with ultralow platinum loading by RF plasma processing of self-assembled arrays of Au@Pt nanoparticles

    NASA Astrophysics Data System (ADS)

    Banerjee, Ipshita; Kumaran, V.; Santhanam, Venugopal

    2016-07-01

    Conductive, carbon-free, electrocatalytically active, nanostructured electrodes with ultra-low platinum loading were fabricated using self-assembly of octadecanethiol-coated Au@Pt nanoparticles followed by RF plasma treatment. Bilayer arrays of Au@Pt nanoparticles with platinum loadings of 0.50, 1.04, 1.44, and 1.75 μg cm‑2 (corresponding to 0.5, 1, 1.5 and 2 atomic layer coverage of platinum on nominally 5 nm gold core) were subjected to RF argon plasma treatment for various durations and their electrical conductivity, morphological evolution, and electrocatalytic activity characterized. Samples with monolayer and above platinum coverages exhibit maximum electrochemically active surface areas values of ∼100 m2/gpt and specific activities that are ∼4× to 6× of a reference platinum nanoparticle bilayer array. The underlying gold core influences the structural evolution of the samples upon RF plasma treatment and leads to the formation of highly active Pt(110) facets on the surface at an optimal plasma treatment duration, which also corresponds to the onset of a sharp decline in lateral sheet resistance. The sample having a two atom thick platinum coating has the highest total mass activity of 48 ± 3 m2/g(pt+au), corresponding to 44% Pt atom utilization, while also exhibiting enhanced CO tolerance as well as high methanol oxidation reaction and oxygen reduction reaction activity.

  10. Fabrication of electrodes with ultralow platinum loading by RF plasma processing of self-assembled arrays of Au@Pt nanoparticles

    NASA Astrophysics Data System (ADS)

    Banerjee, Ipshita; Kumaran, V.; Santhanam, Venugopal

    2016-07-01

    Conductive, carbon-free, electrocatalytically active, nanostructured electrodes with ultra-low platinum loading were fabricated using self-assembly of octadecanethiol-coated Au@Pt nanoparticles followed by RF plasma treatment. Bilayer arrays of Au@Pt nanoparticles with platinum loadings of 0.50, 1.04, 1.44, and 1.75 μg cm-2 (corresponding to 0.5, 1, 1.5 and 2 atomic layer coverage of platinum on nominally 5 nm gold core) were subjected to RF argon plasma treatment for various durations and their electrical conductivity, morphological evolution, and electrocatalytic activity characterized. Samples with monolayer and above platinum coverages exhibit maximum electrochemically active surface areas values of ˜100 m2/gpt and specific activities that are ˜4× to 6× of a reference platinum nanoparticle bilayer array. The underlying gold core influences the structural evolution of the samples upon RF plasma treatment and leads to the formation of highly active Pt(110) facets on the surface at an optimal plasma treatment duration, which also corresponds to the onset of a sharp decline in lateral sheet resistance. The sample having a two atom thick platinum coating has the highest total mass activity of 48 ± 3 m2/g(pt+au), corresponding to 44% Pt atom utilization, while also exhibiting enhanced CO tolerance as well as high methanol oxidation reaction and oxygen reduction reaction activity.

  11. Evidence for non-conservative current-induced forces in the breaking of Au and Pt atomic chains.

    PubMed

    Sabater, Carlos; Untiedt, Carlos; van Ruitenbeek, Jan M

    2015-01-01

    This experimental work aims at probing current-induced forces at the atomic scale. Specifically it addresses predictions in recent work regarding the appearance of run-away modes as a result of a combined effect of the non-conservative wind force and a 'Berry force'. The systems we consider here are atomic chains of Au and Pt atoms, for which we investigate the distribution of break down voltage values. We observe two distinct modes of breaking for Au atomic chains. The breaking at high voltage appears to behave as expected for regular break down by thermal excitation due to Joule heating. However, there is a low-voltage breaking mode that has characteristics expected for the mechanism of current-induced forces. Although a full comparison would require more detailed information on the individual atomic configurations, the systems we consider are very similar to those considered in recent model calculations and the comparison between experiment and theory is very encouraging for the interpretation we propose. PMID:26734525

  12. Evidence for non-conservative current-induced forces in the breaking of Au and Pt atomic chains.

    PubMed

    Sabater, Carlos; Untiedt, Carlos; van Ruitenbeek, Jan M

    2015-01-01

    This experimental work aims at probing current-induced forces at the atomic scale. Specifically it addresses predictions in recent work regarding the appearance of run-away modes as a result of a combined effect of the non-conservative wind force and a 'Berry force'. The systems we consider here are atomic chains of Au and Pt atoms, for which we investigate the distribution of break down voltage values. We observe two distinct modes of breaking for Au atomic chains. The breaking at high voltage appears to behave as expected for regular break down by thermal excitation due to Joule heating. However, there is a low-voltage breaking mode that has characteristics expected for the mechanism of current-induced forces. Although a full comparison would require more detailed information on the individual atomic configurations, the systems we consider are very similar to those considered in recent model calculations and the comparison between experiment and theory is very encouraging for the interpretation we propose.

  13. 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.

  14. 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.

  15. Thin-walled SnO₂ nanotubes functionalized with Pt and Au catalysts via the protein templating route and their selective detection of acetone and hydrogen sulfide molecules.

    PubMed

    Jang, Ji-Soo; Kim, Sang-Joon; Choi, Seon-Jin; Kim, Nam-Hoon; Hakim, Meggie; Rothschild, Avner; Kim, Il-Doo

    2015-10-21

    Bio-inspired Pt (∼2 nm) and Au (∼2.7 nm) catalysts encapsulated by a protein shell, i.e., Pt-apoferritin (Pt@AF) and Au-apoferriten (Au@AF), were synthesized via the hollow protein nanocage (apoferritin) templating route and directly functionalized on the interior and exterior walls of electrospun SnO2 nanotubes (NTs) during controlled single-nozzle electrospinning followed by high temperature calcination with heating rate control. Fast crystallization of the exterior shell and outward diffusion of the interior Sn precursors and crystallites result in the continued growth of a tubular wall, which is related to rapid heating driven Ostwald-ripening behavior. Very importantly, the Pt and Au nanoparticles (NPs) were immobilized onto thin-walled SnO2 NTs with a diameter of ∼350 nm and a shell thickness of ∼40 nm without any aggregation of catalysts due to high dispersibility, which originated from repulsive electrostatic (Coulombic) forces acting on the surface charged protein shells, leading to an enhanced catalytic effect and outstanding gas sensing properties. Pt-loaded SnO2 NTs exhibited superior acetone response (R(air)/R(gas) = 92 at 5 ppm) compared to pure SnO2 NFs (R(air)/R(gas) = 4.8 at 5 ppm) and SnO2 NTs (Rair/Rgas = 11 at 5 ppm) while Au-loaded SnO2 NTs showed a high response when exposed to hydrogen sulfide (R(air)/R(gas) = 34 at 5 ppm), offering selective gas detection with minimal cross-sensitivity against other interfering gases such as NH3, CO, NO, C6H5CH3, and C5H12. Our results provide a new insight into facile, cost-effective, and highly dispersible catalyst loading on the interior and exterior walls of hollow metal oxide NTs via simple electrospinning as a potential breath analyzer.

  16. Thin-walled SnO₂ nanotubes functionalized with Pt and Au catalysts via the protein templating route and their selective detection of acetone and hydrogen sulfide molecules.

    PubMed

    Jang, Ji-Soo; Kim, Sang-Joon; Choi, Seon-Jin; Kim, Nam-Hoon; Hakim, Meggie; Rothschild, Avner; Kim, Il-Doo

    2015-10-21

    Bio-inspired Pt (∼2 nm) and Au (∼2.7 nm) catalysts encapsulated by a protein shell, i.e., Pt-apoferritin (Pt@AF) and Au-apoferriten (Au@AF), were synthesized via the hollow protein nanocage (apoferritin) templating route and directly functionalized on the interior and exterior walls of electrospun SnO2 nanotubes (NTs) during controlled single-nozzle electrospinning followed by high temperature calcination with heating rate control. Fast crystallization of the exterior shell and outward diffusion of the interior Sn precursors and crystallites result in the continued growth of a tubular wall, which is related to rapid heating driven Ostwald-ripening behavior. Very importantly, the Pt and Au nanoparticles (NPs) were immobilized onto thin-walled SnO2 NTs with a diameter of ∼350 nm and a shell thickness of ∼40 nm without any aggregation of catalysts due to high dispersibility, which originated from repulsive electrostatic (Coulombic) forces acting on the surface charged protein shells, leading to an enhanced catalytic effect and outstanding gas sensing properties. Pt-loaded SnO2 NTs exhibited superior acetone response (R(air)/R(gas) = 92 at 5 ppm) compared to pure SnO2 NFs (R(air)/R(gas) = 4.8 at 5 ppm) and SnO2 NTs (Rair/Rgas = 11 at 5 ppm) while Au-loaded SnO2 NTs showed a high response when exposed to hydrogen sulfide (R(air)/R(gas) = 34 at 5 ppm), offering selective gas detection with minimal cross-sensitivity against other interfering gases such as NH3, CO, NO, C6H5CH3, and C5H12. Our results provide a new insight into facile, cost-effective, and highly dispersible catalyst loading on the interior and exterior walls of hollow metal oxide NTs via simple electrospinning as a potential breath analyzer. PMID:26395290

  17. Surface enhanced vibrational spectroscopy and first-principles study of L-cysteine adsorption on noble trimetallic Au/Pt@Rh clusters.

    PubMed

    Loganathan, B; Chandraboss, V L; Senthilvelan, S; Karthikeyan, B

    2015-09-01

    The Rh shell of the Au/Pt/Rh trimetallic nanoparticles induces a wide variety of interesting surface reactions by allowing the adsorption of amino acids like L-cysteine (L-Cys). We present a snapshot of theoretical and experimental investigation of L-Cys adsorption on the surface of noble trimetallic Au/Pt@Rh colloidal nanocomposites. Density functional theoretical (DFT) investigations of L-Cys interaction with the Rhodium (Rh) shell of a trimetallic Au/Pt@Rh cluster in terms of geometry, binding energy (E(B)), binding site, energy gap (E(g)), electronic and spectral properties have been performed. L-Cys establishes a strong interaction with the Rh shell. It binds to Rh by the S1-site, which makes a stable L-Cys-Rh surface complex. DFT can be taken as a valuable tool to assign the vibrational spectra of the adsorption of L-Cys on trimetallic Au/Pt@Rh colloidal nanocomposites and mono-metallic Rh nanoparticles. Surface-enhanced infrared spectroscopy (SEIRS) with L-Cys on a Rh6 cluster surface has been simulated for the first time. Experimental information on the L-Cys-Rh surface complex is included to examine the interaction. The experimental spectral observations are in good agreement with the simulated DFT results. Characterization of the synthesized trimetallic Au/Pt@Rh colloidal nanocomposites has been done by high-resolution transmission electron microscopy (HR-TEM) with selected area electron diffraction (SAED) pattern, energy dispersive X-ray (EDX) spectroscopy, dynamic light scattering (DLS) measurements, zeta potential, zeta deviation analysis and UV-visible (UV-Vis) spectroscopic studies. PMID:25650352

  18. Chemical trend of superconducting transition temperature in hole-doped delafossite of CuAlO2, AgAlO2 and AuAlO2

    NASA Astrophysics Data System (ADS)

    Nakanishi, Akitaka; Katayama-Yoshida, Hiroshi

    2012-12-01

    We have performed the first-principles calculations about the superconducting transition temperature Tc of hole-doped delafossite CuAlO2, AgAlO2 and AuAlO2. Calculated Tc are about 50 K (CuAlO2), 40 K (AgAlO2) and 3 K(AuAlO2) at maximum in the optimum hole-doping concentration. The low Tc of AuAlO2 is attributed to the weak electron-phonon interaction caused by the low covalency and heavy atomic mass.

  19. Ohmic contacts to [ital n]-GaAs with a Pt/Ge/Au contacting layer and a Ta-Si-N barrier: Electrical and metallurgical characteristics

    SciTech Connect

    Chen, J.S.; Kolawa, E.; Nicolet, M. ); Ruiz, R.P. )

    1994-06-01

    Pt/Ge/Au trilayers of various Pt:Ge compositions, overlaid with a Ta-Si-N barrier layer and an Au metallization layer, are investigated as ohmic contacts to [ital n]-type GaAs. After annealing in flowing argon at 450 [degree]C for 15 min, a contact resistivity of 3.7[times]10[sup [minus]6] [Omega] cm[sup 2] is obtained for the sample of atomic ratio Pt/Ge=1. The contact resistivity of this sample degrades only slightly to 5.0[times]10[sup [minus]6] [Omega] cm[sup 2] upon aging at 450 [degree]C for 60 h, while the surface stays smooth. Contact resistivities of samples with other Pt/Ge atomic ratios are in the range of 10[sup [minus]5]--10[sup [minus]4] [Omega] cm[sup 2]. To understand this electrical behavior, the contacts are characterized by backscattering spectrometry, x-ray diffraction, and transmission electron microscopy in conjunction with energy-dispersive analysis of x rays. The reaction products vary with the Pt:Ge compositions due to the difference of the chemical reactivity between Pt, Ge, and GaAs. The formation and distribution of a ternary PtGe:As phase are the determining factors for the contact resistivity. The outstanding thermal stability of the contact is due to the Ta-Si-N barrier layer which closes the GaAs-trilayer system and protects their chemical equilibria from being disrupted by an inflow of Au from the metallization layer. Without the barrier layer, the morphology of the contact degrades badly at 450 [degree]C after 20 h or less.

  20. 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.

  1. Ag@Au core-shell nanoparticles synthesized by pulsed laser ablation in water: Effect of plasmon coupling and their SERS performance.

    PubMed

    Vinod, M; Gopchandran, K G

    2015-01-01

    Ag@Au core-shell nanoparticles are synthesised by pulsed laser ablation in water using low energy laser pulses. The plasmon characteristics of these core-shell nanoparticles are found to be highly sensitive to the thickness of Au coating. In the synthesis, at first silver nanocolloid was prepared by ablating Ag target and then it is followed by ablation of Au target for different time durations to form Ag@Au core-shell nanostructures. The effect of plasmon-plasmon coupling on the absorption spectra is investigated by decreasing the effective distance between the nanoparticles. This is achieved by reducing the total volume of the colloidal suspension by simple evaporation of water, the solvent used. The suitability of these core-shell nanostructures for application as surface enhanced Raman scattering substrates are tested with crystal violet as probe molecules. Influence of plasmon coupling on the enhancement of Raman bands is found to be different for different bands.

  2. Sensitive Glycoprotein Sandwich Assays by the Synergistic Effect of In Situ Generation of Raman Probes and Plasmonic Coupling of Ag Core-Au Satellite Nanostructures.

    PubMed

    Bi, Xiaoshuang; Li, Xueyuan; Chen, Dong; Du, Xuezhong

    2016-05-01

    Sensitive surface-enhanced Raman scattering (SERS) assays of glycoproteins have been proposed using p-aminothiophenol (PATP)-embedded Ag core-Au satellite nanostructures modified with p-mercaptophenylboronic acid (PMBA) and the self-assembled monolayer of PMBA on a smooth gold-coated wafer. The apparent Raman probe PATP on the surfaces of the Ag cores underwent a photodimerization to generate 4,4'-dimercaptoazobenzene (DMAB) in situ upon excitation of laser, and the in situ generated DMAB acted as the actual Raman probe with considerably strong SERS signals, which was further enhanced by the plasmonic coupling of the Ag core-Au satellite nanostructures due to the synergistic effect. The sandwich assays of glycoproteins showed high sensitivity and excellent selectivity against nonglycoproteins. The Ag core-Au satellite SERS nanostructures can be used for highly sensitive SERS assays of other analytes.

  3. Genesis of Middle Miocene Yellowstone hotspot-related bonanza epithermal Au-Ag deposits, Northern Great Basin, USA

    NASA Astrophysics Data System (ADS)

    Saunders, J. A.; Unger, D. L.; Kamenov, G. D.; Fayek, M.; Hames, W. E.; Utterback, W. C.

    2008-09-01

    Epithermal deposits with bonanza Au-Ag veins in the northern Great Basin (NGB) are spatially and temporally associated with Middle Miocene bimodal volcanism that was related to a mantle plume that has now migrated to the Yellowstone National Park area. The Au-Ag deposits formed between 16.5 and 14 Ma, but exhibit different mineralogical compositions, the latter due to the nature of the country rocks hosting the deposits. Where host rocks were primarily of meta-sedimentary or granitic origin, adularia-rich gold mineralization formed. Where glassy rhyolitic country rocks host veins, colloidal silica textures and precious metal-colloid aggregation textures resulted. Where basalts are the country rocks, clay-rich mineralization (with silica minerals, adularia, and carbonate) developed. Oxygen isotope data from quartz (originally amorphous silica and gels) from super-high-grade banded ores from the Sleeper deposit show that ore-forming solutions had δ 18O values up to 10‰ heavier than mid-Miocene meteoric water. The geochemical signature of the ores (including their Se-rich nature) is interpreted here to reflect a mantle source for the “epithermal suite” elements (Au, Ag, Se, Te, As, Sb, Hg) and that signature is preserved to shallow crustal levels because of the similar volatility and aqueous geochemical behavior of the “epithermal suite” elements. A mantle source for the gold in the deposits is further supported by the Pb isotopic signature of the gold ores. Apparently the host rocks control the mineralization style and gangue mineralogy of ores. However, all deposits are considered to have derived precious metals and metalloids from mafic magmas related to the initial emergence of the Yellowstone hotspot. Basalt-derived volatiles and metal(loid)s are inferred to have been absorbed by meteoric-water-dominated geothermal systems heated by shallow rhyolitic magma chambers. Episodic discharge of volatiles and metal(loid)s from deep basaltic magmas mixed with

  4. Descriptive and Grade-Tonnage Models and Database for Iron Oxide Cu-Au Deposits

    USGS Publications Warehouse

    Cox, Dennis P.; Singer, Donald A.

    2007-01-01

    Iron oxide Cu-Au deposits are veins and breccia-hosted bodies of hematite and/or magnetite with disseminated Cu + Au ? Ag ? Pd ? Pt ? Ni ? U ? LREE minerals formed in sedimentary or volcano-sedimentary basins intruded by igneous rocks. Deposits are associated with broad redox boundaries and feature sodic alteration of source rocks and potassic alteration of host rocks.

  5. Strong improvements of localized surface plasmon resonance sensitivity by using Au/Ag bimetallic nanostructures modified with polydopamine films.

    PubMed

    Jia, Kun; Khaywah, Mohammad Y; Li, Yugang; Bijeon, Jean L; Adam, Pierre M; Déturche, Régis; Guelorget, Bruno; François, Manuel; Louarn, Guy; Ionescu, Rodica E

    2014-01-01

    In the present work, the standard monometallic localized surface plasmon resonance (LSPR) biosensing sensitivity is highly improved when using a new system based on glass substrates modified with high-temperature annealed gold/silver bimetallic nanoparticles (Au/Ag bimetallic NPs) coated with polydopamine films before biomolecule specific immobilization. Thus, different zones of bimetallic NPs are spatially created onto a glass support thanks to a commercial transmission electron microscopy (TEM) grid marker in combination with two sequential evaporations of continuous films of gold (4 nm) and silver (2 nm) and followed by annealing at 500 °C for 8 h. By using the scanning electron microscopy (SEM), it is found that annealed Au/Ag bimetallic NPs have uniform size and shape distribution that exhibited a sharper well-defined LSPR resonant peak when compared with that of monometallic Au NPs and thereby contributing to an improved sensitivity in LSPR biosensor application. The controlled micropatterns consisting of bimetallic particles are used in the construction of LSPR biochips for high-throughput detection of different concentrations of a model antigen named bovine serum albumin (BSA) on a single glass sample, with a lower limit of detection of 0.01 ng/mL under the optimized conditions.

  6. An Experimental Study of Transient Liquid Phase Bonding of the Ternary Ag-Au-Cu System Using Differential Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Kuntz, M. L.; Panton, B.; Wasiur-Rahman, S.; Zhou, Y.; Corbin, S. F.

    2013-08-01

    An experimental approach using differential scanning calorimetry (DSC) has been applied to quantify the solid/liquid interface kinetics during the isothermal solidification stage of transient liquid phase (TLP) bonding in an Ag-Au-Cu ternary alloy solid/liquid diffusion couple. Eutectic Ag-Au-Cu foil interlayers were coupled with pure Ag base metal to study the effects of two solutes on interface motion. Experimental effects involving baseline shift and primary solidification contribute to a systematic underestimation of the fraction of liquid remaining. A temperature program has been used to quantify and correct these effects. The experimental results show a linear relationship between the interface position and the square root of the isothermal hold time. The shifting tie line composition at the interface has been shown to affect the DSC results; however, the impact on the calculated interface kinetics has been shown to be minimal in this case. This work has increased the knowledge of isothermal solidification in ternary alloy systems and developed accurate experimental methods to characterize these processes, which is valuable for designing TLP bonding schedules.

  7. Recording-media-related morphology and magnetic properties of crystalline CoPt{sub 3} and CoPt{sub 3}-Au core-shell nanoparticles synthesized via reverse microemulsion

    SciTech Connect

    Bahmanrokh, Ghazaleh Hashim, Mansor; Matori, Khamirul Amin; Kanagesan, Samikannu; Sabbaghizadeh, Rahim; Ezzad Shafie, Mohd Shamsul; Navasery, Manizheh; Soltani, Nayereh; Vaziri, Parisa

    2014-09-07

    A comparative experimental study of the magnetic properties of CoPt{sub 3} and CoPt{sub 3}/Au nanoparticles as well as a detailed study of the structural properties of the samples by X-ray diffraction, Transmission electron microscopy, and vibrating sample magnetometer is presented in this work. In addition, the effect of particle size on the structure and magnetic properties of nanoparticles prepared by microemulsion is studied. The correlation between particle size, crystallinity, and magnetization was studied as well. CoPt nanoparticles have been studied intensively over the last decade because of their increased magnetic anisotropy in the ordered phase that can be interesting for high density magnetic recording. A significant high coercivity for as-prepared CoPt{sub 3} and CoPt{sub 3}-Au nanoparticles was obtained at room temperature and enhanced after annealing. The focused aim of our study is to obtain high coercivity at room temperature that follows the Curie-Weiss law. This indicates an interacting system in which the nanoparticles behave like single domain ferromagnetic materials in the particle size range of 8 to 35 nm. In addition, the interaction increases by cooling the samples to low temperature around 15 K. Temperature dependence 1/M graph was obtained to investigate the behavior of nanoparticles at low temperature and shows the best fit with Curie-Weis mode.

  8. Target-specific near-IR induced drug release and photothermal therapy with accumulated Au/Ag hollow nanoshells on pulmonary cancer cell membranes.

    PubMed

    Noh, Mi Suk; Lee, Somin; Kang, Homan; Yang, Jin-Kyoung; Lee, Hyunmi; Hwang, Doyk; Lee, Jong Woo; Jeong, Sinyoung; Jang, Yoonjeong; Jun, Bong-Hyun; Jeong, Dae Hong; Kim, Seong Keun; Lee, Yoon-Sik; Cho, Myung-Haing

    2015-03-01

    Au/Ag hollow nanoshells (AuHNSs) were developed as multifunctional therapeutic agents for effective, targeted, photothermally induced drug delivery under near-infrared (NIR) light. AuHNSs were synthesized by galvanic replacement reaction. We further conjugated antibodies against the epidermal growth factor receptor (EGFR) to the PEGylated AuHNS, followed by loading with the antitumor drug doxorubicin (AuHNS-EGFR-DOX) for lung cancer treatment. AuHNSs showed similar photothermal efficiency to gold nanorods under optimized NIR laser power. The targeting of AuHNS-EGFR-DOX was confirmed by light-scattering images of A549 cells, and doxorubicin release from the AuHNSs was evaluated under low pH and NIR-irradiated conditions. Multifunctional AuHNS-EGFR-DOX induced photothermal ablation of the targeted lung cancer cells and rapid doxorubicin release following irradiation with NIR laser. Furthermore, we evaluated the effectiveness of AuHNS-EGFR-DOX drug delivery by comparing two drug delivery methods: receptor-mediated endocytosis and cell-surface targeting. Accumulation of the AuHNS-EGFR-DOX on the cell surfaces by targeting EGFR turned out to be more effective for lung cancer treatments than uptake of AuHNS-EGFR-DOX. Taken together, our data suggest a new and optimal method of NIR-induced drug release via the accumulation of targeted AuHNS-EGFR-DOX on cancer cell membranes. PMID:25662498

  9. Target-specific near-IR induced drug release and photothermal therapy with accumulated Au/Ag hollow nanoshells on pulmonary cancer cell membranes.

    PubMed

    Noh, Mi Suk; Lee, Somin; Kang, Homan; Yang, Jin-Kyoung; Lee, Hyunmi; Hwang, Doyk; Lee, Jong Woo; Jeong, Sinyoung; Jang, Yoonjeong; Jun, Bong-Hyun; Jeong, Dae Hong; Kim, Seong Keun; Lee, Yoon-Sik; Cho, Myung-Haing

    2015-03-01

    Au/Ag hollow nanoshells (AuHNSs) were developed as multifunctional therapeutic agents for effective, targeted, photothermally induced drug delivery under near-infrared (NIR) light. AuHNSs were synthesized by galvanic replacement reaction. We further conjugated antibodies against the epidermal growth factor receptor (EGFR) to the PEGylated AuHNS, followed by loading with the antitumor drug doxorubicin (AuHNS-EGFR-DOX) for lung cancer treatment. AuHNSs showed similar photothermal efficiency to gold nanorods under optimized NIR laser power. The targeting of AuHNS-EGFR-DOX was confirmed by light-scattering images of A549 cells, and doxorubicin release from the AuHNSs was evaluated under low pH and NIR-irradiated conditions. Multifunctional AuHNS-EGFR-DOX induced photothermal ablation of the targeted lung cancer cells and rapid doxorubicin release following irradiation with NIR laser. Furthermore, we evaluated the effectiveness of AuHNS-EGFR-DOX drug delivery by comparing two drug delivery methods: receptor-mediated endocytosis and cell-surface targeting. Accumulation of the AuHNS-EGFR-DOX on the cell surfaces by targeting EGFR turned out to be more effective for lung cancer treatments than uptake of AuHNS-EGFR-DOX. Taken together, our data suggest a new and optimal method of NIR-induced drug release via the accumulation of targeted AuHNS-EGFR-DOX on cancer cell membranes.

  10. 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

  11. Electrochemiluminescence immunosensor using poly(l-histidine)-protected glucose dehydrogenase on Pt/Au bimetallic nanoparticles to generate an in situ co-reactant.

    PubMed

    Xiao, Lijuan; Chai, Yaqin; Wang, Haijun; Yuan, Ruo

    2014-08-21

    In this work, Pt/Au bimetallic nanoparticles (Pt/Au NPs) were used as nanocarriers to develop an electrochemiluminescence (ECL) immunosensor for sensitive cardiac troponin I (cTnI) detection, coupling with enzyme-based signal amplification. First, gold nanoparticles modified Ru(phen)3(2+)-doped silica nanoparticles (Au@RuSiO2 NPs) with numerous luminophores were used as a platform, potentially increasing the signal intensity. Second, Pt/Au NPs with large surface area and rich surface atoms were a superior matrix for the immobilization of numerous antibodies (Ab2), poly(l-histidine) (PLH) and glucose dehydrogenase (GDH). More importantly, the PLH-protected GDH exhibited excellent enzymatic activity for the oxidation of glucose accompanied by the reduction of NAD(+) to NADH. The in situ generated NADH acted as a co-reactant of Ru(phen)3(2+), significantly enhancing the ECL signal. In this manner, the designed immunosensor displayed high sensitivity for the detection of cTnI in the range of 0.010 ng mL(-1) to 10 ng mL(-1) with a detection limit of 3.3 pg mL(-1) (S/N = 3). The proposed strategy holds a new promise for highly sensitive bioassays for application in clinical analyses. PMID:24940578

  12. The effect of intermetallic compound evolution on the fracture behavior of Au stud bumps joined with Sn-3.5Ag solder

    NASA Astrophysics Data System (ADS)

    Lee, Young-Kyu; Ko, Yong-Ho; Kim, Jun-Ki; Lee, Chang-Woo; Yoo, Sehoon

    2013-01-01

    The microstructure and joint properties of Au stud bumps joined with Sn-3.5Ag solder were investigated as functions of flip chip bonding temperature and aging time. Au stud bumps were bonded on solder-onpad (SOP) at bonding temperature of 260°C and 300°C for 10 s, respectively. Aging treatment was carried out at 150°C for 100 h, 300 h, and 500 h, respectively. After flip chip bonding, intermetallic compounds (IMCs) of AuSn, AuSn2, and AuSn4 were formed at the interface between the Au stud bump and Sn-3.5Ag solder. At a bonding temperature of 300°C, AuSn2 IMC clusters, which were surrounded by AuSn4 IMCs, were observed in the Sn-3.5Ag solder bump. After flip chip bonding, bonding strength was approximately 220.5mN/bump. As aging time increased, the bonding strength decreased. After 100 h of aging treatment, the bonding strength of the joint bonded at 300°C was lower than that bonded at 260°C due to the fast growth rate of the AuSn2 IMCs. The main failure modes were interface fractures between the AuSn2 IMCs and AuSn4 IMCs, fractures through the AuSn2 IMCs and pad lift. Initial joint microstructures after flip chip bonding strongly affected the bonding strengths of aged samples.

  13. 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

    2016-04-01

    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.

  14. Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters

    DOE PAGES

    Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y.; Nobusada, Katsuyuki; Jin, Rongchao

    2016-02-29

    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 inmore » 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. As a result, 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.« less

  15. One-Pot Polyol Synthesis of Pt/CeO2 and Au/CeO2 Nanopowders as Catalysts for CO Oxidation.

    PubMed

    Pilger, Frank; Testino, Andrea; Lucchini, Mattia Alberto; Kambolis, Anastasios; Tarik, Mohammed; El Kazzi, Mario; Arroyo, Yadira; Rossell, Marta D; Ludwig, Christian

    2015-05-01

    The facile one-pot synthesis of CeO2-based catalysts has been developed to prepare a relatively large amount of nanopowders with relevant catalytic activity towards CO oxidation. The method consists of a two-steps process carried out in ethylene glycol: in the first step, 5 nm well-crystallized pure CeO2 is prepared. In a subsequent second step, a salt of a noble metal is added to the CeO2 suspension and the deposition of the noble metal on the nanocrystalline CeO2 is induced by heating. Two catalysts were prepared: Pt/CeO2 and Au/CeO2. The as-prepared catalysts, the thermally treated catalysts, as well as the pure CeO2, are characterized by XRD, TGA, XPS, FTIR, HR-TEM, STEM, particle size distribution, and N2-physisorption. In spite of the identical preparation protocol, Au and Pt behave in a completely different way: Au forms rather large particles, most of them with triangular shape, easily identifiable and dispersed in the CeO2 matrix. In contrast, Pt was not identified as isolated particles. The high resolution X-ray diffraction carried out on the Pt/CeO2 thermally treated sample (500 degrees C for 1 h) shows a significant CeO2 lattice shrinkage, which can be interpreted as an at least partial incorporation of Pt into the CeO2 crystal lattice. Moreover, only Pt2+ and Pt4+ species were identified by XPS. In literature, the incorporation of Pt into the CeO2 lattice is supported by first-principle calculations and experimentally demonstrated only by combustion synthesis methods. To the best of our knowledge this is the first report where ionically dispersed Pt into the CeO2 lattice is obtained via a liquid synthesis method. The thermally treated Pt/CeO2 sample revealed good activity with 50% CO conversion at almost room temperature.

  16. Nanobiophotonics for molecular imaging of cancer: Au- and Ag-based Epidermal Growth Factor receptor (EGFR) specific nanoprobes

    NASA Astrophysics Data System (ADS)

    Lucas, Leanne J.; Hewitt, Kevin C.

    2012-03-01

    Our aim is to create and validate a novel SERS-based nanoprobe for optical imaging of the epidermal growth factor receptor (EGFR). Gold and silver nanoparticles (Au/AgNPs) of various sizes were synthesized and coupled to epidermal growth factor (EGF) via a short ligand, α-lipoic acid (206 g/mol), which binds strongly to both Au and Ag nanoparticles via its disulfide end group. We used carbodiimide chemistry to couple EGF to α-lipoic acid. These nanoprobes were tested for binding affinity using Enzyme Linked ImmunoSorbent Assay (ELISA) and, in-vitro, using EGFRoverexpressing A431 cells. The nanoprobes show excellent EGFR-specific binding. Time of Flight Mass Spectrometry demonstrate the carbodiimide based linking of the carboxylic acid end-group of α-lipoic acid to one or more of the three (terminal, or 2 lysine) amine groups on EGF. ELISA confirms that the linked EGF is active by itself, and following conjugation with gold or silver nanoparticles. Compared with bare nanoparticles, UV-Vis spectroscopy of Ag-based nanoprobes exhibit significant plasmon red-shift, while there was no discernable shift for Au-based ones. Dark field microscopy shows abundant uptake by EGFR overexpressing A431 cells, and serves to further confirm the excellent binding affinity. Nanoprobe internalization and consequent aggregation is thought to be the basis of enhanced light scattering in the dark field images, supporting the notion that these nanoprobes should provide excellent SERS signals at all nanoprobe sizes. In summary, novel EGFR-specific nanoprobes have been synthesized and validated by standard assay and in cell culture for use as SERS optical imaging probes.

  17. Adjustable coordination of a hybrid phosphine-phosphine oxide ligand in luminescent Cu, Ag and Au complexes.

    PubMed

    Dau, Thuy Minh; Asamoah, Benjamin Darko; Belyaev, Andrey; Chakkaradhari, Gomathy; Hirva, Pipsa; Jänis, Janne; Grachova, Elena V; Tunik, Sergey P; Koshevoy, Igor O

    2016-09-28

    A potentially tridentate hemilabile ligand, PPh2-C6H4-PPh(O)-C6H4-PPh2 (P(3)O), has been used for the construction of a family of bimetallic complexes [MM'(P(3)O)2](2+) (M = M' = Cu (1), Ag (2), Au (3); M = Au, M' = Cu (4)) and their mononuclear halide congeners M(P(3)O)Hal (M = Cu (5-7), Ag (8-10)). Compounds 1-10 have been characterized in the solid state by single-crystal X-ray diffraction analysis to reveal a variable coordination mode of the phosphine-oxide group of the P(3)O ligand depending on the preferable number of coordination vacancies on the metal center. According to the theoretical studies, the interaction of the hard donor P[double bond, length as m-dash]O moiety with d(10) ions becomes less effective in the order Cu > Ag > Au. 1-10 exhibit room temperature luminescence in the solid state, and the intensity and energy of emission are mostly determined by the nature of metal atoms. The photophysical characteristics of the monometallic species were compared with those of the related compounds M(P(3))Hal (11-16) with the non-oxidized ligand P(3). It was found that in the case of the copper complexes 5-7 the P(3)O hybrid ligand introduces effective non-radiative pathways of the excited state relaxation leading to poor emission, while for the silver luminophores the P[double bond, length as m-dash]O group leads mainly to the modulation of luminescence wavelength. PMID:27530362

  18. 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

  19. 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.

  20. 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).

  1. Photodeposition of Ag or Pt onto TiO2 nanoparticles decorated on step edges of HOPG.

    PubMed

    Taing, James; Cheng, Ming H; Hemminger, John C

    2011-08-23

    Ordered linear arrays of titanium dioxide nanoparticles were fabricated on highly oriented pyrolytic graphite utilizing a step edge decoration method. Ag- or Pt-based nanoparticles were then photodeposited onto the titanium dioxide nanoparticles (∼18 nm) to simultaneously verify photocatalytic activity and to demonstrate a viable route to load the titanium dioxide nanoparticles with metals. Scanning electron microscopy and atomic force microscopy determined the morphology, size, and distribution of the particles. X-ray photoelectron spectroscopy confirmed the identity of the titanium dioxide nanoparticles, and transmission electron microscopy showed that some of the particles were rutile single crystals. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy determined the chemical composition of the metal-based nanoparticles selectively loaded on the linear arrays of titanium dioxide nanoparticles.

  2. Investigation of electrode processes on th Pt/. cap alpha. -AgI boundary with the aid of estance measurements

    SciTech Connect

    Tarasov, A.Y.; Filyaev, A.T.; Karpachev, S.V.; Prusov, V.A.

    1985-10-01

    It was established that elemental silver is deposited on Pt after the latter is brought into contact with AgI and the temperature is held constant. The dependence of the estance on the electrode potential is shown; the potential was varied by causing anodic polarization relative to a silver reference electrode. The profile of the oscillogram presented is described. The decrease of estance may be explained on the basis of the theories on the influence of adsorption process on the estance, if it is assumed that the occurrence of the electrode reaction which results in the appearance of adsorbed iodine on the interface, becomes appreciable at potentials more positive than +130 mV.

  3. Ag/GeSx/Pt-based complementary resistive switches for hybrid CMOS/Nanoelectronic logic and memory architectures

    NASA Astrophysics Data System (ADS)

    van den Hurk, Jan; Havel, Viktor; Linn, Eike; Waser, Rainer; Valov, Ilia

    2013-10-01

    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.

  4. New one-pot synthesis of Au and Ag nanoparticles using green rust reactive particle as a micro-reactor.

    PubMed

    Ayadi, Sondra; Perca, Cristian; Legrand, Ludovic

    2013-01-01

    A new, simple, and fast one-pot synthesis of supported Au or Ag nanoparticles is implemented, for which a reactive Fe(II)-bearing green rust inorganic particle is used as an individual micro-reactor acting as both the reducing agent and support for the resulting metal nanoparticles. The mechanism involves both the solid-state oxidation of the green rust support (sulfate or carbonate) and the reduction-precipitation of soluble metal precursor. The resulting nanohybrids have a platy inorganic part supporting about one to ten nanoparticles with sizes in the 20 to 120 nm range. PMID:23433071

  5. New one-pot synthesis of Au and Ag nanoparticles using green rust reactive particle as a micro-reactor