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Sample records for ag au pd

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

    PubMed

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

    1982-05-01

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

  2. 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

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

    PubMed

    Saitoh, Setsuo; Araki, Yoshima; Taira, Masayuki

    2006-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  5. 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.

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

    PubMed

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

    2016-01-28

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

  7. 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

  8. 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

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

    PubMed

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

    2010-05-01

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

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

    PubMed

    Venkatesan, P; Santhanalakshmi, J

    2010-07-20

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

  11. 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

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

    PubMed

    Niemi, L; Herø, H

    1984-02-01

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

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

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

  15. 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...

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

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

    PubMed

    Endo, Kazuhiko; Ohno, Hiroki; Asakura, Shukuji

    2003-05-01

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

  19. [Fatigue properties of dental alloys. 12% Au-Pd-Ag alloy and type III gold alloy].

    PubMed

    Kato, H

    1989-12-01

    Usually the mechanical properties of dental alloys are determined from the values obtained through static tests of their tensile strength, hardness, etc. Generally, high tensile strength and ductility are preferred. However, when small stresses within proportional limits are applied repeatedly (even though not amounting to destructive forces in static tests), they may cause rupture in the alloy or, at least, cause it to lose its original mechanical properties. This phenomenon is called metal fatigue. It is estimated that the intraoral stress loads received by dental restorations during mastication or during insertion and removal of appliances are repeated more than 3 x 10(5) times/year. From this standpoint, it may be more appropriate to estimate the fracture strength of such dental alloys based on the fatigue properties of the restorative materials used for clasps, bars, and fixed bridges. For this reason, it is necessary to obtain data through fatigue tests on the fatigue strength and the fatigue endurance limits of dental alloys, and it is important to find a correlation between these data and the static data on tensile strengths and ductility obtained by tensile tests. Two alloys are used in these experiments. Both wrought specimens and cast specimens of 12% Au-Pd-Ag and Type III gold alloy were prepared for the fatigue tests. The size of the rectangular wrought specimens was 3 x 4 x 110 mm. The 12% Au-Pd-Ag alloy was heated to 800 degrees C for 15 minutes, quenched, and reheated to 400 degrees C for 20 minutes and quenched again according to the manufacturer's instructions for heat treatment. The Type III gold alloy was heated to 700 degrees C for 10 minutes, quenched, and reheated to 350 degrees C for 20 minutes and quenched again. The cylindrical cast specimens were 60 mm long and 2 mm in diameter. They were invested by conventional methods and cast in a centrifugal casting machine, Thermotrol Model 2500. The four point bending test for the wrought specimen

  20. 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.

  1. 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

  2. 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

  3. Leaching of Au, Ag, and Pd from waste printed circuit boards of mobile phone by iodide lixiviant after supercritical water pre-treatment.

    PubMed

    Xiu, Fu-Rong; Qi, Yingying; Zhang, Fu-Shen

    2015-07-01

    Precious metals are the most attractive resources in waste printed circuit boards (PCBs) of mobile phones. In this work, an alternative process for recovering Au, Ag, and Pd from waste PCBs of mobile phones by supercritical water oxidation (SCWO) pre-treatment combined with iodine-iodide leaching process was developed. In the process, the waste PCBs of mobile phones were pre-treated in supercritical water, then a diluted hydrochloric acid leaching (HL) process was used to recovery the Cu, whose leaching efficiency was approximately 100%, finally the resulting residue was subjected to the iodine-iodide leaching process for recovering the Au, Ag, and Pd. Experimental results indicated that SCWO pre-treatment temperature, time, and pressure had significant influence on the Au, Ag, and Pd leaching from (SCWO+HL)-treated waste PCBs. The optimal SCWO pre-treatment conditions were 420°C and 60min for Au and Pd, and 410°C and 30min for Ag. The optimum dissolution parameters for Au, Pd, and Ag in (SCWO+HL)-treated PCBs with iodine-iodide system were leaching time of 120min (90min for Ag), iodine/iodide mole ratio of 1:5 (1:6 for Ag), solid-to-liquid ratio (S/L) of 1:10g/mL (1:8g/mL for Ag), and pH of 9, respectively. It is believed that the process developed in this study is environment friendly for the recovery of Au, Ag, and Pd from waste PCBs of mobile phones by SCWO pre-treatment combined with iodine-iodide leaching process. PMID:25802060

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. Charge effect in S enhanced CO adsorption: A theoretical study of CO on Au, Ag, Cu, and Pd (111) surfaces coadsorbed with S, O, Cl, and Na

    NASA Astrophysics Data System (ADS)

    Gan, Li-Yong; Zhao, Yu-Jun

    2010-09-01

    The extraordinary sulfur enhanced CO adsorption on Au surface creates curiosity to many scientists in the field, and is expected to have potential applications in catalyst design. In this work, we have investigated the interactions of the coadsorption of CO and various adatoms X (X=Na, S, O, and Cl) on Au and Pd(111) surfaces and made further comparison with CO adsorption on charged Au and Pd surfaces by a first-principles study. We find out that the enhancement of CO adsorption by S on Au originates from S-induced positive polarization of Au surface. The d band of metal atoms in the positively polarized Au surface shifts up toward the Fermi level (EF) without remarkable changes of its shape and occupation. In contrast, in the negatively polarized Au(111) surface, achieved by electropositive adatom such as Na adsorption or artificially adding additional electrons to the substrate, d bands shift down relative to EF, and thus CO adsorption is weakened. Further study of CO coadsorption with X on two other noble metal (Ag and Cu) surfaces manifests that Ag shows the same behavior as Au does, while the situation of Cu is just between that on Au and Pd. It suggests that the extraordinary S-induced enhancement of CO adsorption on Au/Ag, different from other transition metals (TMs), ultimately results from the inertness of d bands buried below EF. The S-induced charge can introduce a significant d band shift on Au/Ag with respect to EF due to their narrow density of states at EF and thus strengthens CO adsorption subsequently.

  9. Clathrates with Me = Mg, Pd, Ni, Au, Ag, Cu, Zn, Al, Sn

    NASA Astrophysics Data System (ADS)

    Wunderlich, Wilfried; Amano, Mao; Matsumura, Yoshihito

    2014-06-01

    Clathrate materials of AlSi, CuSi or NiSi type consisting of abundant elements have a realistic chance of becoming useful thermoelectrics in the near future, because the rattling effect due to their crystal cage structure provides a large figure of merit ZT even in experiments measured under large temperature gradients. In the search for better thermoelectrics, new element combinations in the clathrate type I structure with cubic space group Pm3n were calculated using VASP ab initio software. Predictions of the Seebeck coefficient were made by checking the electronic band structure and density of states for a large variety of input data. For x values around 4 to 6 in the structural formula Ba8Me x Si46- x the substituents Cu, Au, and Ag are best for good thermoelectric behavior, which is discussed in this paper as a result of the low electron-phonon interaction parameter.

  10. 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.

  11. 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.

  12. 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.

  13. DFT study of Hg adsorption on M-substituted Pd(1 1 1) and PdM/γ-Al2O3(1 1 0) (M = Au, Ag, Cu) surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Jiancheng; Yu, Huafeng; Geng, Lu; Liu, Jianwen; Han, Lina; Chang, Liping; Feng, Gang; Ling, Lixia

    2015-11-01

    The adsorption of Hgn (n = 1-3) on the Au-, Ag-, Cu-substituted Pd(1 1 1) surfaces as well as the PdM/γ-Al2O3(1 1 0) (M = Au, Ag, Cu) surfaces has been investigated using spin-polarized density functional theory calculations. It is found that M-substituted Pd(1 1 1) surfaces show as good Hg adsorption capacity as the perfect Pd(1 1 1) at low Hg coverage, while the Hg adsorption capacity is only slightly weakened at high Hg coverage. On the basis of stepwise adsorption energies analysis, it is concluded that M-substituted Pd(1 1 1) surfaces can contribute to the binding of Hg atom on the surfaces at high Hg coverage. The electronic properties of the second metal atoms are the main factor contributes to the Hg adsorption capacity. Gas phase Pd2 shows better Hg adsorption capacity than Pd2/γ-Al2O3, while PdM/γ-Al2O3 can adsorb Hg more efficiently than bare PdM clusters. It suggests that the γ-Al2O3 support can enhance the activity of PdM for Hg adsorption and reduces the activity of Pd2. It is also found that Pd is the main active composition responsible for the interaction of mercury with the surface for PdM/γ-Al2O3 sorbent. Taking Hg adsorption capacity and economic costs into account, Cu addition is a comparatively good candidate for Hg capture.

  14. 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.

  15. [Study on the age-hardenable silver alloy (3 rd report). III. On the ageing process of dental Ag-Pd-Cu-Au alloy (author's transl)].

    PubMed

    Ota, M; Hisatsune, K; Yamane, M

    1975-05-01

    The precipitation hardening process of a dental silver base alloy, Ag-28 Pd-10 Cu-12 wt % Au, was studied by means of X-ray diffraction, hardness measurement and metallographic observations. After solution treatment at 900 degrees C for 30 min, specimens were subjected to anisothermal annealing at the rate of 1 degrees C/min. PdCu ordered phase and alpha2 solid solution (Ag rich phase) precipitated hetelogeneously at the grain boundaries and then grew up into each grain. Drastic increase in hardness was recognized with the spread of nodular region. Electron microscopic observation of these precipitates showed very fine lamellar structure. It is concluded that the age hardening of this alloy could be attributed to this grain boundary precipitation and the softening at the overaged stage to the second grain boundary reaction which produced very coarse lamellar structure. PMID:1058263

  16. 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

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  19. 2-(Aminomethyl)phenyl complexes of Au(III), mixed Au(III)/Ag(I), and Pd(II) with the 2,2-diacetyl-1,1-ethylenedithiolato ligand: dancing of palladacycles around a juggler ligand.

    PubMed

    Vicente, José; Chicote, María-Teresa; Martínez-Viviente, Eloísa; Martínez-Martínez, Antonio-Jesús; Sánchez-Moya, Nicolás; Jones, Peter G

    2010-09-01

    The reaction of [Tl(2){mu-S,S-S(2)C=C{C(O)Me}(2)}] with [Au(C,N-C(6)H(4)CH(2)NMe(2)-2)Cl(2)] (1:1) gives [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{S,S-S(2)C=C{C(O)Me}(2)}] (1) which, in turn, reacts with AgClO(4) (1:1) to give [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{Ag(OClO(3))}{S(2)C=C{C(O)Me}(2)}] (2). Complexes [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{Ag(X)(PPh(3))}{S(2)C=C{C(O)Me}(2)}] [X = OClO(3) (3), ONO(2) (4)] have been obtained by reaction of 1 with PPh(3) and AgClO(4) or AgNO(3), respectively (1:1:1). Complex 3 can also be obtained by reacting 2 with PPh(3) (1:1). Complexes [Pd(C,N-C(6)H(4)CH(2)NR(2)-2)(mu-Cl)](2) (R = Me, H) react (i) with [Tl(2){S(2)C=C{C(O)Me}(2)}] and [PPN]Cl (0.5:1:1, PPN = Ph(3)P=N=PPh(3)) to form PPN[Pd(C,N-C(6)H(4)CH(2)NR(2)-2){S,S-S(2)C=C{C(O)Me}(2)}] [R = H (5a), Me (5b)], or (ii) with [Tl(2){S(2)C=C{C(O)Me}(2)}] (1:1) to form [{Pd(C,N-C(6)H(4)CH(2)NR(2)-2)}(2){mu-S,S,O-S(2)C=C{C(O)Me}(2)}] [R = H (6a), Me (6b)]. The trinuclear complexes [{Pd(C,N-C(6)H(4)CH(2)NR(2)-2)}(3){mu(3)-O,S,S,O-S(2)C=C{C(O)Me}(2)}]ClO(4) [R = H (7a), Me (7b)] can be prepared by reacting the corresponding dinuclear complex 6a or 6b with [Pd(C,N-C(6)H(4)CH(2)NR(2)-2)(NCMe)(2)]ClO(4) (1:1). The crystal structures of 1, 6b x CH(2)Cl(2), and 7b x CH(2)Cl(2) have been determined. NMR studies have been carried out to explain the solution behavior of these complexes. VT-NMR and line shape analysis for the species where R = Me (5b, 6b, 7b) have allowed the estimation of the activation parameters for these exchange processes. PMID:20799741

  20. 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

  1. Designer electrode interfaces simultaneously comprising three different metal nanoparticle (Au, Ag, Pd)/carbon microsphere/carbon nanotube composites: progress towards combinatorial electrochemistry.

    PubMed

    Dai, Xuan; Wildgoose, Gregory G; Compton, Richard G

    2006-11-01

    In this report gold, silver and palladium metal nanoparticles are separately supported on glassy carbon microspheres (GCM) using bulk electroless deposition techniques to produce three different materials labelled as GCM-Au, GCM-Ag and GCM-Pd respectively. These three materials are then combined together into a composite film on a glassy carbon (GC) electrode surface using multiwalled carbon nanotubes (MWCNTs). The MWCNTs serve to not only mechanically support this composite film as a "binder" but they also help to "wire up" each modified GCM to the underlying substrate. The intelligently designed structure of this electrode interface allows this single modified electrode to simultaneously behave as if it were a macrodisc electrode constructed of gold, silver or palladium, whilst using only a fraction of the equivalent amount of these precious metals. Furthermore this unique structure allows the possibility of combinatorial electrochemistry to be realised using a relatively facile electrode construction which avoids the problems of alloy formation, co-deposition and the formation of bimetallic species. For instance a mixture of several different analytes, which can each only be detected on a different specific substrate, can simultaneously be determined using one electrode in a single voltammetric experiment! Alternatively a substrate could undergo electrocatalytic reactions on one substrate, whilst the products, and hence the progress of this reaction, can be studied at a different substrate simultaneously at the same electrode surface. Proof-of-concept examples are presented herein and the designer electrode interface is shown to produce analytical responses to model target analytes such as hydrazine, bromide and thallium(I) ions that are comparable, if not better, than those obtained at metal macrodisc electrodes and even at other state-of-the-art nanoparticle modified electrodes. PMID:17066193

  2. Au@Pd core-shell nanobricks with concave structures and their catalysis of ethanol oxidation.

    PubMed

    Wang, Wenjin; Zhang, Jie; Yang, Shengchun; Ding, Bingjun; Song, Xiaoping

    2013-10-01

    Au@Pd core-shell nanobricks (CNBs) with concave surfaces and Pd shells with a thickness of approximately 5 nm were synthesized by co-reduction of HAuCl4 and H2 PdCl4 in the presence of Au seeds and Ag ions. These as-synthesized concave CNBs exhibit significantly enhanced catalytic activity for the electrooxidation of ethanol in alkaline media compared to the commercially-used Pd black. The improved performance of the Au@Pd CNBs can be attributed to the exposed stepped surfaces, high-index facets, and the synergistic effects of the core and shell metals. PMID:23929810

  3. Bimetallic Pt-Ag and Pd-Ag nanoparticles

    SciTech Connect

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

    2005-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

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

    SciTech Connect

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

    2011-05-11

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

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

    SciTech Connect

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

    2011-06-16

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

  7. 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.

  8. 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.

  9. Screening on binary Zr-1X (X = Ti, Nb, Mo, Cu, Au, Pd, Ag, Ru, Hf and Bi) alloys with good in vitro cytocompatibility and magnetic resonance imaging compatibility.

    PubMed

    Zhou, F Y; Qiu, K J; Li, H F; Huang, T; Wang, B L; Li, L; Zheng, Y F

    2013-12-01

    In this study, the microstructures, mechanical properties, corrosion behaviors, in vitro cytocompatibility and magnetic susceptibility of Zr-1X alloys with various alloying elements, including Ti, Nb, Mo, Cu, Au, Pd, Ag, Ru, Hf and Bi, were systematically investigated to explore their potential use in biomedical applications. The experimental results indicated that annealed Zr-1X alloys consisted entirely or primarily of α phase. The alloying elements significantly increased the strength and hardness of pure Zr and had a relatively slight influence on elastic modulus. Ru was the most effective enhancing element and Zr-1Ru alloy had the largest elongation. The results of electrochemical corrosion indicated that adding various elements to Zr improved its corrosion resistance, as indicated by the reduced corrosion current density. The extracts of the studied Zr-1X alloys produced no significant deleterious effects on osteoblast-like cells (MG 63), indicating good in vitro cytocompatibility. All except for Zr-1Ag alloy showed decreased magnetic susceptibility compared to pure Zr, and Zr-1Ru alloy had the lowest magnetic susceptibility value, being comparable to that of α' phase Zr-Mo alloy and Zr-Nb alloy and far lower than that of Co-Cr alloy and Ti-6Al-4V alloy. Among the experimental Zr-1X alloys, Zr-1Ru alloy possessing high strength coupled with good ductility, good in vitro cytocompatibility and low magnetic susceptibility may be a good candidate alloy for medical devices within a magnetic resonance imaging environment. PMID:23928334

  10. Depletion and phase transformation of a submicron Ni(P) film in the early stage of soldering reaction between Sn-Ag-Cu and Au/Pd(P)/Ni(P)/Cu

    NASA Astrophysics Data System (ADS)

    Ho, Cheng-En; Hsieh, Wan-Zhen; Yang, Tsung-Hsun

    2015-01-01

    The early stage of soldering reaction between Sn-3Ag-0.5Cu solder and ultrathin-Ni(P)-type Au/Pd(P)/Ni(P)/Cu pad was investigated by field-emission scanning electron microscopy (FE-SEM) in conjunction with field-emission electron probe microanalysis (FEEPMA) and high-resolution transmission electron microscopy (HRTEM). FE-SEM, FE-EPMA, and HRTEM investigations showed that Ni2SnP and Ni3P were the predominant P-containing intermetallic compounds (IMCs) in the soldering reaction and that their growth behaviors strongly depended on the depletion of Ni(P). The growth of Ni3P dominated over that of Ni2SnP in the early stage of soldering, whereas the Ni3P gradually transformed into Ni2SnP after Ni(P) depletion. This Ni(P)-depletion-induced Ni2SnP growth behavior is different from the reaction mechanisms reported in the literature. Detailed analyses of the microstructural evolution of the IMC during Ni(P) depletion were conducted, and a two-stage reaction mechanism was proposed to rationalize the unique IMC growth behavior.

  11. 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

  12. Substrate-bound growth of Au-Pd diblock nanowire and hybrid nanorod-plate

    NASA Astrophysics Data System (ADS)

    He, Jiating; Wang, Yawen; Fan, Zhanxi; Lam, Zhenhui; Zhang, Hua; Liu, Bin; Chen, Hongyu

    2015-04-01

    We expand the scope of the previously developed Active Surface Growth mode for growing substrate-bound ultrathin Pd (d = 4 nm) and Ag nanowires (d = 30 nm) in aqueous solution under ambient conditions. Using Au nanorods as the seeds, selective growth at the contact line between the rod and the substrate eventually leads to an attached Pd nanoplate. The unique growth mode also allows sequential growth of different materials via a single seed, giving substrate-bound Au-Pd diblock nanowires. The new abilities to use seed shape to pre-define the active sites and to apply sequential growth open windows for new pathways to hybrid nanostructures.We expand the scope of the previously developed Active Surface Growth mode for growing substrate-bound ultrathin Pd (d = 4 nm) and Ag nanowires (d = 30 nm) in aqueous solution under ambient conditions. Using Au nanorods as the seeds, selective growth at the contact line between the rod and the substrate eventually leads to an attached Pd nanoplate. The unique growth mode also allows sequential growth of different materials via a single seed, giving substrate-bound Au-Pd diblock nanowires. The new abilities to use seed shape to pre-define the active sites and to apply sequential growth open windows for new pathways to hybrid nanostructures. Electronic supplementary information (ESI) available: Supporting TEM and SEM images of control experiments with different reaction conditions and another type of diblock nanowires. See DOI: 10.1039/c5nr00361j

  13. Probing the rupture of a Ag atomic junction in a Ag-Au mixed electrode

    NASA Astrophysics Data System (ADS)

    Kim, Taekyeong

    2015-09-01

    We probed that the atomic junction in Ag part ruptures during stretching of atomic sized contacts of Ag-Au mixed electrodes, resulting in Ag-Ag electrodes through a scanning tunneling microscope breaking junction (STM-BJ) technique. We observed that the conductance and tunneling decay constant for a series of amine-terminated oligophenyl molecular junctions are essentially the same for the Ag-Au mixed and the Ag-Ag electrodes. We also found the molecular plateau length and the evolution patterns with the Ag-Au mixed electrodes are similar to those with Ag-Ag electrodes rather than the Au-Au electrodes in the molecular junction elongation. This result is attributed to the smaller binding energy of Ag atoms compared to that of Au atoms, so the Ag junction part is more easily broken than that of Au part in stretching of Ag-Au mixed electrodes. Furthermore, we successfully observed that the rupture force of the atomic junction for the Ag-Au mixed electrodes was identical to that for the Ag-Ag electrodes and smaller than that for the Au-Au electrodes. This study may advance the understanding of the electrical and the mechanical properties in molecular devices with Ag and Au electrodes in future.

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

    SciTech Connect

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

    2012-10-15

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

  15. Strain effects on ensemble populations in AuPd/Pd(100) surface alloys

    NASA Astrophysics Data System (ADS)

    Stephens, J. Adam; Hwang, Gyeong S.

    2013-10-01

    The effects of applied strain on the arrangement of atoms in AuPd/Pd(100) surface alloys are studied using Monte Carlo simulations and cluster expansion Hamiltonians. The strain effects are found to be significant, with heteronuclear (Au-Pd) interactions more strongly enhanced by biaxial compression than homonuclear (Pd-Pd) ones. In particular, compressive strain causes an increase in the population of Pd monomers and second nearest-neighbor pairs of Pd monomers, both of which have been identified previously as important ensembles for various catalytic reactions. We also discuss the origin of these effects using density functional theory calculations of the surface electronic structure of strained AuPd/Pd(100).Our findings may suggest an additional means of employing strain to tune the catalytic properties of surface alloys.

  16. 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. PMID:26611172

  17. Steering epitaxial alignment of Au, Pd, and AuPd nanowire arrays by atom flux change.

    PubMed

    Yoo, Youngdong; Seo, Kwanyong; Han, Sol; Varadwaj, Kumar S K; Kim, Hyun You; Ryu, Ji Hoon; Lee, Hyuck Mo; Ahn, Jae Pyoung; Ihee, Hyotcherl; Kim, Bongsoo

    2010-02-10

    We have synthesized epitaxial Au, Pd, and AuPd nanowire arrays in vertical or horizontal alignment on a c-cut sapphire substrate. We show that the vertical and horizontal nanowire arrays grow from half-octahedral seeds by the correlations of the geometry and orientation of seed crystals with those of as-grown nanowires. The alignment of nanowires can be steered by changing the atom flux. At low atom deposition flux vertical nanowires grow, while at high atom flux horizontal nanowires grow. Similar vertical/horizontal epitaxial growth is also demonstrated on SrTiO(3) substrates. This orientation-steering mechanism is visualized by molecular dynamics simulations. PMID:20050692

  18. Effect of Ag Templates on the Formation of Au-Ag Hollow/Core-Shell Nanostructures

    NASA Astrophysics Data System (ADS)

    Tsai, Chi-Hang; Chen, Shih-Yun; Song, Jenn-Ming; Haruta, Mitsutaka; Kurata, Hiroki

    2015-11-01

    Au-Ag alloy nanostructures with various shapes were synthesized using a successive reduction method in this study. By means of galvanic replacement, twined Ag nanoparticles (NPs) and single-crystalline Ag nanowires (NWs) were adopted as templates, respectively, and alloyed with the same amount of Au+ ions. High angle annular dark field-scanning TEM (HAADF-STEM) images observed from different rotation angles confirm that Ag NPs turned into AuAg alloy rings with an Au/Ag ratio of 1. The shifts of surface plasmon resonance and chemical composition reveal the evolution of the alloy ring formation. On the other hand, single-crystalline Ag NWs became Ag@AuAg core-shell wires instead of hollow nanostructure through a process of galvanic replacement. It is proposed that in addition to the ratio of Ag templates and Au ion additives, the twin boundaries of the Ag templates were the dominating factor causing hollow alloy nanostructures.

  19. Effect of Ag Templates on the Formation of Au-Ag Hollow/Core-Shell Nanostructures.

    PubMed

    Tsai, Chi-Hang; Chen, Shih-Yun; Song, Jenn-Ming; Haruta, Mitsutaka; Kurata, Hiroki

    2015-12-01

    Au-Ag alloy nanostructures with various shapes were synthesized using a successive reduction method in this study. By means of galvanic replacement, twined Ag nanoparticles (NPs) and single-crystalline Ag nanowires (NWs) were adopted as templates, respectively, and alloyed with the same amount of Au(+) ions. High angle annular dark field-scanning TEM (HAADF-STEM) images observed from different rotation angles confirm that Ag NPs turned into AuAg alloy rings with an Au/Ag ratio of 1. The shifts of surface plasmon resonance and chemical composition reveal the evolution of the alloy ring formation. On the other hand, single-crystalline Ag NWs became Ag@AuAg core-shell wires instead of hollow nanostructure through a process of galvanic replacement. It is proposed that in addition to the ratio of Ag templates and Au ion additives, the twin boundaries of the Ag templates were the dominating factor causing hollow alloy nanostructures. PMID:26563266

  20. Biosupported Bimetallic Pd Au Nanocatalysts for Dechlorination of Environmental Contaminants

    SciTech Connect

    De Corte, S.; Fitts, J.; Hennebel, T.; Sabbe, T.; Bliznuk, V.; Verschuere, S.; van der Lelie, D.; Verstraete, W.; Boon, N.

    2011-08-30

    Biologically produced monometallic palladium nanoparticles (bio-Pd) have been shown to catalyze the dehalogenation of environmental contaminants, but fail to efficiently catalyze the degradation of other important recalcitrant halogenated compounds. This study represents the first report of biologically produced bimetallic Pd/Au nanoparticle catalysts. The obtained catalysts were tested for the dechlorination of diclofenac and trichloroethylene. When aqueous bivalent Pd(II) and trivalent Au(III) ions were both added to concentrations of 50 mg L{sup -1} and reduced simultaneously by Shewanella oneidensis in the presence of H{sub 2}, the resulting cell-associated bimetallic nanoparticles (bio-Pd/Au) were able to dehalogenate 78% of the initially added diclofenac after 24 h; in comparison, no dehalogenation was observed using monometallic bio-Pd or bio-Au. Other catalyst-synthesis strategies did not show improved dehalogenation of TCE and diclofenac compared with bio-Pd. Synchrotron-based X-ray diffraction, (scanning) transmission electron microscopy and energy dispersive X-ray spectroscopy indicated that the simultaneous reduction of Pd and Au supported on cells of S. oneidensis resulted in the formation of a unique bimetallic crystalline structure. This study demonstrates that the catalytic activity and functionality of possibly environmentally more benign biosupported Pd-catalysts can be improved by coprecipitation with Au.

  1. 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.

  2. Versatile and efficient catalysts for energy and environmental processes: Mesoporous silica containing Au, Pd and Au-Pd

    NASA Astrophysics Data System (ADS)

    da Silva, Anderson G. M.; Fajardo, Humberto V.; Balzer, Rosana; Probst, Luiz F. D.; Lovón, Adriana S. P.; Lovón-Quintana, Juan J.; Valença, Gustavo P.; Schreine, Wido H.; Robles-Dutenhefner, Patrícia A.

    2015-07-01

    We described a versatile approach for the synthesis of Au/MCM-41, Pd/MCM-41 and Au-Pd/MCM-41 by the direct incorporation of the noble metals into the MCM-41 framework. The structural, textural and chemical properties were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), N2-adsorption (BET and BJH methods), H2-chemisorption, small angle X-ray scattering (SAXS), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). The nanomaterials, being comprised of Au, Pd and Au-Pd nanoparticles and possessing high surface areas were applied as versatile and efficient catalysts in benzene, toluene and o-xylene (BTX) oxidation and in the steam reforming of ethanol for hydrogen production. The results revealed that the catalytic behavior in both processes was influenced by the experimental conditions and the nature of the catalyst employed. The Au-Pd/MCM-41 catalyst was the most active in the BTX total oxidation. On the basis of characterization data, it was proposed that the close contact between Pd and Au and the higher dispersion of Pd may be responsible for the enhanced activity of the bimetallic catalyst. However, the strong interaction between the noble metals did not improve the performance of the bimetallic catalyst in ethanol steam reforming, the Pd/MCM-41 catalyst being the most active and selective for hydrogen production.

  3. The growth and enhanced catalytic performance of Au@Pd core-shell nanodendrites

    NASA Astrophysics Data System (ADS)

    Wang, Haihua; Sun, Zhenhua; Yang, Yi; Su, Dangsheng

    2012-12-01

    Au@Pd core-shell nanodendrites were synthesized by reducing H2PdCl4 with ascorbic acid onto the surface of Au polyhedra at room temperature. The Au@Pd core-shell nanodendrites consisting of a Au core and nanoporous Pd shell, exhibited plasmonic properties and higher catalytic activity in comparison with Au@Pd core-shell nanocubes.Au@Pd core-shell nanodendrites were synthesized by reducing H2PdCl4 with ascorbic acid onto the surface of Au polyhedra at room temperature. The Au@Pd core-shell nanodendrites consisting of a Au core and nanoporous Pd shell, exhibited plasmonic properties and higher catalytic activity in comparison with Au@Pd core-shell nanocubes. Electronic supplementary information (ESI) available: Experimental details, characterization and catalytic performance measurement of Au nanopolyhedra and Au@Pd core-shell nanostructures, TEM image of Au nanopolyhedra and Au@Pd core-shell nanodendrites after four cycles of the Suzuki coupling reaction, TEM and high-resolution images of a single Au@Pd core-shell nanodendrite, and XRD pattern of Au@Pd core-shell nanodendrites, UV-vis spectrum of Au@Pd nanodendrites in the range 200-400 nm, references. See DOI: 10.1039/c2nr32849f

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

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

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

  5. Synthesis and Catalytic Properties of Au Pd Nanoflowers

    SciTech Connect

    Xu, Jianguang; Wilson, Adria; Howe, Jane Y; Chi, Miaofang; Wiley, Benjamin J

    2011-01-01

    Reduction of Pd ions by hydroquinone in the presence of gold nanoparticles and polyvinylpyrrolidone resulted in the formation of nanoflowers with a Au core and Pd petals. Addition of HCl to the synthesis halted the reduction by hydroquinone and enabled the acquisition of snapshots of the nanoflowers at different stages of growth. TEM images of the reaction after 10 s show that the nanoflower morphology resulted from the homogeneous nucleation of Pd clusters in solution and their subsequent attachment to gold seeds coated with a thin (0.8 0.1 nm) shell of Pd. UV visible spectra also indicate Pd clusters formed in the early stages of the reaction and disappeared as the nanoflowers grew. The speed at which this reaction can be halted is useful not only for producing a variety of bimetallic nanostructures with precisely controlled dimensions and morphologies but also for understanding the growth mechanism of these structures. The ability of the AuPd core shell structure to catalyze the Suzuki coupling reaction of iodobenzene to phenylboronic acid was probed and compared against the activity of Pd nanocubes and thin-shelled AuPd core shell nanoparticles. The results of this study suggest that Suzuki coupling was not affected by the surface structure or subsurface composition of the nanoparticles, but instead was primarily catalyzed by molecular Pd species that leached from the nanostructures.

  6. Synthesis of Au-Pd Nanoflowers Through Nanocluster Assembly

    SciTech Connect

    Xu, Jianguang; Howe, Jane Y; Chi, Miaofang; Wilson, Adria; Rathmall, Aaron; Wiley, Benjamin J

    2011-01-01

    Reduction of Pd ions by hydroquinone in the presence of gold nanoparticles and polyvinylpyrrolidone resulted in the formation of nanoflowers with a Au core and Pd petals. Addition of HCl to the synthesis halted the reduction by hydroquinone and enabled the acquisition of snapshots of the nanoflowers at different stages of growth. TEM images of the reaction after 10 s show that the nanoflower morphology resulted from the homogeneous nucleation of Pd clusters in solution and their subsequent attachment to gold seeds coated with a thin (0.8 {+-} 0.1 nm) shell of Pd. UV-visible spectra also indicate Pd clusters formed in the early stages of the reaction and disappeared as the nanoflowers grew. The speed at which this reaction can be halted is useful not only for producing a variety of bimetallic nanostructures with precisely controlled dimensions and morphologies but also for understanding the growth mechanism of these structures. The ability of the AuPd core-shell structure to catalyze the Suzuki coupling reaction of iodobenzene to phenylboronic acid was probed and compared against the activity of Pd nanocubes and thin-shelled AuPd core-shell nanoparticles. The results of this study suggest that Suzuki coupling was not affected by the surface structure or subsurface composition of the nanoparticles, but instead was primarily catalyzed by molecular Pd species that leached from the nanostructures.

  7. Optical absorption engineering in stacked plasmonic Au-SiO₂-Pd nanoantennas.

    PubMed

    Wadell, Carl; Antosiewicz, Tomasz J; Langhammer, Christoph

    2012-09-12

    The nonradiative decay of a localized surface plasmon through absorption of a captured photon and excitation of an energetic electron-hole pair is a potentially very effective way to enhance chemical reactions on metal nanoparticle surfaces, so far limited to Ag (and Au). Here we explore the possibility of efficient and spectrally widely tunable optical absorption engineering based on heterometallic optical nanoantennas. They consist of an optimized antenna element made of Au (or Ag) and a catalytically active second metallic element separated by a thin SiO(2) layer. Specifically, we find that stacked Au-SiO(2)-Pd nanodisk antennas exhibit pronounced local absorption enhancement in the catalytic Pd particle. The effect is caused by efficient power transfer from the Au disk, exhibiting a narrow low-loss resonance and acting as an antenna collecting photons, to the Pd disk due to strong coupling between the two. The Pd element thus acts as receiver that efficiently dissipates energy into electron-hole pairs owing to efficient coupling to intra and interband transitions. In fact, the energy transfer is found to be so effective that the absorption efficiency at a given wavelength can be enhanced up to 6 to 9 times, and the total absorption integrated over a wide spectral range (400-900 nm) up to 2-fold, depending on the antenna dimensions. This finding suggests a novel route toward highly efficient plasmon-enhanced catalysis on widely selectable catalytic metal particle surfaces not limited to the "classic" plasmonic metals Au and Ag. PMID:22916998

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

    PubMed

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

    2016-07-14

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

  9. Laser generated Ag and Ag-Au composite nanoparticles for refractive index sensor

    NASA Astrophysics Data System (ADS)

    Navas, M. P.; Soni, R. K.

    2014-09-01

    Localized surface plasmon resonance (LSPR) wavelength of metal nanoparticles (NPs) is highly sensitive to size, shape and the surrounding medium. Metal targets were laser ablated in liquid for preparation of spherical Ag and Ag@Au core-shell NP colloidal solution for refractive index sensing. The LSPR peak wavelength and broadening of the NPs were monitored in different refractive index liquid. Quasi-static Mie theory simulation results show that refractive index sensitivity of Ag, Ag-Au alloy and Ag@Au core-shell NPs increases nearly linearly with size and shell thickness. However, the increased broadening of the LSPR peak with size, alloy concentration and Au shell thickness restricts the sensing resolution of these NPs. Figure-of-merit (FOM) was calculated to optimize the size of Ag NPs, concentration of Ag-Au alloy NPs and Au shell thickness of Ag@Au core-shell NPs. The refractive index sensitivity (RIS) and FOM were optimum in the size range 20-40 nm for Ag NPs. Laser generated Ag@Au NPs of Au shell thickness in the range of 1-2 nm showed optimum FOM, where thin layer of Au coating can improve the stability of Ag NPs.

  10. 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

  11. 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

  12. Interfacial nanodroplets guided construction of hierarchical Au, Au-Pt, and Au-Pd particles as excellent catalysts.

    PubMed

    Ma, Aijing; Xu, Jie; Zhang, Xuehua; Zhang, Bin; Wang, Dayang; Xu, Haolan

    2014-01-01

    Interfacial nanodroplets were grafted to the surfaces of self-sacrificed template particles in a galvanic reaction system to assist the construction of 3D Au porous structures. The interfacial nanodroplets were formed via direct adsorption of surfactant-free emulsions onto the particle surfaces. The interfacial nanodroplets discretely distributed at the template particle surfaces and served as soft templates to guide the formation of porous Au structures. The self-variation of footprint sizes of interfacial nanodroplets during Au growth gave rise to a hierarchical pore size distribution of the obtained Au porous particles. This strategy could be easily extended to synthesize bimetal porous particles such as Au-Pt and Au-Pd. The obtained porous Au, Au-Pt, and Au-Pd particles showed excellent catalytic activity in catalytic reduction of 4-nitrophenol. PMID:24797697

  13. Crystal Structure of the PdAu24(SR)18(0) Superatom.

    PubMed

    Tofanelli, Marcus A; Ni, Thomas W; Phillips, Billy D; Ackerson, Christopher J

    2016-02-01

    The single-crystal X-ray structure of Pd-doped Au25(SR)18 was solved. The crystal structure reveals that in PdAu24(SR)18, the Pd atom is localized only to the centroid of the Au25(SR)18 cluster. This single-crystal X-ray structure shows that PdAu24(SR)18(0) is well conceptualized with the superatom theory. The PdAu24(SR)18(0) charge state is isoelectronic with Au25(SR)18(+1) as determined by a first order Jahn-Teller effect of similar magnitude and by electrochemical comparison. The previously reported increased stability of PdAu24(SR)18 can be rationalized in terms of Pd-Au bonds that are shorter than the Au-Au bonds in Au25(SR)18. PMID:26760220

  14. Using supported Au nanoparticles as starting material for preparing uniform Au/Pd bimetallic catalysts

    SciTech Connect

    Villa, Alberto; Prati, Laura; Su, Dangshen; Wang, Di; Veith, Gabriel M

    2010-01-01

    One of the best methods for producing bulk homogeneous (composition) supported bimetallic AuPd clusters involves the immobilization of a protected Au seed followed by the addition of Pd. This paper investigates the importance of this gold seed in controlling the resulting bimetallic AuPd clusters structures, sizes and catalytic activities by investigating three different gold seeds. Uniform Au-Pd alloy were obtained when a steric/electrostatic protecting group, poly(vinyl alcohol) (PVA), was used to form the gold clusters on activated carbon (AC). In contrast Au/AC precursors prepared using Au nanoparticles with only electrostatic stabilization (tetrakis(hydroxypropyl)phosphonium chloride (THPC)), or no stabilization (magnetron sputtering) produced inhomogeneous alloys and segregation of the gold and palladium. The uniform alloyed catalyst (Pd{at}Au{sub PVA}/AC) is the most active and selective catalyst, while the inhomogenous catalysts are less active and selective. Further study of the PVA protected Au clusters revealed that the amount of PVA used is also critical for the preparation of uniform alloyed catalyst, their stability, and their catalytic activity.

  15. Pd versus Au as evaporated metal contacts to molecules

    SciTech Connect

    Haick, Hossam; Ghabboun, Jamal; Cahen, David

    2005-01-24

    Indirect e-beam evaporation of metal on a cooled substrate that allows making reproducible and gentle electrical contact to molecular films of organic molecules yields strikingly different results with Pd and Au. This is attributed to different growth modes of the metals, which lead to different molecule/metal interactions and to Au penetration in between the molecules. These differences can radically change the effect of the molecules on the resulting junctions.

  16. Bimetallic Pt-Ag and Pd-Ag nanoparticles

    SciTech Connect

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

    2005-04-19

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

  17. 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.

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

    PubMed

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

    2015-06-01

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

  19. Deposition of Au and Ag nanoparticles on PEDOT.

    PubMed

    Danieli, Tamar; Colleran, John; Mandler, Daniel

    2011-12-01

    The deposition of Au and Ag, locally and from bulk solution, on poly(3,4-ethylenedioxythiophene) (PEDOT) was studied. Specifically, PEDOT was electrochemically polymerized onto a glassy carbon (GC) electrode and used for bulk deposition of Au and Ag from their respective ions dissolved in the solution as well as for the local deposition of these metals using scanning electrochemical microscopy (SECM). These two sets of experiments were utilized to investigate the difference between Au and Ag electrochemical deposition on PEDOT. In particular, SECM experiments, which were conducted by the controlled anodic dissolution of Au and Ag microelectrodes close to GC/PEDOT, probed the effect of different PEDOT oxidation states on local deposition. The current-time transients recorded during the deposition, combined with scanning electron microscopy and EDX analysis provided insight into the reduction processes. AuCl(4)(-) and Ag(+) ions were electrochemically reduced at a potential equal to and more negative than the ions redox potentials (0.4 and 0.2 V, respectively) and more positive than -0.7 V, where the PEDOT starts transforming into the reduced, i.e. insulating, state. We found that the electroreduction of Ag(+) ions was diffusion-controlled and the PEDOT film served as a simple conductor. On the other hand, the reduction of AuCl(4)(-) ions was enhanced on GC/PEDOT as compared with bare GC, indicating that PEDOT catalyzes the reduction of AuCl(4)(-) to Au. PMID:21993698

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

    SciTech Connect

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

    2013-10-21

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

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

    PubMed

    Philip, Daizy

    2009-07-15

    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 approximately 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 (111) 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. PMID:19324587

  2. 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.

  3. Selective Hydrogenation of Acetylene over Pd, Au, and PdAu Supported Nanoparticles

    NASA Astrophysics Data System (ADS)

    Walker, Michael P.

    The removal of trace amounts of acetylene in ethylene streams is a high-volume industrial process that must possess high selectivity of alkyne hydrogenation over hydrogenation of alkenes. Current technology uses metallic nanoparticles, typically palladium or platinum, for acetylene removal. However, problems arise due to the deactivation of the catalysts at high temperatures as well as low selectivities at high conversions. Pore expanded MCM-41 is synthesized via a two-step strategy in which MCM-41 was prepared via cetyltrimethylammonium bromide (CTMABr) followed by the hydrothermal treatment with N,N-dimethyldecylamine (DMDA). This material was washed with ethanol to remove DMDA, or calcined to remove both surfactants. PE-MCM-41 based materials were impregnated with palladium, gold, and palladium-gold nanoparticles. The removal of DMDA had an effect on both the conversion and selectivity, in which they were found to drop significantly. However, by using the bimetallic PdAu catalysts, higher selectivity could be achieved due to increased electron density.

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

    PubMed

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

    2016-08-17

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

  5. 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

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

    PubMed

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

    2014-10-21

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

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

    SciTech Connect

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

    2008-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  9. Fermi surfaces of surface states on Si(111)-Ag, Au

    NASA Astrophysics Data System (ADS)

    Crain, J. N.; Altmann, K. N.; Bromberger, C.; Himpsel, F. J.

    2002-11-01

    Metallic surface states on semiconducting substrates provide an opportunity to study low-dimensional electrons decoupled from the bulk. Angle resolved photoemission is used to determine the Fermi surface, group velocity, and effective mass for surface states on Si(111)(3)×(3)-Ag, Si(111)(3)×(3)-Au, and Si(111)(21)×(21)-(Ag+Au). For Si(111)(3)×(3)-Ag the Fermi surface consists of small electron pockets populated by electrons from a few % excess Ag. For Si(111)(21)×(21)-(Ag+Au) the pockets increase their size corresponding to a filling by three electrons per unit cell. The (21)×(21) superlattice leads to an intricate surface umklapp pattern and to minigaps of 110 meV, giving an interaction potential of 55 meV for the (21)×(21) superlattice.

  10. 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.

  11. 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.

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

    PubMed

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

    2016-01-01

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

  13. 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.

  14. 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.

  15. Hysteresis-free nanoplasmonic Pd-Au alloy hydrogen sensors.

    PubMed

    Wadell, Carl; Nugroho, Ferry Anggoro Ardy; Lidström, Emil; Iandolo, Beniamino; Wagner, Jakob B; Langhammer, Christoph

    2015-05-13

    The recent market introduction of hydrogen fuel cell cars and the prospect of a hydrogen economy have drastically accelerated the need for safe and accurate detection of hydrogen. In this Letter, we investigate the use of arrays of nanofabricated Pd-Au alloy nanoparticles as plasmonic optical hydrogen sensors. By increasing the amount of Au in the alloy nanoparticles up to 25 atom %, we are able to suppress the hysteresis between hydrogen absorption and desorption, thereby increasing the sensor accuracy to below 5% throughout the investigated 1 mbar to 1 bar hydrogen pressure range. Furthermore, we observe an 8-fold absolute sensitivity enhancement at low hydrogen pressures compared to sensors made of pure Pd, and an improved sensor response time to below one second within the 0-40 mbar pressure range, that is, below the flammability limit, by engineering the nanoparticle size. PMID:25915663

  16. Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Hsu, Chiajen; Huang, Chienwen; Hao, Yaowu; Liu, Fuqiang

    2013-03-01

    A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet-visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies.

  17. Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation

    PubMed Central

    2013-01-01

    A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet–visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies. PMID:23452438

  18. Enhanced optical responses of Au@Pd core/shell nanobars.

    PubMed

    Zhang, Ke; Xiang, Yanjuan; Wu, Xiaochun; Feng, Lili; He, Weiwei; Liu, Jianbo; Zhou, Weiya; Xie, Sishen

    2009-01-20

    A Pd nanoshell was epitaxially grown on a Au nanorod (NR) via simple seed-mediated growth. Compared with the cylindrical shape of the Au NR, the Au core/Pd shell (Au@Pd) nanorods change to a rectangular shape due to the disappearance of {110} facets. The Au NRs exhibit a strong longitudinal surface plasmon resonance (LSPR). As Pd is deposited, damping and broadening occur to the LSPR band. Interestingly, the LSPR band maximum first shows a small red-shift (ca. 40 nm) which then is followed by a blue-shift as the amount of Pd is increased. A thickness-dependent LSPR feature of the Pd shell is believed to contribute to the shift. At a thinner Pd thickness, the Au@Pd nanobars exhibit a well-defined LSPR band in the visible and near-infrared region, which demonstrates a higher dielectric sensitivity than that of the corresponding Au NRs. It thus opens up the potential of Pd nanostructures for SPR-based sensing. Investigations on the surface-enhanced Raman scattering (SERS) indicate that the SERS activities of the Au@Pd nanobars at thicknesses smaller than 2.5 nm mainly originate from the Au cores; thus, the SERS activities can be improved by tuning the aspect ratio of the Au core and/or the Pd shell thickness. PMID:19090666

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

    SciTech Connect

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

    2014-03-28

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

  20. Au-Ag@Au Hollow Nanostructure with Enhanced Chemical Stability and Improved Photothermal Transduction Efficiency for Cancer Treatment.

    PubMed

    Jiang, Tongtong; Song, Jiangluqi; Zhang, Wenting; Wang, Hao; Li, Xiaodong; Xia, Ruixiang; Zhu, Lixin; Xu, Xiaoliang

    2015-10-01

    Despite the fact that Au-Ag hollow nanoparticles (HNPs) have gained much attention as ablation agents for photothermal therapy, the instability of the Ag element limits their applications. Herein, excess Au atoms were deposited on the surface of a Au-Ag HNP by improving the reduction power of l-ascorbic acid (AA) and thereby preventing the reaction between HAuCl4 and the Ag element in the Au-Ag alloy nanostructure. Significantly, the obtained Au-Ag@Au HNPs show excellent chemical stability in an oxidative environment, together with remarkable increase in extinction peak intensity and obvious narrowing in peak width. Moreover, finite-difference time-domain (FDTD) was used to simulate the optical properties and electric field distribution of HNPs. The calculated results show that the proportion of absorption cross section in total extinction cross section increases with the improvement of Au content in HNP. As predicted by the theoretical calculation results, Au-Ag@Au nanocages (NCs) exhibit a photothermal transduction efficiency (η) as high as 36.5% at 808 nm, which is higher than that of Au-Ag NCs (31.2%). Irradiated by 808 nm laser at power densities of 1 W/cm(2), MCF-7 breast cancer cells incubated with PEGylated Au-Ag@Au NCs were seriously destroyed. Combined together, Au-Ag@Au HNPs with enhanced chemical stability and improved photothermal transduction efficiency show superior competitiveness as photothermal agents. PMID:26371629

  1. Carbon nanofiber supported bimetallic PdAu nanoparticles for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Qin, Yuan-Hang; Jiang, Yue; Niu, Dong-Fang; Zhang, Xin-Sheng; Zhou, Xing-Gui; Niu, Li; Yuan, Wei-Kang

    2012-10-01

    Carbon nanofiber (CNF) supported PdAu nanoparticles are synthesized with sodium citrate as the stabilizing agent and sodium borohydride as the reducing agent. High resolution transmission electron microscopy (HRTEM) characterization indicates that the synthesized PdAu particles are well dispersed on the CNF surface and X-ray diffraction (XRD) characterization indicates that the alloying degree of the synthesized PdAu nanoparticles can be improved by adding tetrahydrofuran to the synthesis solution. The results of electrochemical characterization indicate that the addition of Au can promote the electrocatalytic activity of Pd/C catalyst for formic acid oxidation and the CNF supported high-alloying PdAu catalyst possesses better electrocatalytic activity and stability for formic acid oxidation than either the CNF supported low-alloying PdAu catalyst or the CNF supported Pd catalyst.

  2. Synthesis of novel AuPd nanoparticles decorated one-dimensional ZnO nanorod arrays with enhanced photoelectrochemical water splitting activity.

    PubMed

    Lu, Yan; Zhang, Junlong; Ge, Lei; Han, Changcun; Qiu, Ping; Fang, Siman

    2016-12-01

    The vertically aligned one-dimensional (1D) ZnO nanorod arrays decorated with AuPd alloy nanoparticles have been synthesized with ZnO nanorod arrays as template via a mild hydrothermal method. In this work, the as-prepared AuPd/ZnO nanorod arrays demonstrated high light-harvesting efficiency. The microstructures, morphologies and chemical properties of the obtained AuPd/ZnO composite photocatalyst were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectra (DRS) and X-ray photoelectron spectroscopy (XPS). The photoelectrochemical (PEC) performances of as-obtained AuPd/ZnO nanorod arrays were examined, and the photocurrent density was up to 0.98mAcm(-2) at 0.787V versus Ag/AgCl, which was about 2.4 times higher than the pure ZnO sample. A possible photocatalytic mechanism of the AuPd/ZnO hybrid nanostructures under the simulated sunlight irradiation was proposed to guide further improvement of other desirable materials. According to the above experiment results, it can be clearly found that AuPd/ZnO composite nanorod arrays showed excellent PEC performance and had promising applications in the utilization of solar energy. PMID:27552423

  3. Shape-controlled synthesis of Au-Pd bimetallic nanocrystals for catalytic applications.

    PubMed

    Zhang, Lei; Xie, Zhaoxiong; Gong, Jinlong

    2016-07-21

    Au-Pd nanostructured materials have been recognized as important heterogeneous catalysts in various reactions, due to their superior activities caused by the ensemble and ligand effects. In recent years, shape-controlled synthesis of noble metal nanocrystals (NCs) provided a brand-new insight for improving the performance of catalysts. The electronic properties and catalytic activities of Au-Pd NCs could be optimized by tuning their shape and composition engineering. This review describes recent progress in the design and synthesis of shape-controlled Au-Pd bimetallic NCs and their emerging catalytic applications. The review starts with a general discussion of various applications of Au-Pd catalysts and the significance of preparing shape-controlled Au-Pd NCs, followed by an overview of synthetic strategies for two different structures of Au-Pd bimetallic catalysts: a core-shell structure and an alloy structure. We also put forward the key factors for the preparation of Au-Pd core-shell and alloy structures. Additionally, we discussed the unique optical properties and structural effects of shape-controlled Au-Pd NCs. These recent advancements in the methodology development of Au-Pd bimetallic NCs offer numerous insights for generating Au-Pd NCs with a number of unique geometries in the future. Furthermore, the systematic synthesis of core-shell or alloy structures would provide insights for the preparation of other bimetallic NCs. PMID:27095006

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1990-06-01

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

  6. Biogenic synthesis of Ag, Au and bimetallic Au/Ag alloy nanoparticles using aqueous extract of mahogany (Swietenia mahogani JACQ.) leaves.

    PubMed

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

    2011-02-01

    In this paper, we have demonstrated for the first time, the superb efficiency of aqueous extract of dried leaves of mahogany (Swietenia mahogani JACQ.) in the rapid synthesis of stable monometallic Au and Ag nanoparticles and also Au/Ag bimetallic alloy nanoparticles having spectacular morphologies. Our method was clean, nontoxic and environment friendly. When exposed to aqueous mahogany leaf extract, competitive reduction of Au(III) and Ag(I) ions present simultaneously in same solution leads to the production of bimetallic Au/Ag alloy nanoparticles. UV-visible spectroscopy was used to monitor the kinetics of nanoparticles formation. UV-visible spectroscopic data and TEM images revealed the formation of bimetallic Au/Ag alloy nanoparticles. Mahogany leaf extract contains various polyhydroxy limonoids which are responsible for the reduction of Au(III) and Ag(I) ions leading to the formation and stabilization of Au and Ag nanopaticles. PMID:21030220

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

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

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

    NASA Technical Reports Server (NTRS)

    Mccabe, R. W.

    1987-01-01

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

  9. Intermetallic compounds, copper and palladium alloys in Au-Pd ore of the Skaergaard pluton, Greenland

    NASA Astrophysics Data System (ADS)

    Rudashevsky, N. S.; Rudashevsky, V. N.; Nielsen, T. F. D.

    2015-12-01

    Copper-palladium intermetallic compounds and alloys (2314 grains) from the Au-Pd ore of the Skaergaard layered gabbroic pluton have been studied. Skaergaardite PdCu, nielsenite PdCu3, (Cu,Pd)β, (Cu,Pd)α, (Pd,Cu,Au,Pt) alloys, and native palladium have been identified as a result of 1680 microprobe analyses. The average compositions and various chemical varieties of these minerals are characterized, as well as vertical and lateral zoning in distribution of noble metals. The primary Pd-Cu alloys were formed within a wide temperature interval broadly synchronously with cooling and crystallization of host gabbro and in close association with separation of Fe-Cu sulfide liquid. In the course of crystallization of residual gabbroic melt enriched in iron, noble and heavy metals and saturated with the supercritical aqueous fluid, PGE and Au are selectively concentrated in the Fe-Cu sulfide phase as Pd-Cu and Cu-Au alloys.

  10. Hydrodechlorination Catalysis of Pd-on-Au Nanoparticles Varies with Particle Size

    SciTech Connect

    Pretzer, Lori A.; Song, Hyun J.; Fang, Yu-Lun; Zhao, Zhun; Guo, Neng; Wu, Tianpin; Arslan, Ilke; Miller, Jeffrey T.; Wong, Michael S.

    2013-02-01

    The dependence of bimetallic PdAu catalytic activity on the relative ratios of Pd and Au has been theoretically predicted and experimentally observed for a number of reactions. Trichloroethene (TCE), a common carcinogenic solvent that is difficult to remove from contaminated groundwater in many industrialized nations, can be chemically degraded especially rapidly with Au nanoparticles partially coated with Pd ("Pd-on-Au NPs"). These NPs catalyze the room-temperature water-phase TCE hydrodechlorination (HDC) reaction with activities that follow a volcano-shape dependence on Pd surface coverage. The effect of particle size is not known, though. Pd-on-Au NPs synthesized with 3, 7, and 10 nm Au NPs and Pd surface coverages between 0 and 150% were studied in detail. Volcano-shape dependence on Au particle size and Pd surface coverage was observed, with 7 nm Au NPs with a Pd coverage of 60-70% having the highest TCE HDC activity. Extended x-ray absorption fine-structure spectroscopy (EXAFS) revealed the correlation was strongest between catalytic activity and the presence of non-oxidized Pd ensembles of ~2-3 atoms in contact with ~8-10 Au atoms. Isolated Pd atoms and Pd ensembles were visualized for the first time through aberration-corrected scanning transmission electron microscopy (STEM). This study provides the most direct evidence yet for Pd-on-Au NPs containing 2-dimensional Pd ensembles as the active sites for TCE HDC and likely for other chemical reactions. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. This research was supported by the Laboratory Directed Research and Development program at Pacific Northwest National Laboratory. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

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

    PubMed

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

    2007-02-28

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

  12. Ti/Pd/Ag Contacts to n-Type GaAs for High Current Density Devices

    NASA Astrophysics Data System (ADS)

    Huo, Pengyun; Rey-Stolle, Ignacio

    2016-06-01

    The metallization stack Ti/Pd/Ag on n-type Si has been readily used in solar cells due to its low metal/semiconductor specific contact resistance, very high sheet conductance, bondability, long-term durability, and cost-effectiveness. In this study, the use of Ti/Pd/Ag metallization on n-type GaAs is examined, targeting electronic devices that need to handle high current densities and with grid-like contacts with limited surface coverage (i.e., solar cells, lasers, or light emitting diodes). Ti/Pd/Ag (50 nm/50 nm/1000 nm) metal layers were deposited on n-type GaAs by electron beam evaporation and the contact quality was assessed for different doping levels (from 1.3 × 1018 cm-3 to 1.6 × 1019 cm-3) and annealing temperatures (from 300°C to 750°C). The metal/semiconductor specific contact resistance, metal resistivity, and the morphology of the contacts were studied. The results show that samples doped in the range of 1018 cm-3 had Schottky-like I- V characteristics and only samples doped 1.6 × 1019 cm-3 exhibited ohmic behavior even before annealing. For the ohmic contacts, increasing annealing temperature causes a decrease in the specific contact resistance ( ρ c,Ti/Pd/Ag ~ 5 × 10-4 Ω cm2). In regard to the metal resistivity, Ti/Pd/Ag metallization presents a very good metal conductivity for samples treated below 500°C ( ρ M,Ti/Pd/Ag ~ 2.3 × 10-6 Ω cm); however, for samples treated at 750°C, metal resistivity is strongly degraded due to morphological degradation and contamination in the silver overlayer. As compared to the classic AuGe/Ni/Au metal system, the Ti/Pd/Ag system shows higher metal/semiconductor specific contact resistance and one order of magnitude lower metal resistivity.

  13. One pot green synthesis of Ag, Au and Au-Ag alloy nanoparticles using isonicotinic acid hydrazide and starch.

    PubMed

    Malathi, Sampath; Ezhilarasu, Tamilarasu; Abiraman, Tamilselvan; Balasubramanian, Sengottuvelan

    2014-10-13

    Gold-silver alloy nanoparticles were synthesized via chemical reduction of varying mole fractions of chloroauric acid (HAuCl4) and silver nitrate (AgNO3) by environmentally benign isonicotinic acid hydrazide (INH) in the presence of starch as a capping agent in aqueous medium. The absorption spectra of Au-Ag nanoparticles show blue shift with increasing silver content indicating the formation of alloy nanoparticles. When the Ag content in the alloy decreases the size of the nanoparticles increases and as a result of which the oxidation potential also increases. The emission maximum undergoes a red shift from 443 to 614 nm. The nanoparticles are monodisperse and spherical with an average particle size of 3-18 nm. The catalytic behavior of alloy nanoparticles indicate that the rate constant for the reduction of 4-nitro phenol to 4-amino phenol increases exponentially from metallic Ag to metallic Au as Au content increases in the Au-Ag alloy nanoparticles. PMID:25037410

  14. Seed-mediated growth of Au nanorings with size control on Pd ultrathin nanosheets and their tunable surface plasmonic properties

    NASA Astrophysics Data System (ADS)

    Wang, Wenxing; Yan, Yucong; Zhou, Ning; Zhang, Hui; Li, Dongsheng; Yang, Deren

    2016-02-01

    Nanorings made of noble metals such as Au and Ag have attracted particular interest in plasmonic properties since they allow remarkable tunability of plasmon resonance wavelengths associated with their unique structural features. Unfortunately, most of the syntheses for Au nanorings involve complex procedures and/or require highly specialized and expensive facilities. Here, we report a seed-mediated approach for selective deposition of Au nanorings on the periphery of Pd seeds with the structure of an ultrathin nanosheet through the island growth mode. In combination with selective etching of Pd nanosheets, Au nanorings are eventually produced. We can control the outer diameter and wall thickness of the nanorings by simply varying the size of the Pd nanosheets and reaction time. By taking the advantage of this size controllability, the nanorings show tunable surface plasmonic properties in the near infrared (NIR) region arising from both the in-plane dipole and face resonance modes. Owing to their good surface plasmonic properties, the nanorings show substantially enhanced surface-enhanced Raman spectroscopy (SERS) performance for rhodamine 6G, and are therefore confirmed as good SERS substrates to detect trace amounts of molecules.Nanorings made of noble metals such as Au and Ag have attracted particular interest in plasmonic properties since they allow remarkable tunability of plasmon resonance wavelengths associated with their unique structural features. Unfortunately, most of the syntheses for Au nanorings involve complex procedures and/or require highly specialized and expensive facilities. Here, we report a seed-mediated approach for selective deposition of Au nanorings on the periphery of Pd seeds with the structure of an ultrathin nanosheet through the island growth mode. In combination with selective etching of Pd nanosheets, Au nanorings are eventually produced. We can control the outer diameter and wall thickness of the nanorings by simply varying the

  15. Chemical stability and degradation mechanisms of triangular Ag, Ag@Au, and Au nanoprisms.

    PubMed

    Lee, Kee Eun; Hesketh, Amelia V; Kelly, Timothy L

    2014-06-28

    Anisotropic metal nanoparticles have found use in a variety of plasmonic applications because of the large near-field enhancements associated with them; however, the very features that give rise to these enhancements (e.g., sharply curved edges and tips) often have high surface energies and are easily degraded. This paper describes the stability and degradation mechanisms of triangular silver, gold-coated silver, and gold nanoprisms upon exposure to a wide variety of adverse conditions, including halide ions, thiols, amines and elevated temperatures. The silver nanoprisms were immediately and irreversibly degraded under all of the conditions studied. In contrast, the core-shell Ag@Au nanoprisms were less susceptible to etching by chlorides and bromides, but were rapidly degraded by iodides, amines and thiols by a different degradation pathway. Only the pure gold nanoprisms were stable to all of the conditions tested. These results have important implications for the suitability of triangular nanoprisms in many applications; this is particularly true in biological or environmental fields, where the nanoparticles would inevitably be exposed to a wide variety of chemical stimuli. PMID:24827005

  16. 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

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

  18. 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

  19. 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.

  20. Phytosynthesis of Au, Ag and Au-Ag bimetallic nanoparticles using aqueous extract and dried leaf of Anacardium occidentale

    NASA Astrophysics Data System (ADS)

    Sheny, D. S.; Mathew, Joseph; Philip, Daizy

    2011-06-01

    Present study reports a green chemistry approach for the biosynthesis of Au, Ag, Au-Ag alloy and Au core-Ag shell nanoparticles using the aqueous extract and dried powder of Anacardium occidentale leaf. The effects of quantity of extract/powder, temperature and pH on the formation of nanoparticles are studied. The nanoparticles are characterized using UV-vis and FTIR spectroscopies, XRD, HRTEM and SAED analyses. XRD studies show that the particles are crystalline in the cubic phase. The formation of Au core-Ag shell nanoparticles is evidenced by the dark core and light shell images in TEM and is supported by the appearance of two SPR bands in the UV-vis spectrum. FTIR spectra of the leaf powder before and after the bioreduction of nanoparticles are used to identify possible functional groups responsible for the reduction and capping of nanoparticles. Water soluble biomolecules like polyols and proteins are expected to bring about the bio-reduction.

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

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

    PubMed Central

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

    2014-01-01

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

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

    SciTech Connect

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

    1997-06-20

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

  4. 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.

  5. XPS/STM study of model bimetallic Pd-Au/HOPG catalysts

    NASA Astrophysics Data System (ADS)

    Bukhtiyarov, Andrey V.; Prosvirin, Igor P.; Bukhtiyarov, Valerii I.

    2016-03-01

    The preparation of model bimetallic Pd-Au/HOPG catalysts has been investigated using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) techniques. Initially, model "core-shell" type Pd-Au/HOPG catalysts with similar particle size distribution (5-8 nm), but with different densities of particle locations on the HOPG surface and Pd/Au atomic ratios are prepared. Further, their thermal stability is studied within a temperature range of 50-500 °C at UHV conditions. It has been shown that annealing the model catalysts at a temperature range of 300-400 °C leads to formation of Pd-Au alloyed particles. Enhancement of heating temperature up to 500 °C results in sintering of bimetallic nanoparticles. Contribution of different parameters controlling the properties of Pd-Au alloyed particles has been discussed.

  6. Understanding the effect of ultrathin AuPd alloy shells of irregularly shaped Au@AuPd nanoparticles with high-index facets on enhanced performance of ethanol oxidation.

    PubMed

    Bi, Cuixia; Feng, Cong; Miao, Tingting; Song, Yahui; Wang, Dayang; Xia, Haibing

    2015-12-21

    In this study, irregularly shaped, concave cuboidal Au@AuPd nanoparticles (ISCC-Au@AuPd NPs) with high-index facets were synthesized via Pd overgrowth on pre-formed ISCC-Au NPs with a concentration of Pd precursors as low as 2%. The AuPd alloy nature of the resulting shells was confirmed by X-ray photoelectron spectroscopy, cyclic voltammogram analysis, and energy dispersive X-ray spectroscopy. Among the irregularly shaped NPs obtained, the ISCC-Au97.5@Au0.5Pd2.0 NPs display the largest electrochemically active surface area (up to 92.11 m(2) g(-1)), as their closed-packed agglomeration was prevented, and the best long-term stability with respect to ethanol oxidation (0.50 M) in alkaline media (0.30 KOH) by efficiently removing intermediates. Their mass- and ECSA-normalized current densities (4.15 A mgPd(-1) and 4.51 mA cm(-2)) are about 20.7 times and 6.9 times higher than those of commercial Pd/C catalysts (0.20 A mgPd(-1) and 0.65 mA cm(-2)), respectively. PMID:26567631

  7. One step electrochemical synthesis of bimetallic PdAu supported on nafion–graphene ribbon film for ethanol electrooxidation

    SciTech Connect

    Shendage, Suresh S. Singh, Abilash S.; Nagarkar, Jayashree M.

    2015-10-15

    Highlights: • Electrochemical deposition of bimetallic PdAu NPs. • Highly loaded PdAu NPs are obtained. • Nafion–graphene supported PdAu NPs shows good activity for ethanol electrooxidation. - Abstract: A nafion–graphene ribbon (Nf–GR) supported bimetallic PdAu nanoparticles (PdAu/Nf–GR) catalyst was prepared by electrochemical codeposition of Pd and Au at constant potential. The prepared catalyst was characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), transmission electron microscopy (TEM) and X-ray diffraction analysis (XRD). The average particle size of PdAu nanoparticles (NPs) determined from XRD was 3.5 nm. The electrocatalytic activity of the PdAu/Nf–GR catalyst was examined by cyclic voltametry. It was observed that the as prepared catalyst showed efficient activity and good stability for ethanol electrooxidation in alkaline medium.

  8. Nanocap array of Au:Ag composite for surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Zhang, Yongjun; Wang, Cong; Wang, Jinpeng; Chen, Lei; Li, Jia; Liu, Yang; Zhao, Xiaoyu; Wang, Yaxin; Yang, Jinghai

    2016-01-01

    We fabricated Au:Ag nanocap arrays by co-sputtering Au and Ag onto two-dimensional polystyrene (PS) colloidal sphere templates in a magnetron sputtering system for the surface-enhanced Raman scattering (SERS) substrate. In contrast to the bilayer Au/Ag, the co-sputtering Au:Ag bimetal array formed the protrusion network of Ag and Au nanoparticles, which contributed to Raman enhancement in the waxberry-like structure. The metal protrusions formed waxberry-like shell in which the PS beads were encapsulated. At the same time, the Au:Ag bimetal arrays exhibit 4-fold more enhancement in the SERS signal intensity of Rhodamine 6G at the 1649 cm-1 than Au/Ag bilayer array, which is ascribed to the plasmon coupling between the nanoparticles of Au and Ag on the sample. When the PS colloidal particle templates were etched by O2-plasma before sputtering process, the nanogaps affected the surface plasmon resonance (SPR), and the optimal gaps between adjacent Au:Ag nanocaps generated even stronger SERS enhancements. This SERS substrate of Au:Ag showed high sensitivity and reproducibility. The EF of Au:Ag nanocap array substrate onto which Rhodamine 6G (R6G) were adsorbed was evaluated as 6.72 × 1010.

  9. Nanocap array of Au:Ag composite for surface-enhanced Raman scattering.

    PubMed

    Zhang, Yongjun; Wang, Cong; Wang, Jinpeng; Chen, Lei; Li, Jia; Liu, Yang; Zhao, Xiaoyu; Wang, Yaxin; Yang, Jinghai

    2016-01-01

    We fabricated Au:Ag nanocap arrays by co-sputtering Au and Ag onto two-dimensional polystyrene (PS) colloidal sphere templates in a magnetron sputtering system for the surface-enhanced Raman scattering (SERS) substrate. In contrast to the bilayer Au/Ag, the co-sputtering Au:Ag bimetal array formed the protrusion network of Ag and Au nanoparticles, which contributed to Raman enhancement in the waxberry-like structure. The metal protrusions formed waxberry-like shell in which the PS beads were encapsulated. At the same time, the Au:Ag bimetal arrays exhibit 4-fold more enhancement in the SERS signal intensity of Rhodamine 6G at the 1649cm(-1) than Au/Ag bilayer array, which is ascribed to the plasmon coupling between the nanoparticles of Au and Ag on the sample. When the PS colloidal particle templates were etched by O2-plasma before sputtering process, the nanogaps affected the surface plasmon resonance (SPR), and the optimal gaps between adjacent Au:Ag nanocaps generated even stronger SERS enhancements. This SERS substrate of Au:Ag showed high sensitivity and reproducibility. The EF of Au:Ag nanocap array substrate onto which Rhodamine 6G (R6G) were adsorbed was evaluated as 6.72×10(10). PMID:26253437

  10. Cu-Au, Ag-Au, Cu-Ag, and Ni-Au intermetallics: First-principles study of temperature-composition phase diagrams and structures

    NASA Astrophysics Data System (ADS)

    Ozoliņš, V.; Wolverton, C.; Zunger, Alex

    1998-03-01

    The classic metallurgical systems-noble-metal alloys-that have formed the benchmark for various alloy theories are revisited. First-principles fully relaxed general-potential linearized augmented plane-wave (LAPW) total energies of a few ordered structures are used as input to a mixed-space cluster expansion calculation to study the phase stability, thermodynamic properties, and bond lengths in Cu-Au, Ag-Au, Cu-Ag, and Ni-Au alloys. (i) Our theoretical calculations correctly reproduce the tendencies of Ag-Au and Cu-Au to form compounds and Ni-Au and Cu-Ag to phase separate at T=0 K. (ii) Of all possible structures, Cu3Au (L12) and CuAu (L10) are found to be the most stable low-temperature phases of Cu1-xAux with transition temperatures of 530 K and 660 K, respectively, compared to the experimental values 663 K and ~670 K. The significant improvement over previous first-principles studies is attributed to the more accurate treatment of atomic relaxations in the present work. (iii) LAPW formation enthalpies demonstrate that L12, the commonly assumed stable phase of CuAu3, is not the ground state for Au-rich alloys, but rather that ordered (100) superlattices are stabilized. (iv) We extract the nonconfigurational (e.g., vibrational) entropies of formation and obtain large values for the size-mismatched systems: 0.48 kB/atom in Ni0.5Au0.5 (T=1100 K), 0.37 kB/atom in Cu0.141Ag0.859 (T=1052 K), and 0.16 kB/atom in Cu0.5Au0.5 (T=800 K). (v) Using 8 atom/cell special quasirandom structures we study the bond lengths in disordered Cu-Au and Ni-Au alloys and obtain good qualitative agreement with recent extended x-ray-absorption fine-structure measurements.

  11. Seed-mediated growth of Au nanorings with size control on Pd ultrathin nanosheets and their tunable surface plasmonic properties.

    PubMed

    Wang, Wenxing; Yan, Yucong; Zhou, Ning; Zhang, Hui; Li, Dongsheng; Yang, Deren

    2016-02-14

    Nanorings made of noble metals such as Au and Ag have attracted particular interest in plasmonic properties since they allow remarkable tunability of plasmon resonance wavelengths associated with their unique structural features. Unfortunately, most of the syntheses for Au nanorings involve complex procedures and/or require highly specialized and expensive facilities. Here, we report a seed-mediated approach for selective deposition of Au nanorings on the periphery of Pd seeds with the structure of an ultrathin nanosheet through the island growth mode. In combination with selective etching of Pd nanosheets, Au nanorings are eventually produced. We can control the outer diameter and wall thickness of the nanorings by simply varying the size of the Pd nanosheets and reaction time. By taking the advantage of this size controllability, the nanorings show tunable surface plasmonic properties in the near infrared (NIR) region arising from both the in-plane dipole and face resonance modes. Owing to their good surface plasmonic properties, the nanorings show substantially enhanced surface-enhanced Raman spectroscopy (SERS) performance for rhodamine 6G, and are therefore confirmed as good SERS substrates to detect trace amounts of molecules. PMID:26815117

  12. Quantum well state induced oscillation of pure spin currents in Fe/Au/Pd(001) systems.

    PubMed

    Montoya, Eric; Heinrich, Bret; Girt, Erol

    2014-09-26

    Spin pumping at the ferromagnetic metal (Fe)/normal metal (Au) interface and the subsequent spin transport in Au/Pd heterostructures is studied using ferromagnetic resonance. The spin pumping induced damping in the Fe/Pd structure is greatly suppressed by the addition of a Au spacer layer in the structure Fe/Au/Pd. The rapid decrease in the interface damping with an increasing Au layer thickness does not correspond to an expectation based on a simple spin diffusion theory in the Au layer. It is possible to account for this behavior by introducing a partial reflection of spin current at the Au/Pd interface. Furthermore, oscillations in the amplitude of spin pumping damping are observed in the Fe/Au/Pd structure as a function of Au thickness for thicknesses less than half the electron mean free path of bulk Au. This new effect indicates a formation of quantum well states in the accumulated spin density in the Au spacer that affect the time irreversible process of spin pumping. PMID:25302912

  13. Assembly of hybrid oligonucleotide modified gold (Au) and alloy nanoparticles building blocks.

    PubMed

    Kuo, Yu-Ching; Jen, Chun-Ping; Chen, Yu-Hung; Su, Chia-Hao; Tsai, Shu-Hui; Yeh, Chen-Sheng

    2006-01-01

    The alloy-based hybrid materials with macroscopic network arrays were developed by AuAg/Au and AuAgPd/Au nanoparticle composites through oligonucleotides hybridization. AuAg/Au and AuAgPd/Au exhibited distinct organization. The morphology of AuAg/Au conjugation assembled mainly as compact aggregates while AuAgPd/Au hybrid conjugated into the loosen network assemblies. The dehybridization temperatures were studied as a function of molar ratio of alloy/Au. It was found that higher alloy/gold molar ratio led to stronger hybridization for alloy/gold composite, accompanied with increased melting temperature. These results could be interpreted in terms of more alloy nanoparticles bound to a Au particle when the molar ratio of alloy/gold increased. The thermal analysis also showed that AuAg/Au exhibited higher dehybridization temperature. A modified model describing the dehybridization probability of an intact Au/alloy aggregate was performed to support the dehybridization temperature increased with increasing alloy/Au molar ratio. As to more oligonucleotides carried by AuAg (4.9 +/- 1.9 nm) than by AuAgPd (4.4 +/- 1.5 nm) due to larger size in AuAg, the efficient hybridization could result in higher dehybridization temperature in AuAg/Au. PMID:16573077

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    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.

  15. 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

  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. Laccase/AuAg Hybrid Glucose Microfludic Fuel Cell

    NASA Astrophysics Data System (ADS)

    López-González, B.; Cuevas-Muñiz, F. M.; Guerra-Balcázar, M.; Déctor, A.; Arjona, N.; Ledesma-García, J.; Arriaga, L. G.

    2013-12-01

    In this work a hybrid microfluidic fuel cell was fabricated and evaluated with a AuAg/C bimetallic material for the anode and an enzymatic cathode. The cathodic catalyst was prepared adsorbing laccase and ABTS on Vulcan carbon (Lac-ABTS/C). This material was characterized by FTIR-ATR, the results shows the presence of absorption bands corresponding to the amide bounds. The electrochemical evaluation for the materials consisted in cyclic voltammetry (CV). The glucose electrooxidation reaction in AuAg/C occurs around - 0.3 V vs. NHE. Both electrocatalytic materials were placed in a microfluidic fuel cell. The fuel cell was fed with PBS pH 5 oxygen saturated solution in the cathodic compartment and 5 mM glucose + 0.3 M KOH in the anodic side. Several polarization curves were performed and the maximum power density obtained was 0.3 mWcm-2 .

  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

    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. Synthesis, Annealing and Performance of Pd-Au Asymmetric Composite Membranes for Hydrogen Purification

    SciTech Connect

    Ma, Yi Hua; Chen, Chao-Huang; Catalano, Jacopo; Guazzone, Federico; Payzant, E Andrew

    2013-01-01

    Composite asymmetric Pd-Au membranes, based on porous Inconel and Hastelloy tubular supports, were prepared by means of electroless deposition and galvanic displacement techniques and tested, before and after Au deposition, in pure H2 atmosphere. The final membranes, with Au average bulk composition up to 16.7 wt%, were 9 15 m thick and showed, for the entire duration of characterization, H2/He ideal selectivity in excess of 900. The annealing of the as-prepared membranes was conducted through the coating and diffusion mechanism in He and H2 atmospheres at 500 C. The annealing conditions were chosen after non-isothermal and isothermal HT-XRD studies on coupons synthetized with similar preparation methods. After the formation of the Pd-Au layer, the membranes showed steady flux and a stable Au gradient on the membrane top layer. Comparisons between permeance for Pd/Au and pure Pd membranes indicated that the membranes with an Au average bulk composition of 4.5 and 5.4 wt% had an enhancement, up to 20%, of the H2 permeability in the temperature range 250 450 C with respect to pure Pd membranes. On the other hand, the membrane having the highest Au composition, 16.7 wt%, even though characterized by a lower H2 permeability (77% of pure Pd) had a rather high surface Au composition (approximately 46 wt%), which might provide good H2S poisoning tolerance.

  1. Impact of surface roughness of Au core in Au/Pd core-shell nanoparticles toward formic acid oxidation - Experiment and simulation

    NASA Astrophysics Data System (ADS)

    Hsu, Chiajen; Huang, Chienwen; Hao, Yaowu; Liu, Fuqiang

    2013-12-01

    The Au/Pd core-shell nanoparticles (NPs) were synthesized via galvanic replacement of Cu by Pd on hollow Au cores by adding different concentrations of Na2SO3 solution. It was found that the higher concentration of Na2SO3 that was used, the rougher the Au nanospheres became. However, the rougher Au surface may cause more defects in the Pd layers and decrease the catalytic abilities. The Au/Pd NPs synthesized using 0 M Na2SO3 (denoted as 0 M-Au/Pd NPs) have the smoothest Pd surface and demonstrate higher formic acid oxidation (FAO) activity (0.714 mA cm-2, normalized to the surface area of Pd) than other Au/Pd NPs and commercial Pd black (0.47 mA cm-2). Additional electrochemical characterization of the 0 M-Au/Pd NPs also demonstrated lower CO-stripping onset and peak potentials, higher stability (8× improvement in stabilized oxidation current), and superior durability (by 1.6×) than the Pd black. In addition, a simple simulation of FAO was adopted to predict the anodic curve by including reaction intermediates of formate and hydroxyl. The 0 M-Au/Pd NPs were found to show higher formate and lower hydroxyl coverage than the Pd black.

  2. Controlling Hydrogen Activation, Spillover, and Desorption with Pd-Au Single-Atom Alloys.

    PubMed

    Lucci, Felicia R; Darby, Matthew T; Mattera, Michael F G; Ivimey, Christopher J; Therrien, Andrew J; Michaelides, Angelos; Stamatakis, Michail; Sykes, E Charles H

    2016-02-01

    Key descriptors in hydrogenation catalysis are the nature of the active sites for H2 activation and the adsorption strength of H atoms to the surface. Using atomically resolved model systems of dilute Pd-Au surface alloys and density functional theory calculations, we determine key aspects of H2 activation, diffusion, and desorption. Pd monomers in a Au(111) surface catalyze the dissociative adsorption of H2 at temperatures as low as 85 K, a process previously expected to require contiguous Pd sites. H atoms preside at the Pd sites and desorb at temperatures significantly lower than those from pure Pd (175 versus 310 K). This facile H2 activation and weak adsorption of H atom intermediates are key requirements for active and selective hydrogenations. We also demonstrate weak adsorption of CO, a common catalyst poison, which is sufficient to force H atoms to spill over from Pd to Au sites, as evidenced by low-temperature H2 desorption. PMID:26747698

  3. Real-Time Imaging of the Formation of Au-Ag Core-Shell Nanoparticles.

    PubMed

    Tan, Shu Fen; Chee, See Wee; Lin, Guanhua; Bosman, Michel; Lin, Ming; Mirsaidov, Utkur; Nijhuis, Christian A

    2016-04-27

    We study the overgrowth process of silver-on-gold nanocubes in dilute, aqueous silver nitrate solution in the presence of a reducing agent, ascorbic acid, using in situ liquid-cell electron microscopy. Au-Ag core-shell nanostructures were formed via two mechanistic pathways: (1) nuclei coalescence, where the Ag nanoparticles absorbed onto the Au nanocubes, and (2) monomer attachment, where the Ag atoms epitaxially deposited onto the Au nanocubes. Both pathways lead to the same Au-Ag core-shell nanostructures. Analysis of the Ag deposition rate reveals the growth modes of this process and shows that this reaction is chemically mediated by the reducing agent. PMID:27043921

  4. Pd-Au bimetallic catalysts: understanding alloy effects from planar models and (supported) nanoparticles.

    SciTech Connect

    Gao, Feng; Goodman, Wayne D.

    2012-12-21

    Pd-Au bimetallic catalysts often display enhanced catalytic activities and selectivities compared with Pd-alone catalysts. This enhancement is often caused by two alloy effects, i.e., ensemble and ligand effects. The ensemble effect is dilution of surface Pd by Au. With increasing surface Au coverages, contiguous Pd ensembles disappear and isolated Pd ensembles form. For certain reactions, for example vinyl acetate synthesis, this effect is responsible for reaction rate enhancement via the formation of highly active surface sites, e.g., isolated Pd pairs. The disappearance of contiguous Pd ensembles also switches off side reactions catalyzed by these sites. This explains selectivity increase of certain reactions, for example direct H2O2 synthesis. The ligand effect is electronic perturbation of Au to Pd. By direct charge transfer or affecting bond length, the ligand effect causes the Pd d band to be more filled and the d-band center away from the Fermi level. Both changes make Pd more "atomic like" therefore binding reactants and products weaker. For certain reactions, this eliminates the so-called "self poisoning" and enhances activity/selectivity.

  5. 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

  6. Understanding the effect of ultrathin AuPd alloy shells of irregularly shaped Au@AuPd nanoparticles with high-index facets on enhanced performance of ethanol oxidation

    NASA Astrophysics Data System (ADS)

    Bi, Cuixia; Feng, Cong; Miao, Tingting; Song, Yahui; Wang, Dayang; Xia, Haibing

    2015-11-01

    In this study, irregularly shaped, concave cuboidal Au@AuPd nanoparticles (ISCC-Au@AuPd NPs) with high-index facets were synthesized via Pd overgrowth on pre-formed ISCC-Au NPs with a concentration of Pd precursors as low as 2%. The AuPd alloy nature of the resulting shells was confirmed by X-ray photoelectron spectroscopy, cyclic voltammogram analysis, and energy dispersive X-ray spectroscopy. Among the irregularly shaped NPs obtained, the ISCC-Au97.5@Au0.5Pd2.0 NPs display the largest electrochemically active surface area (up to 92.11 m2 g-1), as their closed-packed agglomeration was prevented, and the best long-term stability with respect to ethanol oxidation (0.50 M) in alkaline media (0.30 KOH) by efficiently removing intermediates. Their mass- and ECSA-normalized current densities (4.15 A mgPd-1 and 4.51 mA cm-2) are about 20.7 times and 6.9 times higher than those of commercial Pd/C catalysts (0.20 A mgPd-1 and 0.65 mA cm-2), respectively.In this study, irregularly shaped, concave cuboidal Au@AuPd nanoparticles (ISCC-Au@AuPd NPs) with high-index facets were synthesized via Pd overgrowth on pre-formed ISCC-Au NPs with a concentration of Pd precursors as low as 2%. The AuPd alloy nature of the resulting shells was confirmed by X-ray photoelectron spectroscopy, cyclic voltammogram analysis, and energy dispersive X-ray spectroscopy. Among the irregularly shaped NPs obtained, the ISCC-Au97.5@Au0.5Pd2.0 NPs display the largest electrochemically active surface area (up to 92.11 m2 g-1), as their closed-packed agglomeration was prevented, and the best long-term stability with respect to ethanol oxidation (0.50 M) in alkaline media (0.30 KOH) by efficiently removing intermediates. Their mass- and ECSA-normalized current densities (4.15 A mgPd-1 and 4.51 mA cm-2) are about 20.7 times and 6.9 times higher than those of commercial Pd/C catalysts (0.20 A mgPd-1 and 0.65 mA cm-2), respectively. Electronic supplementary information (ESI) available: High magnification TEM

  7. Interference removals on Pd, Ru and Au with ICP-QQQ-MS in PGE RM

    NASA Astrophysics Data System (ADS)

    Nadeem Hussain Bokhari, Syed; Meisel, Thomas; Walkner, Christoph

    2015-04-01

    Gold and platinum group elements (PGE) are essential industrial precious metals with high world demand due to their unique properties. Struggle for natural exploration of PGE is on great pace and recycling from industrial wastes, electronics and catalytic convertor is on the rise for PGE supply chain. Along with these developments it is becoming more challenging for analytical chemists to determine gold and PGE out of complex matrix which causes severe interferences. The current state of art is online analysis coupled with chromatographic separation of interferences. The ICP-QQQ-MS Agilent 8800 has the capability of using multi tunes and mass shifts. We aim to remove interferences on Pd+ (for direct and isotope dilution analysis) Au+ and Ru+ in lieu of chemical separations. YO+, SrOH+, ZnAr+, NiAr+, ZrO+, CuAr+, MoO+ , Ru+and Cd+ are expected interferences on Pd+ while Au+ is interfered by TaO+, HfOH+, GdAr+ and 102Ru+ ,104Ru+ by 102Pd+ ,104Pd+ etc. Initial test were performed on pure solutions of 1mg/l (interfering elements): 1 ng/l (Pd, Ru & Au) respectively. The outcomes of initial tests were applied on PGE reference material (RM) WMG-1 and SARM-7 (digested with Na2O2 sintering). The results obtained show that YO+, SrOH+ interfere (104Pd,105Pd), 104 Ru+ on (104Pd), ZnAr+ has slight interference on (104Pd and106Pd), ZrO+, NiAr+, CuAr+ interferences are negligible, MoO+ has severe interference on (108Pd, 110Pd) and that Cd+ has severe isobaric interference on (106Pd,108Pd, 110Pd). These interference have been removed by formation of Pd(NH3)3+complex. The TaO+, HfOH+ and GdAr+ interferences on Au+ are best removed by formation of Au(NH3)+ and Au(NH3)2+ complexes. 102Pd+,104Pd+interference on 102Ru+ ,104Ru+ can be removed by formation of Ru(NH3)4+ and RuO+ compounds. The results obtained comply with certified values of RM. The developed method is being tested on low concentration PGE reference materials. References: Sugiyama, N. " Removal of complex spectral

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  9. 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.

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

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

  12. Immobilization of Ag-deposited Au nanoprisms by thiol-coupling and oil-coating methods

    NASA Astrophysics Data System (ADS)

    Noda, Yuta; Hayakawa, Tomokatsu

    2016-01-01

    We have demonstrated the immobilization of Ag-deposited Au (Au@Ag) nanoprisms on glass substrates by two different methods: self-assembly on a thiol-modified glass (thiol-coupling method) and evaporation of the Au@Ag nanoprism colloidal solution in silicone oil (oil-coating method). In the thiol-coupling method, the Au@Ag nanoprisms were well dispersed and accumulated on the substrates as single or stacked layers. On the other hand, the oil-coating method allowed Au@Ag nanoprisms to accumulate as multilayers without excessive agglomeration. The multilayers of Au@Ag nanoprisms were subjected to surface-enhanced Raman scattering (SERS), and a very low concentration (2.1 × 10-5 M) of rhodamine 6G molecules was sensitively detected.

  13. 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.

  14. Remarkable enhancement of electrocatalytic activity by tuning the interface of Pd-Au bimetallic nanoparticle tubes.

    PubMed

    Cui, Chun-Hua; Yu, Jin-Wen; Li, Hui-Hui; Gao, Min-Rui; Liang, Hai-Wei; Yu, Shu-Hong

    2011-05-24

    The interface, which formed in a bimetallic system, is a critical issue to investigate the fundamental mechanism of enhanced catalytic activity. Here, we designed unsupported Pd-Au bimetallic nanoparticle tubes with a tunable interface, which was qualitatively controlled by the proportion of Pd and Au nanoparticles (NPs), to demonstrate the remarkably enhanced effect of Pd and Au NPs in electro-oxidation of ethanol. The results demonstrated that the electrocatalytic activity is highly relative to the interface and has no direct relation with individual metal component in the Pd-Au system. This effect helps us in achieving a fundamental understanding of the relationship between their activity and the interface structure and chemical properties and, consequently, is helpful in designing new catalysts with high performances. PMID:21506570

  15. Structured Pd-Au/Cu-fiber catalyst for gas-phase hydrogenolysis of dimethyl oxalate to ethylene glycol.

    PubMed

    Zhang, Li; Han, Lupeng; Zhao, Guofeng; Chai, Ruijuan; Zhang, Qiaofei; Liu, Ye; Lu, Yong

    2015-07-01

    Galvanic co-deposition of 0.5 wt% Au and 0.1 wt% Pd on a microfibrous-structure using 8 μm Cu-fibers delivers a Pd-Au/Cu-fiber catalyst, which is highly active, selective and stable for the hydrogenolysis of dimethyl oxalate to ethylene glycol. Au and Pd synergistically promote the hydrogenolysis activity of Cu(+) sites, while Au also critically stabilizes Cu(+) sites to prevent deep reductive deactivation. PMID:26040855

  16. Magnetism of CoPd self-organized alloy clusters on Au(111)

    NASA Astrophysics Data System (ADS)

    Ohresser, P.; Otero, E.; Wilhelm, F.; Rogalev, A.; Goyhenex, C.; Joly, L.; Bulou, H.; Romeo, M.; Speisser, V.; Arabski, J.; Schull, G.; Scheurer, F.

    2013-12-01

    Magnetic properties of gold-encapsulated CoxPd1-x self-organized nano-clusters on Au(111) are analyzed by x-ray magnetic circular dichroism for x = 0.5, 0.7, and 1.0. The clusters are superparamagnetic with a blocking temperature decreasing with increasing Pd concentration, due to a reduction of the out-of-plane anisotropy strength. No magnetic moment is detected on Pd in these clusters, within the detection limit, contrary to thick CoPd films. Both reduction of anisotropy and vanishing Pd moment are attributed to strain.

  17. 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.

  18. Investigation of finite-size effects in chemical bonding of AuPd nanoalloys

    SciTech Connect

    Zhu, Beien; Oğuz, Ismail Can; Guesmi, Hazar

    2015-10-14

    In this paper, the size-dependent changes in energetic, vibrational, and electronic properties of C–O gas molecule interacting with surface Pd atom of a variety of AuPd nanoalloy structures are investigated by means of first principles calculations. The variation in C–O adsorption energies, C–O vibration frequencies (ν{sub C−O}), and Pd d-bond centers (ε{sub d}) on a series of non-supported Au{sub n−1}–Pd{sub 1} nanoparticles (with n varying from 13 to 147) and on two semi-finite surfaces are inspected with cluster size. We demonstrate for the first time that, with small AuPd bimetallic three-dimensional clusters as TOh{sub 38}, one can reach cluster size convergence even for such a sensitive observable as the adsorption energy on a metal surface. Indeed, the results show that the adsorbate-induced perturbation is extremely local and it only concerns the isolated Pd interacting with the reactive gas molecule. Except for 13 atom clusters, in which molecular behaviour is predominant, no finite-size effects are observed for surface Pd atom substituted in AuPd free nanoclusters above 38 atoms.

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

    NASA Astrophysics Data System (ADS)

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

    2011-08-01

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

  20. Spin and structural features of oxygen dissociation on tetrahedral Ag20 and Ag19Au clusters.

    PubMed

    Pichugina, D A; Polynskaya, Y G; Kuz'menko, N E

    2016-07-21

    The spin-crossing mechanism of oxygen dissociation on Ag20 and monodoped Ag19Au clusters was investigated via spin-polarized scalar-relativistic DFT calculations using the PBE, TPSSh, M06L, mPBE, BLYP, OLYP, and B3LYP functionals. In particular, the singlet and triplet O-O bond rupture pathways at vertex-edge and facet-edge sites on the tetrahedral clusters were studied. The calculations reveal that for the Ag20O2 and Ag19AuO2 complexes, the spin inversion from the triplet to singlet state occurs during the last step, which involves O-O bond rupture through a singlet transition state (TS). When spin crossing during oxygen dissociation on the clusters is considered, the activation energies decrease by 10-29 kJ mol(-1); however, they are still high due to the magic nature of the clusters and high vertical spin excitation energies. For these silver clusters, size effects based on the relationship between the TS structure and oxidation activation energy were predicted. PMID:27327106

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

    NASA Astrophysics Data System (ADS)

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

    1991-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Murugavelu, M.; Karthikeyan, B.

    2014-11-01

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

  6. Supported Pd-Au Membrane Reactor for Hydrogen Production: Membrane Preparation, Characterization and Testing.

    PubMed

    Iulianelli, Adolfo; Alavi, Marjan; Bagnato, Giuseppe; Liguori, Simona; Wilcox, Jennifer; Rahimpour, Mohammad Reza; Eslamlouyan, Reza; Anzelmo, Bryce; Basile, Angelo

    2016-01-01

    A supported Pd-Au (Au 7wt%) membrane was produced by electroless plating deposition. Permeation tests were performed with pure gas (H₂, H₂, N₂, CO₂, CH₄) for long time operation. After around 400 h under testing, the composite Pd-Au membrane achieved steady state condition, with an H₂/N₂ ideal selectivity of around 500 at 420 °C and 50 kPa as transmembrane pressure, remaining stable up to 1100 h under operation. Afterwards, the membrane was allocated in a membrane reactor module for methane steam reforming reaction tests. As a preliminary application, at 420 °C, 300 kPa of reaction pressure, space velocity of 4100 h(-1), 40% methane conversion and 35% hydrogen recovery were reached using a commercial Ni/Al₂O₃ catalyst. Unfortunately, a severe coke deposition affected irreversibly the composite membrane, determining the loss of the hydrogen permeation characteristics of the supported Pd-Au membrane. PMID:27171067

  7. Investigation of finite-size effects in chemical bonding of AuPd nanoalloys.

    PubMed

    Zhu, Beien; Oğuz, Ismail Can; Guesmi, Hazar

    2015-10-14

    In this paper, the size-dependent changes in energetic, vibrational, and electronic properties of C-O gas molecule interacting with surface Pd atom of a variety of AuPd nanoalloy structures are investigated by means of first principles calculations. The variation in C-O adsorption energies, C-O vibration frequencies (νC-O), and Pd d-bond centers (εd) on a series of non-supported Aun-1-Pd1 nanoparticles (with n varying from 13 to 147) and on two semi-finite surfaces are inspected with cluster size. We demonstrate for the first time that, with small AuPd bimetallic three-dimensional clusters as TOh38, one can reach cluster size convergence even for such a sensitive observable as the adsorption energy on a metal surface. Indeed, the results show that the adsorbate-induced perturbation is extremely local and it only concerns the isolated Pd interacting with the reactive gas molecule. Except for 13 atom clusters, in which molecular behaviour is predominant, no finite-size effects are observed for surface Pd atom substituted in AuPd free nanoclusters above 38 atoms. PMID:26472381

  8. Synthesis and biosensor application of Ag@Au bimetallic nanoparticles based on localized surface plasmon resonance

    NASA Astrophysics Data System (ADS)

    Ghodselahi, T.; Arsalani, S.; Neishaboorynejad, T.

    2014-05-01

    This work demonstrates a simple method for synthesizing gold-silver bimetallic nanoparticles (Ag@Au BNPs). Ag@Au BNPs on the carbon thin film are prepared by co-deposition of RF-sputtering and RF-PECVD using acetylene gas and gold-silver target. X-ray diffraction analysis indicates that Au and Ag NPs with FCC crystal structure are formed in our samples. From AFM image and data, average particles size of gold and silver are estimated to be about 5 and 8 nm, respectively. XRD profile and localized surface plasmon resonance (LSPR) spectroscopy indicate that Ag NPs in Ag@Au BNPs composite have a more chemical activity with respect to bare Ag NPs. Biosensor application of Ag@Au BNPs without probe immobilization is introduced too. The change in LSPR absorption peak of Ag@Au BNPs in presence of DNA primer decamer (ten-deoxycytosine) at fM concentrations is investigated. The LSPR absorption peak of Au NPs has a blue shift and the LSPR absorption peak of Ag NPs has a red shift by addition of DNA primer and under DNA exposure up to 1 h. Our sample shows a good response to low concentration of DNA and has a short response time. Both of these are prerequisite for applying this sample as LSPR biosensor chip.

  9. 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.

  10. Ag/Au mixed sites promote oxidative coupling of methanol on the alloy surface.

    PubMed

    Xu, Bingjun; Siler, Cassandra G F; Madix, Robert J; Friend, Cynthia M

    2014-04-14

    Nanoporous gold, a dilute alloy of Ag in Au, activates molecular oxygen and promotes the oxygen-assisted catalytic coupling of methanol. Because this trace amount of Ag inherent to nanoporous gold has been proposed as the source of oxygen activation, a thin film Ag/Au alloy surface was studied as a model system for probing the origin of this reactivity. Thin alloy layers of Ag(x)Au(1-x), with 0.15≤x≤0.40, were examined for dioxygen activation and methanol self-coupling. These alloy surfaces recombine atomic oxygen at different temperatures depending on the alloy composition. Total conversion of methanol to selective oxidation products, that is, formaldehyde and methyl formate, was achieved at low initial oxygen coverage and at low temperature. Reaction channels for methyl formate formation occurred on both Au and Au/Ag mixed sites with a ratio, as was predicted from the local 2-dimensional composition. PMID:24633724

  11. Platinum(iv) prodrug conjugated Pd@Au nanoplates for chemotherapy and photothermal therapy

    NASA Astrophysics Data System (ADS)

    Shi, Saige; Chen, Xiaolan; Wei, Jingping; Huang, Yizhuan; Weng, Jian; Zheng, Nanfeng

    2016-03-01

    Owing to the excellent near infrared (NIR) light absorption and efficient passive targeting toward tumor tissue, two-dimensional (2D) core-shell PEGylated Pd@Au nanoplates have great potential in both photothermal therapy and drug delivery systems. In this work, we successfully conjugate Pd@Au nanoplates with a platinum(iv) prodrug c,c,t-[Pt(NH3)2Cl2(O2CCH2CH2CO2H)2] to obtain a nanocomposite (Pd@Au-PEG-Pt) for combined photothermal-chemotherapy. The prepared Pd@Au-PEG-Pt nanocomposite showed excellent stability in physiological solutions and efficient Pt(iv) prodrug loading. Once injected into biological tissue, the Pt(iv) prodrug was easily reduced by physiological reductants (e.g. ascorbic acid or glutathione) into its cytotoxic and hydrophilic Pt(ii) form and released from the original nanocomposite, and the NIR laser irradiation could accelerate the release of Pt(ii) species. More importantly, Pd@Au-PEG-Pt has high tumor accumulation (29%ID per g), which makes excellent therapeutic efficiency at relatively low power density possible. The in vivo results suggested that, compared with single therapy the combined thermo-chemotherapy treatment with Pd@Au-PEG-Pt resulted in complete destruction of the tumor tissue without recurrence, while chemotherapy using Pd@Au-PEG-Pt without irradiation or photothermal treatment using Pd@Au-PEG alone did not. Our work highlights the prospects of a feasible drug delivery strategy of the Pt prodrug by using 2D Pd@Au nanoplates as drug delivery carriers for multimode cancer treatment.Owing to the excellent near infrared (NIR) light absorption and efficient passive targeting toward tumor tissue, two-dimensional (2D) core-shell PEGylated Pd@Au nanoplates have great potential in both photothermal therapy and drug delivery systems. In this work, we successfully conjugate Pd@Au nanoplates with a platinum(iv) prodrug c,c,t-[Pt(NH3)2Cl2(O2CCH2CH2CO2H)2] to obtain a nanocomposite (Pd@Au-PEG-Pt) for combined photothermal-chemotherapy. The

  12. Ductility of a dental Ag-Pd-Cu-Au alloy.

    PubMed

    Syverud, M; Herø, H

    1984-02-01

    A silver-palladium type of dental alloy for fixed restorations has been investigated with regard to the ability of the material to be plastically deformed in uniaxial tensile testing after two different age-hardening treatments. A certain degree of ductility is required for the burnishing of the margins. Aged to peak hardness at 350 degrees C after solid-solution annealing at 900 degrees C, the material was found to be brittle owing to a reaction zone along the grain boundaries, promoting an intergranular fracture. When the age-hardening temperature was lowered to 275 degrees C, a less pronounced reaction zone along the grain boundaries could be observed. The accompanying mechanical properties after precipitation hardening at 275 degrees C are probably an acceptable compromise between mechanical strength and ductility. Small particles along grain boundaries and brittleness were also found after solid-solution annealing at 900 degrees C and quenching. It is suggested that the improved ductility after subsequent aging at 275 degrees C is due to a coarsening of these small particles. In the as-cast condition the alloy was softer and more ductile than in the age-hardened state. PMID:6585123

  13. Photoelectron spectroscopic and computational study of (M-CO2)- anions, M = Cu, Ag, Au

    NASA Astrophysics Data System (ADS)

    Zhang, Xinxing; Lim, Eunhak; Kim, Seong K.; Bowen, Kit H.

    2015-11-01

    In a combined photoelectron spectroscopic and computational study of (M-CO2)-, M = Au, Ag, Cu, anionic complexes, we show that (Au-CO2)- forms both the chemisorbed and physisorbed isomers, AuCO 2- and Au-(CO2), respectively; that (Ag-CO2)- forms only the physisorbed isomer, Ag-(CO2); and that (Cu-CO2)- forms only the chemisorbed isomer, CuCO 2- . The two chemisorbed complexes, AuCO 2- and CuCO 2- , are covalently bound, formate-like anions, in which their CO2 moieties are significantly reduced. These two species are examples of electron-induced CO2 activation. The two physisorbed complexes, Au-(CO2) and Ag-(CO2), are electrostatically and thus weakly bound.

  14. Effect of trimetallization in thiolate-protected Au24-nCunPd clusters

    NASA Astrophysics Data System (ADS)

    Sharma, Sachil; Kurashige, Wataru; Nobusada, Katsuyuki; Negishi, Yuichi

    2015-06-01

    We synthesized a mixture of Au24-nCunPd(SC12H25)18 (n = 0-3) and Au25-nCun(SC12H25)18 (n = 0-7) and compared their stability. The results showed that, in a cluster containing one Cu atom, the presence of Pd is effective in improving the cluster stability. Conversely, the presence of Pd has different effects depending on the number of Cu atoms in the cluster: cluster formation was inhibited for clusters containing four or more Cu atoms.We synthesized a mixture of Au24-nCunPd(SC12H25)18 (n = 0-3) and Au25-nCun(SC12H25)18 (n = 0-7) and compared their stability. The results showed that, in a cluster containing one Cu atom, the presence of Pd is effective in improving the cluster stability. Conversely, the presence of Pd has different effects depending on the number of Cu atoms in the cluster: cluster formation was inhibited for clusters containing four or more Cu atoms. Electronic supplementary information (ESI) available: Details of product characterization data. See DOI: 10.1039/c5nr01491c

  15. Thermal diffusivity of nanofluids containing Au/Pd bimetallic nanoparticles of different compositions.

    PubMed

    Sánchez-Ramírez, J F; Jiménez Pérez, J L; Cruz Orea, A; Gutierrez Fuentes, R; Bautista-Hernández, A; Pal, U

    2006-03-01

    Colloidal suspensions of bimetallic Au/Pd nanoparticles were prepared by simultaneous reduction of the metal ions from their corresponding chloride salts with polymer (PVP) stabilizer. Thermal properties of water containing bimetallic nanoparticles with different nominal compositions (Au/Pd = 12/1, 5/1, 1/1, 1/5) were measured using the mode mismatched dual-beam thermal lens technique to determine the effect of particle composition on the thermal diffusivity of the nanofluids. The characteristic time constant of the transient thermal lens was estimated by fitting the experimental data to the theoretical expression for transient thermal lens. The thermal diffusivity of the nanofluids (water, containing Au/Pd bimetallic nanoparticles) is seen to be strongly dependent on the composition of the particles. The maximum diffusivity was achieved for the nanoparticles with highest Au/Pd molar ratio. A possible mechanism for such high thermal diffusivity of the nanofluids with bimetallic particles is given. UV-Vis spectroscopy, TEM and high-resolution electron microscopy (HREM) techniques were used to characterize the Au/Pd bimetallic nanoparticles. PMID:16573121

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

  17. Site-specific growth of Au-Pd alloy horns on Au nanorods: a platform for highly sensitive monitoring of catalytic reactions by surface enhancement Raman spectroscopy.

    PubMed

    Huang, Jianfeng; Zhu, Yihan; Lin, Ming; Wang, Qingxiao; Zhao, Lan; Yang, Yang; Yao, Ke Xin; Han, Yu

    2013-06-12

    Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized a novel Au-Pd bimetallic nanostructure (HIF-AuNR@AuPd) through site-specific epitaxial growth of Au-Pd alloy horns as catalytic sites at the ends of Au nanorods. Using high-resolution electron microscopy and tomography, we successfully reconstructed the complex three-dimensional morphology of HIF-AuNR@AuPd and identified that the horns are bound with high-index {11l} (0.25 < l < 0.43) facets. With an electron beam probe, we visualized the distribution of surface plasmon over the HIF-AuNR@AuPd nanorods, finding that strong longitudinal surface plasmon resonance concentrated at the rod ends. This unique crystal morphology led to the coupling of high catalytic activity with a strong SERS effect at the rod ends, making HIF-AuNR@AuPd an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. Using the hydrogenation of 4-nitrothiophenol as a model reaction, we demonstrated that its first-order reaction kinetics could be accurately determined from this platform. Moreover, we clearly identified the superior catalytic activity of the rod ends relative to that of the rod bodies, owing to the different SERS activities at the two positions. In comparison with other reported Au-Pd bimetallic nanostructures, HIF-AuNR@AuPd offered both higher catalytic activity and greater detection sensitivity. PMID:23675958

  18. 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

  19. Nanosized {Pd4(μ4-C)}Pd32(CO)28(PMe3)14 Containing Tetrahedrally Deformed Pd4 Cage with Encapsulated Carbide Atom: Formal Substitution of Geometrically Analogous Interior Au4 Entity in Isostructural Au4Pd32(CO)28(PMe3)14 by Electronically Equivalent Pd4(μ4-C) and Computational/Catalytic Implications.

    PubMed

    Mednikov, Evgueni G; Ivanov, Sergei A; Dahl, Lawrence F

    2015-07-01

    This first homopalladium carbido cluster, {Pd4(μ4-C)}Pd32(CO)28(PMe3)14 (1), was isolated (3-7% yields) from an ultimately simplified procedure-the reaction of CHCl3 under N2 with either Pd8(CO)8(PMe3)7 or Pd10(CO)12(PMe3)6 at room temperature. Charge-coupled device (CCD) X-ray diffraction data at 100 K for 1·2.5 C6H14 (1a) and 1·3 CHCl3 (1b) produced closely related molecular parameters for 1. This {Pd4C}Pd32 cluster (1) possesses a highly unusual tetracoordinated carbide atom that causes a major distortion of a central regular Pd4 tetrahedron into a new symmetry type of encapsulated Pd4 cage of pseudo-D2 (222) symmetry. Mean Pd-Pd distances for the three pairs of opposite twofold-equivalent Pd-Pd tetrahedral-like edges for 1a are 2.71, 2.96, and 3.59 Å; the mean of the four Pd-C distances [range, 1.87(2)-1.94(2) Å] is 1.91 Å. An astonishing molecular feature is that this {Pd4C}Pd32 cluster (1) is an isostructural and electronically equivalent analogue of the nanosized Au4Pd32(CO)28(PMe3)14 (2). Cluster 2, likewise a pseudo-D2 molecule, contains a geometrically analogous tetrahedrally deformed interior Au4 entity encapsulated within an identical Pd32(CO)28(PMe3)14 shell; mean distances for the three corresponding symmetry-equivalent pairs of slightly smaller opposite tetrahedral-distorted Au-Au edges are 2.64, 2.90, and 3.51 Å. A computational study by both a natural population analysis (NPA) and an atoms-in-molecules (AIM) method performed on model analogues {Pd4C}Pd32(CO)28(PH3)14 (1-mod) and Au4Pd32(CO)28(PH3)14 (2-mod) suggested that the negatively charged Au4 entity in 2-mod may be described as two weakly interacting electron-pair Au2 intradimers. In contrast, an NPA of the {Pd4C} entity in 1-mod revealed that two similarly oriented identical Pd2 intradimers of 2.71 Å are primarily stabilized by Pd-C bonding with a negatively charged carbide atom. The isostructural stabilizations of 1 and 2 are then attributed to the similar sizes, shapes, and overall

  20. Hydrogen sensing with optical microfibers coated with Pd/Au nanoparticles

    NASA Astrophysics Data System (ADS)

    Monzón-Hernández, David; Luna-Moreno, Donato; Martínez-Escobar, Dalia; Villatoro, Joel

    2010-10-01

    Optical microfibers decorated with PdAu nanoparticles are proposed for fast hydrogen sensing. The microfibers were obtained by simply tapering conventional telecommunications fiber down to dimensions comparable to the wavelength of the guided light. A few millimeters of the microfiber were coated with a PdAu layer in island form by depositing the layer at low evaporation rate (0.1 Å/s). Then the islands were grown with a thermal annealing process until composite nanoparticles were formed. The PdAu nanoparticles deposited on the optical microfibers experience optical and physical changes when they exposed to hydrogen. This gives rise to reversible transmission changes with an unusual pulsed like behavior which is attributed to scattering of the guided light. The devices are promising for detecting low concentrations of hydrogen (up to 8%) at room temperature with response and recovery times on the order of seconds.

  1. Sensitive voltammetric determination of vanillin with an AuPd nanoparticles-graphene composite modified electrode.

    PubMed

    Shang, Lei; Zhao, Faqiong; Zeng, Baizhao

    2014-05-15

    In this work, graphene oxide was reduced to graphene with an endogenous reducing agent from dimethylformamide, and then AuPd alloy nanoparticles were electrodeposited on the graphene film. The obtained AuPd-graphene hybrid film was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and voltammetry. The electrochemical behavior of vanillin was studied using the AuPd-graphene hybrid based electrode. It presented high electrocatalytic activity and vanillin could produce a sensitive oxidation peak at it. Under the optimal conditions, the peak current was linear to the concentration of vanillin in the ranges of 0.1-7 and 10-40 μM. The sensitivities were 1.60 and 0.170 mA mM(-1) cm(-2), respectively; the detection limit was 20 nM. The electrode was successfully applied to the detection of vanillin in vanilla bean, vanilla tea and biscuit samples. PMID:24423501

  2. Squeezing and stretching Pd thin films: A high-resolution STM study of Pd/Au(111) and Pd/Cu(111) bimetallics

    NASA Astrophysics Data System (ADS)

    Blecher, Mishan E.; Lewis, Emily A.; Pronschinske, Alex; Murphy, Colin J.; Mattera, Michael F. G.; Liriano, Melissa L.; Sykes, E. Charles H.

    2016-04-01

    Pd bimetallic alloys are promising catalysts, especially for heterogeneous reactions involving hydrogen, as they exhibit increased activity and reduced demand for expensive precious metals. Using scanning tunneling microscopy, we examine the structure of Pd thin films on Cu(111) and Au(111) and demonstrate compression and expansion, respectively, of the bulk Pd lattice constant in the film. The relative binding strength of H to the two surfaces, inferred via tip-induced diffusion barriers, suggests that the strain in these systems may alter adsorbate binding and corroborates well-known trends in d-band shifts calculated by the density functional theory. Modification to the topography and activity of Pd films based on the choice of substrate metal illustrates the value of bimetallic systems for designing less expensive, tunable catalysts.

  3. Microbial synthesis of Pd/Fe3O4, Au/Fe3O4 and PdAu/Fe3O4 nanocomposites for catalytic reduction of nitroaromatic compounds

    PubMed Central

    Tuo, Ya; Liu, Guangfei; Dong, Bin; Zhou, Jiti; Wang, Aijie; Wang, Jing; Jin, Ruofei; Lv, Hong; Dou, Zeou; Huang, Wenyu

    2015-01-01

    Magnetically recoverable noble metal nanoparticles are promising catalysts for chemical reactions. However, the chemical synthesis of these nanocatalysts generally causes environmental concern due to usage of toxic chemicals under extreme conditions. Here, Pd/Fe3O4, Au/Fe3O4 and PdAu/Fe3O4 nanocomposites are biosynthesized under ambient and physiological conditions by Shewanella oneidensis MR-1. Microbial cells firstly transform akaganeite into magnetite, which then serves as support for the further synthesis of Pd, Au and PdAu nanoparticles from respective precursor salts. Surface-bound cellular components and exopolysaccharides not only function as shape-directing agent to convert some Fe3O4 nanoparticles to nanorods, but also participate in the formation of PdAu alloy nanoparticles on magnetite. All these three kinds of magnetic nanocomposites can catalyze the reduction of 4-nitrophenol and some other nitroaromatic compounds by NaBH4. PdAu/Fe3O4 demonstrates higher catalytic activity than Pd/Fe3O4 and Au/Fe3O4. Moreover, the magnetic nanocomposites can be easily recovered through magnetic decantation after catalysis reaction. PdAu/Fe3O4 can be reused in at least eight successive cycles of 4-nitrophenol reduction. The biosynthesis approach presented here does not require harmful agents or rigorous conditions and thus provides facile and environmentally benign choice for the preparation of magnetic noble metal nanocatalysts. PMID:26310728

  4. 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

  5. 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.

  6. An Atomically Precise Au10 Ag2 Nanocluster with Red-Near-IR Dual Emission.

    PubMed

    Lei, Zhen; Guan, Zong-Jie; Pei, Xiao-Li; Yuan, Shang-Fu; Wan, Xian-Kai; Zhang, Jin-Yuan; Wang, Quan-Ming

    2016-08-01

    A red-near-IR dual-emissive nanocluster with the composition [Au10 Ag2 (2-py-C≡C)3 (dppy)6 ](BF4 )5 (1; 2-py-C≡C is 2-pyridylethynyl, dppy=2-pyridyldiphenylphosphine) has been synthesized. Single-crystal X-ray structural analysis reveals that 1 has a trigonal bipyramidal Au10 Ag2 core that contains a planar Au4 (2-py-C≡C)3 unit sandwiched by two Au3 Ag(dppy)3 motifs. Cluster 1 shows intense red-NIR dual emission in solution. The visible emission originates from metal-to-ligand charge transfer (MLCT) from silver atoms to phosphine ligands in the Au3 Ag(dppy)3 motifs, and the intense NIR emission is associated with the participation of 2-pyridylethynyl in the frontier orbitals of the cluster, which is confirmed by a time-dependent density functional theory (TD-DFT) calculation. PMID:27305386

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

    NASA Astrophysics Data System (ADS)

    Bell, A.; Simon, A.

    2009-05-01

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

  8. Facile synthesis of PdAgTe nanowires with superior electrocatalytic activity

    NASA Astrophysics Data System (ADS)

    Hong, Wei; Wang, Jin; Wang, Erkang

    2014-12-01

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

  9. 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

  10. Structural studies of Au-Pd bimetallic nanoparticles by a genetic algorithm method

    NASA Astrophysics Data System (ADS)

    Shao, Gui-Fang; Tu, Na-Na; Liu, Tun-Dong; Xu, Liang-You; Wen, Yu-Hua

    2015-06-01

    Metallic nanoparticles have attracted particular interests due to their excellent electronic, catalytic and optical properties over the past decades. Atomic-level understanding of structural characteristics of metallic nanoparticles is of great importance for their syntheses and applications because the structural characteristics strongly determine their chemical and physical properties. In this article, we systematically investigated the structural stability and structural features of Au-Pd nanoparticles by using the genetic algorithm with the quantum correction Sutton-Chen potentials. Layered coordinate ranking method and an effective fitness function have been introduced into the genetic algorithm to enhance its searching ability of low-energy configurations. Here were addressed eight representative nanoshapes including single-crystalline and multiple-twinned structures. The results reveal that the developed genetic algorithm exhibits superior searching ability. In all polyhedra, the truncated octahedron possessed the best stability, while the icosahedron did the worst. Moreover, segregation of Au to the surface and that of Pd to the core were disclosed in these polyhedral Au-Pd nanoparticles. Particularly, for Au composition of 50%, the optimized structures of Au-Pd nanoparticles were predicted to exhibit core-shell structures.

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

    PubMed Central

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

    2016-01-01

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

  12. Sulfur Tolerant Pd/Cu and Pd/Au Alloy Membranes for H2 Separation with High Pressure CO2 for Sequestration

    SciTech Connect

    Yi Hua Ma; Natalie Pomerantz; Chao-Huang Chen

    2008-09-30

    The effect of H{sub 2}S poisoning on Pd, Pd/Cu, and Pd/Au alloy composite membranes prepared by the electroless deposition method on porous Inconel supports was investigated to provide a fundamental understanding of the durability and preparation of sulfur tolerant membranes. X-ray photoelectron spectroscopy (XPS) studies showed that the exposure of pure Pd to 50 ppm H{sub 2}S/H{sub 2} mixtures caused bulk sulfide formation at lower temperatures and surface sulfide formation at higher temperatures. Lower temperatures, longer exposure times, and higher H{sub 2}S concentrations resulted in a higher degree of sulfidation. In a Pd membrane, the bulk sulfide formation caused a drastic irrecoverable H{sub 2} permeance decline and an irreparable loss in selectivity. Pd/Cu and Pd/Au alloy membranes exhibited permeance declines due to surface sulfide formation upon exposure to 50 ppm H{sub 2}S/H{sub 2} gas mixtures. However in contrast to the pure Pd membrane, the permeances of the Pd/Cu and Pd/Au alloy membranes were mostly recovered in pure H{sub 2} and the selectivity of the Pd alloy layers remained essentially intact throughout the characterization in H{sub 2}, He and H{sub 2}S/H{sub 2} mixtures which lasted several thousand hours. The amount of irreversible sulfur poisoning decreased with increasing temperature due to the exothermicity of H{sub 2}S adsorption. Longer exposure times increased the amount of irreversible poisoning of the Pd/Cu membrane but not the Pd/Au membrane. Pd/Au coupon studies of the galvanic displacement method showed that higher Au{sup 3+} concentrations, lower pH values, higher bath temperatures and stirring the bath at a rate of 200 rpm yielded faster displacement rates, more uniform depositions, and a higher Au content within the layers. While 400 C was found to be sufficient to form a Pd/Au alloy on the surface, high temperature X-ray diffraction (HTXRD) studies showed that even after annealing between 500-600 C, the Pd/Cu alloys could have

  13. 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.

  14. Controlled synthesis and synergistic effects of graphene-supported PdAu bimetallic nanoparticles with tunable catalytic properties

    NASA Astrophysics Data System (ADS)

    Liu, Chang-Hai; Liu, Rui-Hua; Sun, Qi-Jun; Chang, Jian-Bing; Gao, Xu; Liu, Yang; Lee, Shuit-Tong; Kang, Zhen-Hui; Wang, Sui-Dong

    2015-03-01

    Graphene-supported bimetallic nanoparticles are promising nanocatalysts, which can show strong and tunable catalytic activity and selectivity. Herein room-temperature-ionic-liquid-assisted metal sputtering is utilized to synthesize PdAu bimetallic nanoparticles on graphene with bare surface, small size, high surface density and controlled Pd-to-Au ratio. This controllable synthetic approach is green-chemistry compatible and totally free of additives and byproducts. The supported PdAu nanoparticles show excellent catalytic capabilities for both oxidation and reduction reactions, strongly dependent on the Pd-to-Au ratio. A strong correlation among catalytic performance, bimetallic composition and charge redistribution in the PdAu nanoparticles has been demonstrated. The results suggest that sufficient Au d-holes appear to be significant to the catalysis of oxidation reaction, and a metallic Pd surface is critical to the catalysis of reduction reaction. By the present method, the bimetallic combination can be tailored for distinct types of catalytic reactions.Graphene-supported bimetallic nanoparticles are promising nanocatalysts, which can show strong and tunable catalytic activity and selectivity. Herein room-temperature-ionic-liquid-assisted metal sputtering is utilized to synthesize PdAu bimetallic nanoparticles on graphene with bare surface, small size, high surface density and controlled Pd-to-Au ratio. This controllable synthetic approach is green-chemistry compatible and totally free of additives and byproducts. The supported PdAu nanoparticles show excellent catalytic capabilities for both oxidation and reduction reactions, strongly dependent on the Pd-to-Au ratio. A strong correlation among catalytic performance, bimetallic composition and charge redistribution in the PdAu nanoparticles has been demonstrated. The results suggest that sufficient Au d-holes appear to be significant to the catalysis of oxidation reaction, and a metallic Pd surface is critical

  15. Alloyed Crystalline Au-Ag Hollow Nanostructures with High Chemical Stability and Catalytic Performance.

    PubMed

    Liu, Renxiao; Guo, Jianhua; Ma, Gang; Jiang, Peng; Zhang, Donghui; Li, Dexing; Chen, Lan; Guo, Yuting; Ge, Guanglu

    2016-07-01

    For bimetallic nanoparticles (NPs), the degree of alloying is beginning to be recognized as a significant factor affecting the NP properties. Here, we report an alloyed crystalline Au-Ag hollow nanostructure that exhibits a high catalytic performance, as well as structural and chemical stability. The Au-Ag alloyed hollow and porous nanoshell structures (HPNSs) with different morphologies and subnanoscale crystalline structures were synthesized by adjusting the size of the sacrificial Ag NPs via a galvanic replacement reaction. The catalytic activities of the nanomaterials were evaluated by the model reaction of the catalytic reduction of p-nitrophenol by NaBH4 to p-aminophenol. The experimental results show that the subnanoscale crystalline structure of the Au-Ag bimetallic HPNSs has much greater significance than the apparent morphology does in determining the catalytic ability of the nanostructures. The Au-Ag alloyed HPNSs with better surface crystalline alloying microstructures and open morphologies were found to exhibit much higher catalytic reaction rates and better cyclic usage efficiencies, probably because of the better dispersion of active Au atoms within these materials. These galvanic replacement-synthesized alloyed Au-Ag HPNSs, fabricated by a facile method that avoids Ag degradation, have potential applications in catalysis, nanomedicine (especially in drug/gene delivery and cancer theranostics), and biosensing. PMID:27268019

  16. 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. PMID:25456348

  17. Nanoscale electrical characteristics of metal (Au, Pd)-graphene-metal (Cu) contacts

    NASA Astrophysics Data System (ADS)

    Ruffino, F.; Meli, G.; Grimaldi, M. G.

    2016-01-01

    Free-standing graphene presents exceptional physical properties (as a high carrier mobility) making it the ideal candidate for the next generation nanoelectronics. However, when graphene layers are inserted in real electronics devices, metal contacting is required. The metal-graphene interaction significantly affects the graphene electrical properties, drastically changing its behavior with respect to the free-standing configuration. So, this work presents an experimental study on the nanoscale electric characteristics of metal/graphene/metal contacts. In particular, starting from single-layer graphene grown on Cu foil we deposited on the graphene surface two different metal films (Au or Pd) and the Au/graphene/Cu and Pd/graphene/Cu current-voltage characteristics are acquired, on the nanometric scale, by the conductive atomic force microscopy. Both systems presented a current voltage rectifying behavior. However, the Au/graphene/Cu system conducts significantly at negative applied bias (graphene behaves as a p-type semiconductor in a meta/semiconductor contact), while in the Pd/graphene/Cu at positive applied bias (graphene behaves as a n-type semiconductor in a metal/semiconductor contact). This difference is discussed on the basis of the band energy diagram at the metal/graphene interface and the modification of the graphene Fermi level due to the Au/graphene or Pd/graphene interaction.

  18. Electrochemical synthesis of reduced graphene sheet-AuPd alloy nanoparticle composites for enzymatic biosensing.

    PubMed

    Yang, Jiang; Deng, Shengyuan; Lei, Jianping; Ju, Huangxian; Gunasekaran, Sundaram

    2011-11-15

    A simple, fast, green and controllable approach was developed for electrochemical synthesis of a novel nanocomposite of electrochemically reduced graphene oxide (ERGO) and gold-palladium (1:1) bimetallic nanoparticles (AuPdNPs), without the aid of any reducing reagent. The electrochemical reduction efficiently removed oxygen-containing groups in ERGO, which was then modified with homogeneously dispersed AuPdNPs in a good size distribution. ERGO-AuPdNPs nanocomposite showed excellent biocompatibility, enhanced electron transfer kinetics and large electroactive surface area, and were highly sensitive and stable towards oxygen reduction. A biosensor was constructed by immobilizing glucose oxidase as a model enzyme on the nanocomposites for glucose detection through oxygen consumption during the enzymatic reaction. The biosensor had a detection limit of 6.9μM, a linear range up to 3.5mM and a sensitivity of 266.6μAmM(-1)cm(-2). It exhibited acceptable reproducibility and good accuracy with negligible interferences from common oxidizable interfering species. These characteristics make ERGO-AuPdNPs nanocomposite highly suitable for oxidase-based biosensing. PMID:21903376

  19. 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...

  20. Schottky barrier heights for Au and Pd contacts to MoS2

    NASA Astrophysics Data System (ADS)

    Kaushik, Naveen; Nipane, Ankur; Basheer, Firdous; Dubey, Sudipta; Grover, Sameer; Deshmukh, Mandar M.; Lodha, Saurabh

    2014-09-01

    The search of a p-type metal contact on MoS2 has remained inconclusive, with high work function metals such as Au, Ni, and Pt showing n-type behavior and mixed reports of n as well as p-type behavior for Pd. In this work, we report quantitative Schottky barrier heights for Au and Pd contacts to MoS2 obtained by analysing low temperature transistor characteristics and contact resistance data obtained using the transfer length method. Both Au and Pd exhibit n-type behavior on multilayer as well as monolayer MoS2 transistors with Schottky barrier heights of 0.126 eV and 0.4 eV, and contact resistances of 42 Ω.mm and 18 × 104 Ω.mm respectively. Scanning photocurrent spectroscopy data is in agreement with the resulting energy band alignment in Au-MoS2-Pd devices further reinforcing the observation that the Fermi-level is pinned in the upper half of MoS2 bandgap.

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

    PubMed

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

    2016-01-01

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

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

    PubMed

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

    2014-01-01

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

  3. Volcano-like Behavior of Au-Pd Core-shell Nanoparticles in the Selective Oxidation of Alcohols

    PubMed Central

    Silva, Tiago A. G.; Teixeira-Neto, Erico; López, Núria; Rossi, Liane M.

    2014-01-01

    Gold-palladium (AuPd) nanoparticles have shown significantly enhanced activity relative to monometallic Au and Pd catalysts. Knowledge of composition and metal domain distributions is crucial to understanding activity and selectivity, but these parameters are difficult to ascertain in catalytic experiments that have primarily been devoted to equimolar nanoparticles. Here, we report AuPd nanoparticles of varying Au:Pd molar ratios that were prepared by a seed growth method. The selective oxidation of benzyl alcohol was used as a model reaction to study catalytic activity and selectivity changes that occurred after varying the composition of Pd in bimetallic catalysts. We observed a remarkable increase in catalytic conversion when using a 10:1 Au:Pd molar ratio. This composition corresponds to the amount of Pd necessary to cover the existing Au cores with a monolayer of Pd as a full-shell cluster. The key to increased catalytic activity derives from the balance between the number of active sites and the ease of product desorption. According to density functional theory calculations, both parameters are extremely sensitive to the Pd content resulting in the volcano-like activity observed. PMID:25042537

  4. Spectral Tuning of Plasmon Resonance in a Core/Shell (Au)Ag Nanocomposite

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    A bimetallic (Au)Ag nanocomposite with a core/shell structure was synthesized in aqueous solution and a H2O/EtOH mixture (1:1) containing polymers (carboxymethylcellulose, sodium polystyrenesulfonate, polyvinylpyrrolidone, dextran). Its structure and optical properties were characterized. The shape and position of scattering bands of colloidal noble-metal nanoparticles with optical density <0.1 were undistorted by solvent absorption. Scattering spectra had to be corrected for solutions of greater optical density. A method for correcting the resonant lightscattering spectra of Au and (Au)Ag nanoparticles was proposed for a single-beam apparatus. The possibility of surface plasmon resonance tuning for (Au)Ag with a short-wavelength shift of ~150 nm for the absorption band maximum and of ~84 nm for the resonant scattering band was demonstrated by varying the AgNO3 concentration during formation of the silver shell on the gold core.

  5. Growth of Ag nanowires on Au-pre-facetted 4° vicinal Si(0 0 1)

    NASA Astrophysics Data System (ADS)

    Meyer zu Heringdorf, Frank-J.; Roos, Kimberly L.; Wiethoff, Christian; Horn-von Hoegen, Michael; Roos, Kelly R.

    2008-05-01

    We studied the self-assembly of wire-shaped Ag islands at high temperature with low energy electron microscopy and photoemission electron microscopy. A Au-faceted vicinal Si(0 0 1) surface was used as a substrate. The initial Ag deposit at 600-620 °C induces a surface phase change from the (5 × 3.2) reconstruction of the Au-covered (0 0 1) terraces, to a (3 × 2) reconstruction, but leaves the structure of the Au-induced step bunches intact. Subsequent Ag growth produces two distinct types of 3D crystalline islands: compact and wire-like. The total Ag deposit is comprised mostly of compact islands, with only a small minority of wire-like islands. We attribute the wire formation to local step bunches that create the proper quasi-one-dimensional diffusion environment for the Ag islands to grow with a high aspect ratio.

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

    PubMed

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

    2013-11-01

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

  7. 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.

  8. Phospholipid Encapsulated AuNR@Ag/Au Nanosphere SERS Tags with Environmental Stimulus Responsive Signal Property.

    PubMed

    Su, Xueming; Wang, Yunqing; Wang, Wenhai; Sun, Kaoxiang; Chen, Lingxin

    2016-04-27

    Surface-enhanced Raman scattering (SERS) tags draw much attention due to the ultrasensitivity and multiplex labeling capability. Recently, a new kind of SERS tags was rationally designed by encapsulating metal nanoparticles with phospholipid bilayers, showing great potential in theranostics. The lipid bilayer coating confers biocompatibility and versatility to changing surface chemistry of the tag; however, its "soft" feature may influence SERS signal stability, which is rarely investigated. Herein, we prepared phospholipid-coated AuNR@Ag/Au nanosphere SERS tags by using three different kinds of Raman reporters, i.e., thio-containing 4-nitrothiophenol (NT), nitrogen-containing hydrophobic chromophore cyanine 7 monoacid (Cy7), and alkyl chain-chromophore conjugate 1,1'-dioctadecyl-3,3,3',3'-tetramethylindodicarbocyanine (DiD). It was found that signal responses were different upon additional stimulation which the tags may encounter in theranostic applications including the presence of detergent Triton X-100, lipid membrane, and photothermal treatment. Living-cell imaging also showed signal changing distinction. The different SERS signal performances were attributed to the different Raman reporter releasing behaviors from the tags. This work revealed that Raman reporter structure determined signal stability of lipid-coated SERS tags, providing guidance for the design of stimulus responsive tags. Moreover, it also implied the potential of SERS technique for real time drug release study of lipid based nanomedicine. PMID:27052206

  9. 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

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  13. The effect of CNTs on structures and catalytic properties of AuPd clusters for H2O2 synthesis.

    PubMed

    Yang, Hua-feng; Xie, Peng-yang; Yu, Hui-you; Li, Xiao-nian; Wang, Jian-guo

    2012-12-28

    The structures and catalytic properties of AuPd clusters supported on carbon nanotubes (CNTs) for H(2)O(2) synthesis have been investigated by means of density functional theory calculations. Firstly, the structures of AuPd clusters are strongly influenced by CNTs, in which the bottom layers are mainly composed of Pd and the top layers are a mix of Au and Pd due to the stronger binding of Pd than Au on CNTs. Especially, it is found that O(2) adsorption on the Pd/CNTs interfacial sites is much weaker than that on the only Pd sites, which is in contrast to transition metal oxide (for example TiO(2), Al(2)O(3), CeO(2)) supported metal clusters. Furthermore, Pd ensembles on the interfacial sites have far superior catalytic properties for H(2)O(2) formation than those away from CNT supports due to the changes in electronic structures caused by the CNTs. Therefore, our study provides a physical insight into the enhanced role of carbon supports in H(2)O(2) synthesis over supported AuPd catalysts. PMID:23032860

  14. 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

  15. The bifurcation point of the oxygen reduction reaction on Au-Pd nanoalloys.

    PubMed

    Staszak-Jirkovský, Jakub; Ahlberg, Elisabet; Panas, Itai; Schiffrin, David J

    2016-07-01

    The oxygen reduction reaction is of major importance in energy conversion and storage. Controlling electrocatalytic activity and its selectivity remains a challenge of modern electrochemistry. Here, first principles calculations and analysis of experimental data unravel the mechanism of this reaction on Au-Pd nanoalloys in acid media. A mechanistic model is proposed from comparison of the electrocatalysis of oxygen and hydrogen peroxide reduction on different Au-Pd ensembles. A H2O production channel on contiguous Pd sites proceeding through intermediates different from H2O2 and OOH(σ) adsorbate is identified as the bifurcation point for the two reaction pathway alternatives to yield either H2O or H2O2. H2O2 is a leaving group, albeit reduction of H2O2 to H2O can occur by electrocatalytic HO-OH dissociation that is affected by the presence of adsorbed OOH(σ). Similarities and differences between electrochemical and direct synthesis from H2 + O2 reaction on Au-Pd nanoalloys are discussed. PMID:27089504

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  18. Synergistic catalysis of metal-organic framework-immobilized Au-Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage.

    PubMed

    Gu, Xiaojun; Lu, Zhang-Hui; Jiang, Hai-Long; Akita, Tomoki; Xu, Qiang

    2011-08-10

    Bimetallic Au-Pd nanoparticles (NPs) were successfully immobilized in the metal-organic frameworks (MOFs) MIL-101 and ethylenediamine (ED)-grafted MIL-101 (ED-MIL-101) using a simple liquid impregnation method. The resulting composites, Au-Pd/MIL-101 and Au-Pd/ED-MIL-101, represent the first highly active MOF-immobilized metal catalysts for the complete conversion of formic acid to high-quality hydrogen at a convenient temperature for chemical hydrogen storage. Au-Pd NPs with strong bimetallic synergistic effects have a much higher catalytic activity and a higher tolerance with respect to CO poisoning than monometallic Au and Pd counterparts. PMID:21761819

  19. Formation of Ag 2, Au 2 and AgAu particles on MgO(1 0 0): DFT study on the role of support-induced charge transfer in metal-metal interactions

    NASA Astrophysics Data System (ADS)

    Fuente, Silvia A.; Belelli, Patricia G.; Branda, María M.; Ferullo, Ricardo M.; Castellani, Norberto J.

    2009-05-01

    The formation of Ag 2, Au 2 and AgAu particles oriented perpendicularly to the MgO(1 0 0) surface was studied using the density functional theory. While the support induces a slight enhancement of the Ag-Ag bond (by 0.3-0.4 eV), the Au-Au bond is strongly enhanced (by 0.8-1.1 eV). Concerning the bimetallic particle, the Ag-Au bond stabilization depends on the relative position of each atom. Thus, in general terms, the strength of the metal-metal bond is determined by the nature of the terminal atom; the bond is stronger in Au-terminal particles. The partial electronic charge transfer to the terminal Au atom and its ability to polarize this charge are responsible for this energetic stabilization.

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

    PubMed

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

    2005-03-01

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

  1. Optical properties of ZnSe doped with Ag and Au

    NASA Astrophysics Data System (ADS)

    Dean, P. J.; Fitzpatrick, B. J.; Bhargava, R. N.

    1982-08-01

    We present bound-exciton (BE) and donor-acceptor-pair (DAP) spectra of ZnSe grown by liquid-phase epitaxy and doped with the transition metals (TM) Ag and Au. Luminescence, luminescence excitation, and time decay spectra establish the assignments of the spectral features and show that Ag forms a medium deep acceptor, (EA)Ag=431+/-2 meV, consistent with the activation energy for thermal quenching of the DAP spectra. This thermal technique, together with the less precise spectral measurements available for the more-strongly-phonon-coupled Au acceptor indicate that (EA)Au~550 meV, appreciably less than the probable value for Cu, ~650 meV. Peculiarities in the BE properties within this TM sequence are discussed with reference to the influence of their d-state characteristics. Strong BE luminescence with no-phonon energy near 2.747 eV is attributed to a neutral AgZn-AgI associate, possibly a split interstitial. Reasons for its absence in ZnSe: Au are discussed. Isotope effects in this spectrum and that of the Li neutral acceptor BE are contrasted. The latter provides proof that LiZn is the persistent shallow Td site acceptor in ZnSe. Further associate BE luminescence is tentatively identified for ZnSe: Ag and ZnSe: Au.

  2. Au and Pd nanoparticles supported on CeO2, TiO2, and Mn2O3 oxides

    NASA Astrophysics Data System (ADS)

    Nascente, P. A. P.; Maluf, S. S.; Afonso, C. R. M.; Landers, R.; Pinheiro, A. N.; Leite, E. R.

    2014-10-01

    Gold and palladium nanoparticles were incorporated on CeO2, TiO2, and Mn2O3 supports prepared by a sol-gel method. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), high resolution TEM (HRTEM), scanning TEM (STEM) in high angle annular dark field mode (HAADF), and energy filtered TEM (EFTEM) using electron energy loss spectroscopy (EELS). The XRD diffractograms presented sharp and intense peaks indicating that the samples are highly crystalline, but it did not detected any peak corresponding to Au or Pd phases. This indicates that the Au and Pd NPs were incorporated into the structures of the oxides. It was not possible to obtain an Au 4f spectrum for Au/Mn2O3 due to an overlap with the Mn 3p spectrum. The XPS Au 4f spectra for Au/CeO2 and Au/TiO2 present negative chemical shifts that could be attributed to particle-size-related properties. The XPS Pd 3d spectra indicate that for both CeO2 and TiO2 substrates, the Pd NPs were in the metallic state, while for the Mn2O3 substrate, the Pd NPs were oxidized. The HRTEM results show the formation of nanocrystalline oxides having particles sizes between 50 and 200 nm. TEM micrographs show that the addition of Au caused the formation of Au clusters in between the CeO2 NPS, formation of Au NPs for the TiO2 support, and homogeneous distribution of Au clusters for the Mn2O3 support. The addition of Pd yielded a homogeneous dispersion throughout the CeO2 and TiO2, but caused the formation of Pd clusters for the Mn2O3 support.

  3. Study of thermal diffusivity of nanofluids with bimetallic nanoparticles with Au(core)/Ag(shell) structure

    NASA Astrophysics Data System (ADS)

    Gutierrez Fuentes, R.; Pescador Rojas, J. A.; Jiménez-Pérez, J. L.; Sanchez Ramirez, J. F.; Cruz-Orea, A.; Mendoza-Alvarez, J. G.

    2008-11-01

    The thermal diffusivity of Au/Ag nanoparticles with core/shell structure, at different compositions (Au/Ag = 3/1, 1/1, 1/3, 1/6), was measured by using the mismatched mode of the dual-beam thermal lens (TL) technique. This study determines the effect of the bimetallic composition on the thermal diffusivity of the nanofluids. In these results we find a lineal increment of the nanofluid it thermal diffusivity when the Ag shell thickness is increased. Our results show that the nanoparticle structure is an important parameter to improve the heat transport in composites and nanofluids. These results could have importance for applications in therapies and photothermal deliberation of drugs. Complementary measurements with UV-vis spectroscopy and TEM, were used to characterize the Au(core)/Ag(shell) nanoparticles.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  5. 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.

  6. 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. PMID:26035249

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

    NASA Astrophysics Data System (ADS)

    Wang, Long-De; Zhang, Tong; Zhang, Xiao-Yang; Song, Yuan-Jun; Li, Ruo-Zhou; Zhu, Sheng-Qing

    2014-03-01

    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.

  8. 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.

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

    SciTech Connect

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

    2009-10-22

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

  10. The adsorption and reaction of vinyl acetate on Au/Pd(100) alloy surfaces

    SciTech Connect

    Li, Zhenjun; Calaza, Florencia C; Tysoe, Wilfred

    2012-01-01

    The surface chemistry of vinyl acetate monomer (VAM) is studied on Au/Pd(100) alloys as a function of alloy composition using temperature-programmed desorption and reflection adsorption infrared spectroscopy. VAM adsorbs weakly on isolated palladium sites on the alloy with a heat of adsorption of ~55 kJ/mol, with the plane of the VAM adsorbed close to parallel to the surface. The majority of the VAM adsorbed on isolated sites desorbs molecularly with only a small portion decomposing. At lower gold coverages (below ~0.5 ML of gold), where palladium palladium bridge sites are present, VAM binds to the surface in a distorted geometry via a rehybridized vinyl group. A larger proportion of this VAM decomposes and this reaction is initiated by C\\O bond scission in the VAM to form adsorbed acetate and vinyl species. The implication of this surface chemistry for VAM synthesis on Au/Pd(100) alloys is discussed.

  11. 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.

  12. Nanocrystalline Pd alloy films coated by electroless deposition.

    PubMed

    Strukov, G V; Strukova, G K; Batov, I E; Sakharov, M K; Kudrenko, E A; Mazilkin, A A

    2011-10-01

    The structures of palladium and palladium alloys thin films deposited from organic electrolytes onto metallic substrates by electroless plating method have been investigated. The coatings are dense, pore-free 0.005-1 microm thick films with high adhesive strength to the substrate surface. EDX, XRD, SEM and TEM methods were used to determine the composition and structure of alloy coatings of the following binary systems: Pd-Au, Pd-Ag, Pd-Ni, Pd-Pb, and ternary system Pd-Au-Ni. The coatings of Pd-Au, Pd-Ag and Pd-Ni have a solid solution structure, whereas Pd-Pb is intermetallic compound. It has been found that the deposited films consist of nanocrystalline grains with sizes in the range of 11-35 nm. Scanning and transmission electron microscopy investigations reveal the existence of clusters formed by nanocrystalline grains. The origin for the formation of nanocrystalline structures of coating films is discussed. PMID:22400291

  13. A Bis(Diphosphanyl N-Heterocyclic Carbene) Gold Complex: A Synthon for Luminescent Rigid AuAg2 Arrays and Au5 and Cu6 Double Arrays.

    PubMed

    Ai, Pengfei; Mauro, Matteo; De Cola, Luisa; Danopoulos, Andreas A; Braunstein, Pierre

    2016-03-01

    A mononuclear bis(NHC)/Au(I) (NHC=N-heterocyclic carbene) cationic complex with a rigid bis(phosphane)-functionalized NHC ligand (PCNHC P) was used to construct linear Au3 and Ag2 Au arrays, a Au5 cluster with two intersecting crosslike Au3 arrays, and an unprecedented Cu6 complex with two parallel Cu3 arrays. The impact of metallophilic interactions on photoluminescence was studied experimentally. PMID:26823329

  14. First principles calculation of the structural, electronic, and magnetic properties of Au-Pd atomic chains

    SciTech Connect

    Dave, Mudra R.; Sharma, A. C.

    2015-06-24

    The structural, electronic and magnetic properties of free standing Au-Pd bimetallic atomic chain is studied using ab-initio method. It is found that electronic and magnetic properties of chains depend on position of atoms and number of atoms. Spin polarization factor for different atomic configuration of atomic chain is calculated predicting a half metallic behavior. It suggests a total spin polarised transport in these chains.

  15. 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

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

    PubMed

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

    1983-12-01

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

  17. Third-order optical nonlinearity studies of bilayer Au/Ag metallic films

    NASA Astrophysics Data System (ADS)

    Mezher, M. H.; Chong, W. Y.; Zakaria, R.

    2016-05-01

    This paper presents nonlinear optical studies of bilayer metallic films of gold (Au) and silver (Ag) on glass substrate prepared using electron beam evaporation. The preparation of Au and Ag nanoparticles (NPs) on the substrate involved the use of electron beam deposition, then thermal annealing at 600 °C and 270 °C, respectively, to produce a randomly distributed layer of Au and a layer of Ag NPs. Observation of field-effect scanning electron microscope images indicated the size of the NPs. Details of the optical properties related to peak absorption of surface plasmon resonance of the nanoparticle were revealed by use of UV-Vis spectroscopy. The Z-scan technique was used to measure the nonlinear absorption and nonlinear refraction of the fabricated NP layers. The third-order nonlinear refractive index coefficients for Au and Ag are (-9.34 and  -1.61)  ×  10-11 cm2 W-1 given lower n 2, in comparison with bilayer (Au and Ag) NPs at  -1.24  ×  10-10 cm2 W-1. The results show bilayer NPs have higher refractive index coefficients thus enhance the nonlinearity effects.

  18. 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.

  19. 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. PMID:24370431

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

    NASA Astrophysics Data System (ADS)

    Zhang, Xilin; Lu, Zhansheng; Yang, Zongxian

    2016-07-01

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

  1. Potential anticancer heterometallic Fe-Au and Fe-Pd agents: initial mechanistic insights.

    PubMed

    Lease, Nicholas; Vasilevski, Vadim; Carreira, Monica; de Almeida, Andreia; Sanaú, Mercedes; Hirva, Pipsa; Casini, Angela; Contel, María

    2013-07-25

    A series of gold(III) and palladium(II) heterometallic complexes with new iminophosphorane ligands derived from ferrocenylphosphanes [{Cp-P(Ph2)═N-Ph}2Fe] (1), [{Cp-P(Ph2)═N-CH2-2-NC5H4}2Fe] (2), and [{Cp-P(Ph2)═N-CH2-2-NC5H4}Fe(Cp)] (3) have been synthesized and structurally characterized. Ligands 2 and 3 afford stable coordination complexes [AuCl2(3)]ClO4, [{AuCl2}2(2)](ClO4)2, [PdCl2(3)], and [{PdCl2}2(2)]. The complexes have been evaluated for their antiproliferative properties in human ovarian cancer cells sensitive and resistant to cisplatin (A2780S/R), in human breast cancer cells (MCF7) and in a nontumorigenic human embryonic kidney cell line (HEK-293T). The highly cytotoxic trimetallic derivatives M2Fe (M = Au, Pd) are more cytotoxic to cancer cells than their corresponding monometallic fragments. Moreover, these complexes were significantly more cytotoxic than cisplatin in the resistant A2780R and the MCF7 cell lines. Studies of the interactions of the trimetallic compounds with DNA and the zinc-finger protein PARP-1 indicate that they exert anticancer effects in vitro based on different mechanisms of actions with respect to cisplatin. PMID:23786413

  2. Potential Anticancer Heterometallic Fe-Au and Fe-Pd Agents: Initial Mechanistic Insights

    PubMed Central

    Lease, Nicholas; Vasilevski, Vadim; Carreira, Monica; de Almeida, Andreia; Sanaú, Mercedes; Hirva, Pipsa; Casini, Angela; Contel, Maria

    2013-01-01

    A series of gold(III) and palladium(II) heterometallic complexes with new iminophosphorane ligands derived from ferrocenyl-phosphanes [{Cp-P(Ph2)=N-Ph}2Fe] (1), [{Cp-P(Ph2)=N-CH2-2-NC5H4}2Fe] (2) and [{Cp-P(Ph2)=N-CH2-2-NC5H4}Fe(Cp)] (3) have been synthesized and structurally characterized. Ligands 2 and 3 afford stable coordination complexes [AuCl2(3)]ClO4, [{AuCl2}2(2)](ClO4)2, [PdCl2(3)] and [{PdCl2}2(2)]. The complexes have been evaluated for their antripoliferative properties in human ovarian cancer cells sensitive and resistant to cisplatin (A2780S/R), in human breast cancer cells (MCF7) and in a non-tumorigenic human embryonic kidney cell line (HEK-293T). The highly cytotoxic trimetallic derivatives M2Fe (M = Au, Pd) are more cytotoxic to cancer cells than their corresponding monometallic fragments. Moreover, these complexes were significantly more cytotoxic than cisplatin in the resistant A2780R and the MCF7 cell lines. Studies of the interactions of the trimetallic compounds with DNA and the zinc-finger protein PARP-1 indicate that they exert anticancer effects in vitro based on different mechanisms of actions with respect to cisplatin. PMID:23786413

  3. Isolation of atomically precise mixed ligand shell PdAu24 clusters.

    PubMed

    Sels, Annelies; Barrabés, Noelia; Knoppe, Stefan; Bürgi, Thomas

    2016-06-01

    Exposure of PdAu24(2-PET)18 (2-PET: 2-phenylethylthiolate) to BINAS (1,1-binaphthyl-2,2-dithiol) leads to species of composition PdAu24(2-PET)18-2x(BINAS)x due to ligand exchange reactions. The BINAS adsorbs in a specific mode that bridges the apex and one core site of two adjacent S(R)-Au-S(R)-Au-S(R) units. Species with different compositions of the ligand shell can be separated by HPLC. Furthermore, site isomers can be separated. For the cluster with exactly one BINAS in its ligand shell only one isomer is expected due to the symmetry of the cluster, which is confirmed by High-Performance Liquid Chromatography (HPLC). Addition of a second BINAS to the ligand shell leads to several isomers. In total six distinguishable isomers are possible for PdAu24(2-PET)14(BINAS)2 including two pairs of enantiomers concerning the adsorption pattern. At least four distinctive isomers are separated by HPLC. Calculations indicate that one of the six possibilities is energetically disfavoured. Interestingly, diastereomers, which have an enantiomeric relationship concerning the adsorption pattern of chiral BINAS, have significantly different stabilities. The relative intensity of the observed peaks in the HPLC does not reflect the statistical weight of the different isomers. This shows, as supported by the calculations, that the first adsorbed BINAS molecule influences the adsorption of the second incoming BINAS ligand. In addition, experiments with the corresponding Pt doped gold cluster reveal qualitatively the same behaviour, however with slightly different relative abundances of the corresponding isomers. This finding points towards the influence of electronic effects on the isomer distribution. Even for clusters containing more than two BINAS ligands a limited number of isomers were found, which is in contrast to the corresponding situation for monothiols, where the number of possible isomers is much larger. PMID:27180647

  4. 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.

  5. 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

  6. 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.

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

    PubMed

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

    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 Cd(2+) 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

  8. 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

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    SciTech Connect

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

    2014-09-01

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

  12. 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. PMID:26227074

  13. 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.

  14. 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.

  15. Constraints on Variable Ag:Au:Cu Ore-Metal Ratios in Felsic Arc-Magmas

    NASA Astrophysics Data System (ADS)

    Piccoli, P.; Englander, L.; Candela, P.

    2004-12-01

    Silver:gold:copper ratios are variable in porphyry-type ore systems. In an attempt to better understand why, we have employed experimental techniques to determine how silver and copper, and gold from previous experiments, are sequestered in felsic magmas. To this end, we are performing sealed silica tube experiments on the equilibria among pyrrhotite-magnetite-silver alloy at 800C and at vapor pressure. Run times for the preliminary experiments were 144 hours; runs had magnetite/pyrrhotite ratio of 4. The source of silver in the runs was AgCl. Analysis of reconnaissance experiments demonstrates the stability of magnetite, pyrrhotite and a silver sulfide solid solution under the conditions of the experiments. Equilibrium concentrations of ore metals in the run products are ~3000 ppm Ag and 3500 ppm Cu in the pyrrhotite. However, the concentrations in magnetite are significantly different: 100 ppm Ag and ~20 ppm Cu. Like copper and gold (Jugo et al., 1999; Lithos), silver is concentrated in pyrrhotite relative to magnetite. The equilibrium Ag-sulfide composition in the run products is Ag53Fe8Cu3S36, with a mole fraction of Ag2S of 0.74. The log fS2 is approximated as ~ -4. The mole fraction of Ag in an ideal metal solid solution in equilibrium with an ideal model Ag2S solid solution, and a log fS2 of -4, is ~0.4. By analogy with Au, the substitution of Ag into pyrrhotite may occur as an AgFeS2 component. The substitutional mechanism for Ag in magnetite is not clear: silver may substitute as AgFe(3+)(Fe(2+))-2, but may also be present in defects in the magnetite structure. The partition coefficient (D(po/mt)) for approximately 30 for Ag. The partition coefficient for Au is higher (~120) based on the data of Simon et al. (2003; Am. Min,) and Jugo et al. (1999; Lithos). These data can be combined with data on the solubility of Ag in silicate melts to calculate mineral-melt partition coefficients. These data suggest that the role of pyrrhotite crystallization in felsic

  16. 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

  17. Preparation and characterization of chitosan/graphene oxide composites for the adsorption of Au(III) and Pd(II).

    PubMed

    Liu, Li; Li, Cui; Bao, Changli; Jia, Qiong; Xiao, Pengfei; Liu, Xiaoting; Zhang, Qiuping

    2012-05-15

    In this work, graphene oxide (GO) was firstly prepared, following by element analysis. Glutaraldehyde cross-linked chitosan (GCCS) and chitosan/graphene oxide (CSGO) composite with three different amounts of GO (5 wt%, 10 wt% and 15 wt%) were also prepared for the adsorption of Au(III) and Pd(II) in aqueous solution. The properties of the adsorbents were investigated by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and surface area analysis. Batch adsorption studies were carried out. The adsorption of Au(III) and Pd(II) onto CSGO composites was optimum at pH 3.0-5.0 for Au(III) and pH 3.0-4.0 for Pd(II), which was much wider than that of GCCS. The adsorption isotherms obeyed the Langmuir isotherm models for the adsorption of Au(III) and Pd(II). Chitosan with 5 wt% graphene oxide (CSGO(5)) composite had the largest adsorption capacity for Au(III) and Pd(II) compared with the other prepared adsorbents, where the maximum adsorption capacity were 1076.649 mg/g for Au(III) and 216.920 mg/g for Pd(II), respectively. The adsorption kinetics of Au(III) and Pd(II) onto CSGO(5) followed a pseudo-second-order kinetic model, indicating that the chemical adsorption was the rate-limiting step. Thermodynamic parameters, such as Gibbs energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°), were calculated, showing that the adsorption of Au(III) and Pd(II) onto CSGO(5) were spontaneous, endothermic and feasible. The desorption studies of Au(III) and Pd(II) onto CSGO(5) showed that CSGO(5) can be used repeatedly without significantly changing its adsorption capacity and desorption percentage after 3 cycles. Besides CSGO(5) was successfully applied for the determination and separation of Au(III) and Pd(II) in ore samples. PMID:22483922

  18. 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

  19. Experimental partitioning studies near the Fe-FeS eutectic, with an emphasis on elements important to iron meteorite chronologies (Pb, Ag, Pd, and Tl)

    NASA Technical Reports Server (NTRS)

    Jones, J. H.; Hart, S. R.; Benjamin, T. M.

    1993-01-01

    Partitioning coefficients for metal/sulfide liquid, troilite/sulfide liquid, and schreibersite/sulfide liquid were determined for Ag, Au, Mo, Ni, Pd, and Tl (using EMPA and proton-induced X-ray microprobe and ion microprobe analyses) in order to understand the chronometer systems of iron meteorites. In general, the obtained schreibersite/metal and troilite/metal partition coefficients for 'compatible' elements were quite similar to those inferred from natural assemblages, reinforcing an earlier made conclusion that there is a class of elements for which experimental troilite/metal and schreibersite/metal partition coefficients approximate those inferred from natural samples. The consistency between experimental and natural assemblages, however, was not observed for Ag, Pb, and Tl, indicating that the abundances of these elements determined in 'metal' and 'troilite' separates from iron meteorites are influenced by trace minerals that concentrate incompatible elements.

  20. Pd-on-Au Supra-nanostructures Decorated Graphene Oxide: An Advanced Electrocatalyst for Fuel Cell Application.

    PubMed

    Tao, Yingzhou; Dandapat, Anirban; Chen, Liming; Huang, Youju; Sasson, Yoel; Lin, Zhenyu; Zhang, Jiawei; Guo, Longhua; Chen, Tao

    2016-08-30

    We report a very easy and effective approach for synthesizing unique palladium-on-gold supra-nanostructure (Au@Pd-SprNS)-decorated graphene oxide (GO) nanosheets. The SprNSs comprising Au nanorods as core and a unique close-packed assembly of tiny anisotropic Pd nanoparticles (NPs) as shell were homogeneously distributed on the GO surface via electrostatic self-assembly. Compared with the traditional one-pot method for synthesis of metal NPs on GO sheets, the size and shape of core-shell Au@Pd SprNSs can be finely controlled and uniformly distributed on the GO carrier. Interestingly, this Au@Pd-SprNSs/GO nanocomposite displayed high electrocatalytic activities toward the oxidation of methanol, ethanol, and formic acid, which can be attributed to the abundance of intrinsic active sites including high density of atomic steps, ledges and kinks, Au-Pd heterojunctions and cooperative action of the two metals of the SprNSs. Additionally, uniform dispersion of the SprNSs over the GO nanosheets prevent agglomeration between the SprNSs, which is of great significance to enhance the long-term stability of catalyst. This work will introduce a highly efficient Pd-based nanoelectrocatalyst to be used in fuel cell application. PMID:27482606

  1. Electron correlation and relativistic effects in the coinage metal compounds. II. Heteronuclear dimers: CuAg, CuAu, and AgAu

    NASA Astrophysics Data System (ADS)

    Kellö, Vladimir; Sadlej, Andrzej J.

    1995-08-01

    Electric properties of heteronuclear dimers of the coinage metals are calculated at the level of the CCSD(T) approximation applied to 38 electrons of the valence and next-to-valence atomic shells. The relativistic effects are accounted for by using the scalar approximation to the Pauli hamiltonian. Both the pure relativistic and mixed relativistic-correlation contributions to energies and electric properties are computed. All calculations have been carried out by using the recently developed first-order polarized basis sets of the coinage metal atoms. In the non-relativistic approximation all studied dimers show only a moderate degree of polarity; the non-relativistic CuAg turns out to be the most polar dimer with the Cu(-)Ag(+) polarity. The relativistic effects considerably reduce the negative value of the CuAg dipole moment, change the sign of the CuAu dipole moment, and make the AgAu molecule the most polar species in the series. Simultaneously, the parallel component of the dipole polarizability shows only a small relativistic contraction. The calculated quasirelativistic interaction potentials have a correct behavior in the vicinity of their minima and give the Re and ωe values in complete agreement with experiment. Much less satisfactory are the dissociation energy data which seem to suffer from the single reference configuration approximation.

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

    NASA Astrophysics Data System (ADS)

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

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

  3. Plasmonic-induced inhibition and enhancement of the electrocatalytic activity of Pd-Au hetero-nanoraspberries for ethanol oxidation

    NASA Astrophysics Data System (ADS)

    Wang, Qiyu; Zheng, Weitao; Chen, Hong; Zhang, Bingsen; Su, Dangsheng; Cui, Xiaoqiang

    2016-06-01

    Plasmonic modulation of the catalytic performances of metallic nanostructures shows great potential in the development of novel materials for catalysis. In addition to the challenges of devising new catalysts with high activity while maintaining controllable plasmonic properties, the mechanisms underlying the enhancement of the activity by surface plasmon resonance (SPR) are still under exploration. Here, we design a Pd-Au bimetallic hetero structure and use the well-defined SPR property of the core Au NPs to tune its surface electro catalytic activity. The hot electrons are transferred into the Pd nanopetals from the Au core with visible-light irradiation, resulting in an enhancement of the electrocatalytic oxidation of ethanol on Au concurrent with an inhibition on Pd. The anti-poisoning and stability of the as-prepared heterostructures is also enhanced by visible-light irradiation.

  4. 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.

  5. Noble metals (Ag, Au) nanoparticles addition effects on superconducting properties of CuTl-1223 phase

    NASA Astrophysics Data System (ADS)

    Jabbar, Abdul; Mumtaz, Muhammad; Nadeem, Kashif

    2015-03-01

    Low anisotropic (Cu0.5Tl0.5) Ba2Ca2Cu3O10 - δ (CuTl-1223) high temperature superconducting phase was synthesized by solid-state reaction, silver (Ag) nanoparticles were prepared by sol-gel method and gold (Au) nanoparticles were extracted from colloidal solution. We added Ag and Au nanoparticles in CuTl-1223 matrix separately with same concentration during the final sintering process to get (M)x/CuTl-1223; M = Ag nanoparticles or Au nanoparticles (x = 0 and 1.0 wt.%) nano-superconductor composites. We investigated and compared the effects of these noble metals nanoparticles addition on structural, morphological and superconducting transport properties of CuTl-1223 phase. The crystal structure of the host CuTl-1223 superconducting phase was not affected significantly after the addition of these nanoparticles. The enhancement of superconducting properties was observed after the addition of both Ag and Au nanoparticles, which is most probably due to improved inter-grains weak-links and reduction of defects such as oxygen deficiencies, etc. The reduction of normal state room temperature resistivity is the finger prints of the reduction of barriers and facilitation to the carriers transport across the inter-crystallite sites due to improved inter-grains weak-links. The greater improvement of superconducting properties in Ag nanoparticles added samples is attributed to the higher conductivity of silver as compared to gold, which also suits for practical applications due to lower cost and easy synthesis of Ag nanoparticles as compared to Au nanoparticles.

  6. Isolation of atomically precise mixed ligand shell PdAu24 clusters

    NASA Astrophysics Data System (ADS)

    Sels, Annelies; Barrabés, Noelia; Knoppe, Stefan; Bürgi, Thomas

    2016-05-01

    Exposure of PdAu24(2-PET)18 (2-PET: 2-phenylethylthiolate) to BINAS (1,1-binaphthyl-2,2-dithiol) leads to species of composition PdAu24(2-PET)18-2x(BINAS)x due to ligand exchange reactions. The BINAS adsorbs in a specific mode that bridges the apex and one core site of two adjacent S(R)-Au-S(R)-Au-S(R) units. Species with different compositions of the ligand shell can be separated by HPLC. Furthermore, site isomers can be separated. For the cluster with exactly one BINAS in its ligand shell only one isomer is expected due to the symmetry of the cluster, which is confirmed by High-Performance Liquid Chromatography (HPLC). Addition of a second BINAS to the ligand shell leads to several isomers. In total six distinguishable isomers are possible for PdAu24(2-PET)14(BINAS)2 including two pairs of enantiomers concerning the adsorption pattern. At least four distinctive isomers are separated by HPLC. Calculations indicate that one of the six possibilities is energetically disfavoured. Interestingly, diastereomers, which have an enantiomeric relationship concerning the adsorption pattern of chiral BINAS, have significantly different stabilities. The relative intensity of the observed peaks in the HPLC does not reflect the statistical weight of the different isomers. This shows, as supported by the calculations, that the first adsorbed BINAS molecule influences the adsorption of the second incoming BINAS ligand. In addition, experiments with the corresponding Pt doped gold cluster reveal qualitatively the same behaviour, however with slightly different relative abundances of the corresponding isomers. This finding points towards the influence of electronic effects on the isomer distribution. Even for clusters containing more than two BINAS ligands a limited number of isomers were found, which is in contrast to the corresponding situation for monothiols, where the number of possible isomers is much larger.Exposure of PdAu24(2-PET)18 (2-PET: 2-phenylethylthiolate) to BINAS (1

  7. Surface structure characterization of ultra-thin films of Au deposited on Pd(111)

    NASA Astrophysics Data System (ADS)

    Pancotti, A.; de Siervo, A.; Nascente, P. A. P.; Landers, R.

    2016-06-01

    Ultra-thin films of Au were deposited on the Pd(111) surface and then characterized by X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), and X-ray photoelectron diffraction (XPD) generated by synchrotron radiation. The Au films were deposited at room temperature (300 K) and subsequently annealed at 400 °C (673 K) and 610 °C (883 K). XPD analyses indicated that the gold films were 7 and 6 ML thick, for the annealing temperatures of 400 °C and 610 °C, respectively. The film interlayer distances exhibited an oscillatory behavior, with a 5% contraction between the top and the second layers, a 3% expansion between the second and the third layers, for the film annealed at 400 °C, and a 2% expansion in the interlayer distance between the top and the second layers and a 4% contraction between the second and the third layers, for the film annealed at 610 °C. For both annealing temperatures, the interlayer distances between the third and the fourth layers and between the fourth and the fifth layers exhibited a 1% expansion and a 2% contraction. For the film annealed at 610 °C, XPD results revealed that the Pd(111) surface was covered by Au islands, with some bare patches exposed.

  8. Isolation of atomically precise mixed ligand shell PdAu24 clusters

    NASA Astrophysics Data System (ADS)

    Sels, Annelies; Barrabés, Noelia; Knoppe, Stefan; Bürgi, Thomas

    2016-05-01

    Exposure of PdAu24(2-PET)18 (2-PET: 2-phenylethylthiolate) to BINAS (1,1-binaphthyl-2,2-dithiol) leads to species of composition PdAu24(2-PET)18-2x(BINAS)x due to ligand exchange reactions. The BINAS adsorbs in a specific mode that bridges the apex and one core site of two adjacent S(R)-Au-S(R)-Au-S(R) units. Species with different compositions of the ligand shell can be separated by HPLC. Furthermore, site isomers can be separated. For the cluster with exactly one BINAS in its ligand shell only one isomer is expected due to the symmetry of the cluster, which is confirmed by High-Performance Liquid Chromatography (HPLC). Addition of a second BINAS to the ligand shell leads to several isomers. In total six distinguishable isomers are possible for PdAu24(2-PET)14(BINAS)2 including two pairs of enantiomers concerning the adsorption pattern. At least four distinctive isomers are separated by HPLC. Calculations indicate that one of the six possibilities is energetically disfavoured. Interestingly, diastereomers, which have an enantiomeric relationship concerning the adsorption pattern of chiral BINAS, have significantly different stabilities. The relative intensity of the observed peaks in the HPLC does not reflect the statistical weight of the different isomers. This shows, as supported by the calculations, that the first adsorbed BINAS molecule influences the adsorption of the second incoming BINAS ligand. In addition, experiments with the corresponding Pt doped gold cluster reveal qualitatively the same behaviour, however with slightly different relative abundances of the corresponding isomers. This finding points towards the influence of electronic effects on the isomer distribution. Even for clusters containing more than two BINAS ligands a limited number of isomers were found, which is in contrast to the corresponding situation for monothiols, where the number of possible isomers is much larger.Exposure of PdAu24(2-PET)18 (2-PET: 2-phenylethylthiolate) to BINAS (1

  9. Fabrication and evaluation of Au-Pd core-shell nanocomposites for dechlorination of diclofenac in water.

    PubMed

    Wang, Xu; Li, Jian-Rong; Fu, Ming-Lai; Yuan, Baoling; Cui, Hao-Jie; Wang, Ya-Fen

    2015-01-01

    Nanocomposites with core-shell structure usually exhibit excellent catalytic properties due to unique interfaces and synergistic effect among composites. In this study, Au-Pd bimetallic nanoparticles (NPs) with core-shell structure (Au-Pd cs) by using Au NPs as core and Pd as shell were successfully fabricated and, for the first time, were used to investigate the dechlorination of diclofenac (DCF) at H2 atmosphere in water at room temperature. The degradation products were studied as well by using HPLC/Q-ToF MS/MS. The operational factors such as pH and composition of the Au-Pd cs were also studied. The results showed that nearly 100% of DCF (30 mg L(-1), 50 mL, pH=7) was dechlorinated in 4.5 h by 10 mL of 56 mg L(-1) of Au-Pd cs. Ninety per cent of DCF was degraded in 6.5 h by the mixture of Au and Pd NPs. However, the individual Au NPs had no obvious effect in degrading DCF and the monometallic Pd NPs with comparable concentration only degraded less than 20% of DCF. Furthermore, the reaction mechanism of this catalytic process was studied in detail. It was found that the degradation was a second-order exponential reaction. The two main degradation products were obtained by cleaving the carbon-halogen bond of DCF and this made the degradation products more environmentally friendly. PMID:25441536

  10. Dodecahedral Au@Pd nanocrystals with high-index facets and excellent electrocatalytic activity and highly efficient surface-enhanced Raman scattering enhancement.

    PubMed

    Zhang, Lin-Fei; Zhang, Chun-Yang

    2013-07-01

    We synthesize the three-fold symmetric shield-like Au@Pd core-shell nanocrystals, enclosed predominantly by high-index {541} facets with kinks, through the simultaneous reduction of Au and Pd ions in the presence of triangular Au nanocrystal seeds in aqueous solution at room-temperature. The obtained shield-like Au@Pd core-shell nanocrystals exhibit superior electrocatalytic activity for the oxidation of ethanol and unique near-field enhancement property with a highly sensitive surface-enhanced Raman scattering (SERS) response. These excellent properties can be ascribed to the presence of sharp corners and edges as well as high-index faceted Pd-rich shell in the shield-like Au@Pd core-shell structure. We also investigate the mechanism for the formation of three-fold symmetric shield-like Au@Pd core-shell nanocrystals. PMID:23719781

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

    SciTech Connect

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

    2015-10-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  13. Dodecahedral Au@Pd nanocrystals with high-index facets and excellent electrocatalytic activity and highly efficient surface-enhanced Raman scattering enhancement

    NASA Astrophysics Data System (ADS)

    Zhang, Lin-Fei; Zhang, Chun-Yang

    2013-06-01

    We synthesize the three-fold symmetric shield-like Au@Pd core-shell nanocrystals, enclosed predominantly by high-index {541} facets with kinks, through the simultaneous reduction of Au and Pd ions in the presence of triangular Au nanocrystal seeds in aqueous solution at room-temperature. The obtained shield-like Au@Pd core-shell nanocrystals exhibit superior electrocatalytic activity for the oxidation of ethanol and unique near-field enhancement property with a highly sensitive surface-enhanced Raman scattering (SERS) response. These excellent properties can be ascribed to the presence of sharp corners and edges as well as high-index faceted Pd-rich shell in the shield-like Au@Pd core-shell structure. We also investigate the mechanism for the formation of three-fold symmetric shield-like Au@Pd core-shell nanocrystals.We synthesize the three-fold symmetric shield-like Au@Pd core-shell nanocrystals, enclosed predominantly by high-index {541} facets with kinks, through the simultaneous reduction of Au and Pd ions in the presence of triangular Au nanocrystal seeds in aqueous solution at room-temperature. The obtained shield-like Au@Pd core-shell nanocrystals exhibit superior electrocatalytic activity for the oxidation of ethanol and unique near-field enhancement property with a highly sensitive surface-enhanced Raman scattering (SERS) response. These excellent properties can be ascribed to the presence of sharp corners and edges as well as high-index faceted Pd-rich shell in the shield-like Au@Pd core-shell structure. We also investigate the mechanism for the formation of three-fold symmetric shield-like Au@Pd core-shell nanocrystals. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00695f

  14. 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.

  15. 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.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    PubMed Central

    Hong, Jun-Tae

    2014-01-01

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

  20. Kinetic analysis of the reduction of 4-nitrophenol catalyzed by Au/Pd nanoalloys immobilized in spherical polyelectrolyte brushes.

    PubMed

    Gu, Sasa; Lu, Yan; Kaiser, Julian; Albrecht, Martin; Ballauff, Matthias

    2015-11-14

    We present a detailed study of the catalytic activity of Au/Pd nanoalloys with Au : Pd molar ratio 75 : 25 synthesized using spherical polyelectrolyte brushes (SPB) as carrier system. The reduction of 4-nitrophenol (Nip) by sodium borohydride (BH4(-)) has been used as a model reaction. This reaction proceeds in two steps: 4-nitrophenol is first reduced to 4-hydroxylaminophenol which in a second step is reduced to the final product 4-aminophenol. Both steps of the reaction proceed on the surface of the nanoparticles (Langmuir-Hinshelwood-mechanism). We use this model to analyze the experimental data obtained by catalysis with the Au/Pd-nanoalloys. Good agreements between theory and experiments were found up to 30% conversion of Nip. The kinetic parameters were compared with the data derived from neat Au and Pd nanoparticles immobilized in the same SPB carrier system. The addition of 25% molar ratio of Pd to the nanoalloys increases the reaction rate of the first step nearly 10 times compared with that of SPB-Au and 60 times compared with that of SPB-Pd. Analysis of the nanoalloy by high-resolution transmission electron microscopy suggests that the surface defects of the nanoalloys play an important role for the enhanced catalytic activity. PMID:25790094

  1. Dependence of the conductance change on the molecular orbitals in Ag and Au electrodes

    NASA Astrophysics Data System (ADS)

    Kim, Hyun Sung; Kim, Taekyeong

    2016-01-01

    The conductance change in single-molecule junctions due to the molecular orbitals and the metal's Fermi energy was investigated by using a scanning tunneling microscopy break-junction technique with Ag and Au electrodes. 4,4'-diaminobiphenyl and 4,4'-dicyanobiphenyl as the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) junctions were used. The amine-linked HOMO-conducting junction had a lower conductance, and cyano-linked LUMO-conducting junction had a higher conductance for Ag electrode compared to Au electrode. These results are attributed to the difference between the metal electrode Fermi energy and the molecular orbital level in the metal-molecule junction. Furthermore, 2,7-diaminofluorene exhibited a higher conductance but the identical molecular plateau length for the Ag electrodes compared to that of 4,4'-diaminobiphenyl indicating that the twist angle of the molecular backbone affects the conductance.

  2. 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

  3. Highly sensitive electrochemical determination of Sunset Yellow based on the ultrafine Au-Pd and reduced graphene oxide nanocomposites.

    PubMed

    Wang, Jin; Yang, Beibei; Zhang, Ke; Bin, Duan; Shiraishi, Yukihide; Yang, Ping; Du, Yukou

    2016-11-01

    A sensitive and novel electrochemical sensor with Au-Pd and reduced graphene oxide (RGO) nanocomposites modified glassy carbon electrode (Au-Pd-RGO/GCE) was successfully fabricated by one-step synthesis method for the detection of Sunset Yellow. The as-prepared composites were uniformly dispersed on the surface of electrode with an average diameter of approximately 3.44nm, and the ultrafine nanoparticles effectively enhanced the electrochemical active surface area of GCE. The modified electrode had been characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and electrochemical tests. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) results showed high stability and outstanding electrocatalytic activity of Au-Pd-RGO/GCE for the detection of SY with low detection limits (1.5 nM, S/N=3) and wide concentration ranges (0.686-331.686μM). The Au-Pd-RGO/GCE was further applied to detect SY in real samples with good recovery. Herein, the fabricated Au-Pd-RGO/GCE showed excellent sensitivity, stability and repeatability for the detection of SY and will be a promising application in electrochemical sensor. PMID:27475710

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

    DOE PAGESBeta

    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

  5. Influence of Ag-Au microstructure on the photoelectrocatalytic performance of TiO2 nanotube array photocatalysts.

    PubMed

    Wang, Qingyao; Wang, Xiaotong; Zhang, Miao; Li, Guihua; Gao, Shanmin; Li, Mingyang; Zhang, Yiqing

    2016-02-01

    In this work, vertically-aligned TiO2 nanotube arrays (TiO2 NTs) were grown on Ti substrates via a facile electrochemical anodization method followed by calcinations. Then, Ag-Au alloy nanoparticles and Ag@Au core-shell nanoparticles were deposited on the obtained TiO2 NTs via UV reduction and displacement reaction, respectively. X-ray diffraction, scanning electron microscopy and transmission electron microscopy indicated that Ag-Au alloy nanoparticles and Ag@Au core-shell nanoparticles grew uniformly on the walls of TiO2 NTs. Investigation results from removal of methyl orange (MO) and Cr(IV) ions indicated that the as-prepared bimetal plasmonic photocatalysts exhibited excellent photoelectrocatalytic (PEC) activities. The influences of Ag-Au alloy and core-shell microstructures on PEC properties of TiO2 NTs were investigated and the TiO2 NTs/Ag@Au photocatalyst showed more outstanding PEC removal efficiency than that of TiO2 NTs/Ag-Au due to the regular core-shell microstructure and low recombination of photogenerated electrons and holes. PMID:26555961

  6. 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

  7. Nanometer sized electrodes fabricated by electromigration of Au and Pd nanowires

    NASA Astrophysics Data System (ADS)

    Vlad, Alexandru; Faniel, Sébastien; Hackens, Benoît; Bayot, Vincent; Melinte, Sorin

    2008-03-01

    Electromigration-driven metallic nanowire failure is presented. Here, Au and Pd nanowires patterned by electron-beam lithography were electrically stressed up to their breaking point. Feedback control and simple voltage sweep techniques have been successfully used to form nanometer-sized gaps. We observe a material- and geometry-dependent behavior. The Au nanowires showed a Joule-induced reversible resistance increase with the applied voltage up to the breaking point. In contrast, Pd nanowires presented an anomalous resistance decrease close to their failure point. This was associated to the melting and agglomeration of metallic grains within the electrically stressed nanowires. The SEM images acquired at intermediate stages of electromigration agree with the electrical data findings. The influence of the nanowire geometry upon the morphology of fabricated nanoelectrodes is considered. Beside the morphological characterization of our break junctions, we also measured their current-voltage characteristics. We observed single electron tunneling effects, probably due to the presence of metallic clusters formed close to the nanoelectrodes during the electromigration. Our results are consistent with recent findings on Coulomb blockade phenomena in electromigrated gold break junctions.

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

    1996-12-01

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

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

    SciTech Connect

    Morgan, G.

    2010-12-16

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    PubMed

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

    2015-04-01

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

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

    SciTech Connect

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

    1996-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    PubMed Central

    2012-01-01

    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. PMID:22916797

  16. 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.

  17. Sonochemically synthesized mono and bimetallic Au-Ag reduced graphene oxide based nanocomposites with enhanced catalytic activity.

    PubMed

    Neppolian, Bernaurdshaw; Wang, Chang; Ashokkumar, Muthupandian

    2014-11-01

    Graphene oxide (GO) supported Ag and Au mono-metallic and Au-Ag bimetallic catalysts were synthesized using a sonochemical method. Bimetallic catalysts containing different weight ratios of Au and Ag were loaded onto GO utilizing a low frequency horn-type ultrasonicator. High frequency ultrasonication was used to efficiently reduce Ag(I) and Au(III) ions in the presence of polyethylene glycol and 2-propanol. Transmission electron microscopy (TEM-EDX) and X-ray photoelectron spectroscopy were used to analyze the morphology, size, shape and chemical oxidation states of the prepared metallic catalysts on GO. The catalytic efficiency of the prepared catalysts were compared using 4-nitrophenol (4-NP) reduction reaction and the subsequent formation of 4-aminophenol (4-AP) that was also monitored using UV-vis spectrophotometry. The results revealed that Au-Ag-GO bimetallic catalysts showed high activity for the conversion of 4-NP to 4-AP than their monometallic counterparts. Amongst different weight ratios (1:1, 1:2 and 2:1) between Au and Ag, the 1:2 (Au:Ag) catalyst exhibited very good catalytic performance for the conversion of 4-NP to 4-AP. A total reduction of 4-NP took place within a short period of time if Au-GO was reduced first followed by Ag reduction, whereas a lower reduction rate was observed if Ag-GO was reduced first. The same trend was observed for all the ratios of bimetallic catalysts prepared by this method. The initial unfavorable reduction potential of Ag(I) is likely to be responsible for the above order. It was found that applying dual frequency ultrasonication was a highly effective way of preparing bimetallic catalysts requiring relatively low levels of added chemicals and producing bimetallic catalysts with GO with improved catalytic efficiency. PMID:24582660

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

    SciTech Connect

    Wang Yue; Shi Yongfang; Chen Yubiao; Wu Liming

    2012-07-15

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

  19. Long-range chemical orders in Au-Pd nanoparticles revealed by aberration-corrected electron microscopy.

    PubMed

    Nelayah, Jaysen; Nguyen, Nhat Tai; Alloyeau, Damien; Wang, Guillaume Yangshu; Ricolleau, Christian

    2014-09-01

    Despite the importance of gold-palladium nanoalloys in heterogeneous catalysis, the phase stability of Au-Pd alloys still remains unclear. We report here on the alloying and chemical ordering in epitaxially-grown and post-annealed gold-palladium nanoparticles (NPs) using aberration-corrected transmission electron microscopy. Au-Pd NPs with a controlled size, composition and structure were grown by pulsed laser deposition on freshly-cleaved NaCl(001) single crystals heated at 300 °C. After transfer to an amorphous carbon support, the NPs were annealed in vacuum at elevated temperatures above 400 °C for a few hours (6-10 hours) to promote chemical ordering. The as-grown NPs were mostly monocrystalline with a chemically-disordered face-centered cubic structure. Upon high-temperature annealing, a high degree of chemical ordering was observed in nanometer-sized NPs. Electron microscopy measurements showed that both L10 and L12 orders are stabilized in the Au-rich region of the Au-Pd phase diagram. These ordered phases exist at temperatures as high as 600 °C. Moreover, compositional analysis of single annealed particles revealed that the observed chemical ordering occurs in parallel to a two-tiered Ostwald ripening process. Due to this ripening process, a clear dependence between chemical composition and particle size is established during annealing with an enrichment in Pd as the NPs grow in size. Our results, besides clarifying some controversial aspects about long-range order in Au-Pd alloys, shed light on the structural stability of Au-Pd nanoalloys at elevated temperatures. PMID:25079393

  20. 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.

  1. The Role of d-Orbitals in the Rashba Splitting on Au(111) and Ag(111)

    NASA Astrophysics Data System (ADS)

    Lee, Hyungjun; Choi, Hyoung Joon

    2012-02-01

    We investigate the Rashba-type spin splitting in sp-derived Shockley surface states on (111) surfaces of noble metals, such as Au(111) and Ag(111), based on first-principles calculations including the spin-orbit interaction. By turning on and off l-dependent spin-orbit coupling one by one, we find that although the surface states on Au(111) have predominantly p-orbital character, the spin splitting in energy originates mainly from d-orbital character of the surface states. We also demonstrate that the spin splitting in surface states of both metallic surfaces of Au(111) and Ag(111) can be controlled by varying the sizes of d-orbital parts of the surface-state wave functions. These results show that in addition to difference in the atomic spin-orbit strength in Au and Ag, difference in d-orbital contributions to the surface states makes substantial difference in the sizes of the Rashba-type spin splitting in their surface electronic structures. This work was supported by the NRF of Korea (Grant Nos. 2009-0081204 and 2011-0018306) and KISTI Supercomputing Center (Project No. KSC-2011-C2-04).

  2. 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

  3. The adsorption of acetic acid on clean and oxygen-covered Au/Pd(100) alloy surfaces

    NASA Astrophysics Data System (ADS)

    Li, Zhenjun; Tysoe, Wilfred T.

    2012-12-01

    The adsorption of acetic acid is studied on clean and oxygen-covered Au/Pd(100) alloys as a function of gold content by temperature-programmed desorption and reflection-absorption infrared spectroscopy. Au/Pd(100) forms ordered alloys such that, for gold coverages above ~ 0.5 monolayers, only isolated palladium atoms surrounded by gold nearest neighbors are present. Predominantly molecular acetic acid forms on Au/Pd(100) alloy surfaces for gold coverages greater than ~ 0.56 ML, and desorbs with an activation energy of ~ 59 kJ/mol. Heating this surface also forms some η1-acetate species which decompose to form CO and hydrogen. On alloy surfaces with palladium-palladium bridge sites, η1-acetate species initially form, but rapidly convert into η2-species. They thermally decompose to form CO and hydrogen, with a small portion rehydrogenating to form acetic acid between 280 and 321 K depending on gold coverage. The presence of oxygen on both Pd(100) and Au/Pd(100) alloys facilitates acetate dehydrogenation so that only η2-acetate species form on these surfaces. The presence of oxygen also serves to stabilize the acetate species.

  4. 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.

  5. Effect of Thickness and Phosphorus Content on Au/Pd/Ni(P) Metal Finish of Printed Circuit Board

    NASA Astrophysics Data System (ADS)

    Huang, Chih-Kai; Lin, Keh-Wen; Huang, Yu-Ming; Caparanga, Alvin R.; Leron, Rhoda B.; Li, Meng-Hui

    2013-08-01

    Electroless nickel/electroless palladium/immersion gold [Au/Pd/Ni(P) or ENEPIG] pads consisting of layers of Ni(P) (200 μin), pure palladium (Pd) or palladium phosphorus (PdP) (2 μin, 4 μin or 6 μin), and gold (Au) (2 μin or 4 μin) were prepared using two different processes (wire bonding and lead-free soldering). Each of these processes was done with zero- or two-time reflow. Different tests on solderability, wettability, wire-bonding capacity, and corrosion resistance were performed on different combinations of ENEPIG pads formed using different combinations of processes and conditions. Scanning electron microscopy was also performed to examine the surface characteristics of the pads. It was found that the ENEPIG pad sample with the 4- μin-thick Au and 4- μin-thick PdP layers possessed stable wire-bonding capacity and excellent lead-free solder reliability. In addition, the ENEPIG-PdP systems showed better corrosion resistance, which is attributed to the presence of the amorphous PdP layer protecting the nickel layer.

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. Identification of Au-Sn phase in Ag3Sn alloys containing gold.

    PubMed

    Malhotra, M L; Lawless, K R

    1975-03-01

    Substitution of gold in part for silver in Ag3Sn alloys is found to result in two separate phases: gamma (Ag3Sn particles) grains with a uniform distribution of gold within the grain and an Au-Sn phase in a form of ring surrounding the gamma grain. The thickness of this ring increases with increasing gold concentration. The phases were identified by using the techniques of x-ray diffraction, optical metallography, scanning electron microscopy, and x-ray energy dispersive spectroscopy. PMID:1176478

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    Bimetallic palladium-silver nanoparticles (NPs) supported on reduced oxide graphene (RGO) with different Pd/Ag ratios (Pd-Ag/RGO) were prepared by an easy green method which did not use any additional reducing agents or a dispersing agent. During the process, simultaneous redox reactions between AgNO3, K2PdCl4 and graphene oxide (GO) led to bimetallic Pd-Ag NPs. The morphology and composition of the Pd-Ag/RGO were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis and Raman spectroscopy. Cyclic voltammetry and chronoamperometry were used to investigate the electrochemical activities and stabilities of these Pd-Ag/RGO catalysts for the electro-oxidation of methanol and ethanol in alkaline media. Among the different Pd/Ag ratios, the Pd-Ag (1:1)/RGO had the best catalytic activities and stability. So it is a promising catalyst for direct alcohol fuel cell applications.

  12. Deviations from one-electron behavior in the Ag and Pd M4,5-VV Auger spectra of AgcPd1-c alloys

    NASA Astrophysics Data System (ADS)

    Mariot, J.-M.; Hague, C. F.; Dufour, G.

    1981-04-01

    A systematic investigation of the Ag and Pd M4,5-VV Auger spectra in the pure metals and in the AgcPd1-c(0.1<=c<=0.9) alloys is presented. The shape of the Auger spectra is discussed in relation to the values of the effective Coulomb interaction Ueff between the two holes present in the final state of the Auger transition and of the width W of the one-electron local densities of states as obtained from Lβ2,15 soft-x-ray emission bands. The Auger spectra of Ag in the metal and the alloys have a pronounced quasiatomic character, as can be expected from the Ueff2W ratio which is found to be close to unity. The Auger spectrum of pure Pd (Ueff2W~0.4) can be explained in terms of an atomic model in which strong band effects are present. For alloys with low-Pd content where Pd forms an impurity state, it is shown that final states other than the localized [4d2] two-hole state have to be invoked to explain the line shape.

  13. Characteristics of localized surface plasmons excited on mixed monolayers composed of self-assembled Ag and Au nanoparticles.

    PubMed

    Tanaka, Daisuke; Imazu, Keisuke; Sung, Jinwoo; Park, Cheolmin; Okamoto, Koichi; Tamada, Kaoru

    2015-10-01

    The fundamental characteristics of localized surface plasmon resonance (LSPR) excited on mixed monolayers composed of self-assembled Ag and Au nanoparticles (AgNPs and AuNPs, respectively) were investigated. Mixed monolayered films were fabricated at the air-water interface at different mixing ratios. The films retained their phase-segregated morphologies in which AuNPs formed several 10 to 100 nm island domains in a homogeneous AgNP matrix phase. The LSPR bands originating from the self-assembled domains shifted to longer wavelengths as the domain size increased, as predicted by a finite-difference time-domain (FDTD) simulation. The FDTD simulation also revealed that even an alternating-lattice-structured two-dimensional (2D) AgNP/AuNP film retained two isolated LSPR bands, revealing that the plasmon resonances excited on each particle did not couple even in a continuous 2D sheet, unlike in the homologous NP system. The fluorescence quenching test of Cy3 and Cy5 dyes confirmed that the independent functions of AuNPs and AgNPs remained in the mixed films, whereas the AuNPs exhibited significantly higher quenching efficiency for the Cy3 dye compared with AgNPs due to the overlap of the excitation/emission bands of the dyes with the AuNP LSPR band. Various applications can be considered using this nanoheterostructured plasmonic assembly to excite spatially designed, high-density LSPR on macroscopic surfaces. PMID:26332039

  14. Insight on the Interaction of Methanol-Selective Oxidation Intermediates with Au- or/and Pd-Containing Monometallic and Bimetallic Core@Shell Catalysts.

    PubMed

    Czelej, Kamil; Cwieka, Karol; Colmenares, Juan Carlos; Kurzydlowski, Krzysztof J

    2016-08-01

    Using density functional theory (DFT), the interaction of crucial molecules involved in the selective partial oxidation of methanol to methyl formate (MF) with monometallic Au and Pd and bimetallic Au/Pd and Pd/Au core@shell catalysts is systematically investigated. The core@shell structures modeled in this study consist of Au(111) and Pd(111) cores covered by a monolayer of Pd and Au, respectively. Our results indicate that the adsorption strength of the molecules examined as a function of catalytic surface decreases in the order of Au/Pd(111) > Pd(111) > Au(111) > Pd/Au(111) and correlates well with the d-band center model. The preadsorption of oxygen is found to have a positive impact on the selective partial oxidation reaction because of the stabilization of CH3OH and HCHO on the catalyst surface and the simultaneous intensification of MF desorption. On the basis of a dynamical matrix approach combined with statistical thermodynamics, we propose a simple route for evaluating the Gibbs free energy of adsorption as a function of temperature. This method allows us to anticipate the relative temperature stability of molecules involved in the selective partial oxidation of methanol to MF in terms of catalytic surface. PMID:27373791

  15. Structural features and high quasi-static strain rate sensitivity of Au{sub 49}Cu{sub 26.9}Ag{sub 5.5}Pd{sub 2.3}Si{sub 16.3} bulk metallic glass

    SciTech Connect

    Ketov, S. V.; Chen, N.; Inoue, A.; Louzguine-Luzgin, D. V.; Caron, A.

    2012-12-10

    Here we report on the formation of a crystalline Au-based solid solution surface layer on solidification, which is responsible for yellow color of the Au-based bulk metallic glass (BMG) samples. The structure of the BMG alloy was studied by X-ray diffractometry, scanning electron microscopy, and transmission electron microscopy. The deformation behavior of these Au-based BMG samples on heating was studied at temperatures above T{sub g} at different strain rates.

  16. The O, OH and OOH-assisted selective coupling of methanol on Au-Ag(111).

    PubMed

    Zhong, Wenhui; Liang, Jinxia; Hu, Wei; Cao, Xinrui; Jia, Chuanyi; Jiang, Jun

    2016-04-21

    Using density functional theory (DFT) calculations, we performed a thorough theoretical investigation on the catalytic mechanism of oxidative self-coupling of methanol with molecular oxygen on Au-Ag catalysts. It is found that molecular oxygen can be activated via a hydroperoxyl (OOH) intermediate by taking a hydrogen atom from co-adsorbed methanol with an energy barrier of 0.51 eV, which is actually the rate determining step for the overall reaction. The O, OH and OOH oxidant formation proceeds via two channels of I and II with low barriers. We demonstrated that the oxidative coupling of methanol by OOH, atomic oxygen, and hydroxyl is much more favorable than the total oxidation of methanol, and is responsible for the high selectivity of Au-Ag catalysts in methanol oxidation. The revealed activation mechanism provides an efficient pathway for optimizing the selective coupling of methanol with dioxygen. PMID:26947704

  17. 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

  18. 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.

  19. Focused-ion-beam-fabricated Au nanorods coupled with Ag nanoparticles used as surface-enhanced Raman scattering-active substrate for analyzing trace melamine constituents in solution.

    PubMed

    Sivashanmugan, Kundan; Liao, Jiunn-Der; Liu, Bernard Haochih; Yao, Chih-Kai

    2013-10-24

    A well-ordered Au-nanorod array with a controlled tip ring diameter (Au_NRsd) was fabricated using the focused ion beam method. Au_NRsd was then coupled with Ag nanoparticles (Ag NPs) to bridge the gaps among Au nanorods. The effect of surface-enhanced Raman scattering (SERS) on Au_NRsd and Ag NPs/Au_NRsd was particularly verified using crystal violet (CV) as the molecular probe. Raman intensity obtained from a characteristic peak of CV on Au_NRsd was estimated by an enhancement factor of ≈10(7) in magnitude, which increased ≈10(12) in magnitude for that on Ag NPs/Au_NRsd. A highly SERS-active Ag NPs/Au_NRsd was furthermore applied for the detection of melamine (MEL) at very low concentrations. Raman-active peaks of MEL (10(-3) to 10(-12)M) in water or milk solution upon Au_NRsd or Ag NPs/Au_NRsd were well distinguished. The peaks at 680 and 702 cm(-1) for MEL molecules were found suitable to be used as the index for sensing low-concentration MEL in a varied solution, while that at 1051 cm(-1) was practical to interpret MEL molecules in water or milk solution bonded with Au (i.e., Au_NRsd) or Ag (i.e., Ag NPs/Au_NRsd) surface. At the interface of Ag NPs/Au_NRsd and MEL molecules in milk solution, a laser-induced electromagnetic field or hotspot effect was produced and competent to sense low-concentration MEL molecules interacting with Ag and Au surfaces. Accordingly, Ag NPs/Au_NRsd is very promising to be used as a fast and sensitive tool for screening MEL in complex matrices such as adulteration in e.g., food and pharmaceutical products. PMID:24120168

  20. Plasmonic effects of au/ag bimetallic multispiked nanoparticles for photovoltaic applications.

    PubMed

    Sharma, Manisha; Pudasaini, Pushpa Raj; Ruiz-Zepeda, Francisco; Vinogradova, Ekaterina; Ayon, Arturo A

    2014-09-10

    In recent years, there has been considerable interest in the use of plasmons, that is, free electron oscillations in conductors, to boost the performance of both organic and inorganic thin film solar cells. This has been driven by the possibility of employing thin active layers in solar cells in order to reduce materials costs, and is enabled by significant advances in fabrication technology. The ability of surface plasmons in metallic nanostructures to guide and confine light in the nanometer scale has opened up new design possibilities for solar cell devices. Here, we report the synthesis and characterization of highly monodisperse, reasonably stable, multipode Au/Ag bimetallic nanostructures using an inorganic additive as a ligand for photovoltaic applications. A promising surface enhanced Raman scattering (SERS) effect has been observed for the synthesized bimetallic Au/Ag multispiked nanoparticles, which compare favorably well with their Au and Ag spherical nanoparticle counterparts. The synthesized plasmonic nanostructures were incorporated on the rear surface of an ultrathin planar c-silicon/organic polymer hybrid solar cell, and the overall effect on photovoltaic performance was investigated. A promising enhancement in solar cell performance parameters, including both the open circuit voltage (VOC) and short circuit current density (JSC), has been observed by employing the aforementioned bimetallic multispiked nanoparticles on the rear surface of solar cell devices. A power conversion efficiency (PCE) value as high as 7.70% has been measured in a hybrid device with Au/Ag multispiked nanoparticles on the rear surface of an ultrathin, crystalline silicon (c-Si) membrane (∼ 12 μm). This value compares well to the measured PCE value of 6.72% for a similar device without nanoparticles. The experimental observations support the hope for a sizable PCE increase, due to plasmon effects, in thin-film, c-Si solar cells in the near future. PMID:25137194

  1. Spectroscopic monitoring on irradiation-induced formation of AuAg alloy nanoparticles by femtosecond laser

    NASA Astrophysics Data System (ADS)

    Herbani, Yuliati; Nakamura, Takahiro; Sato, Shunichi

    2016-02-01

    The interaction of an intense femtosecond laser pulses with a neat liquid solvent has been known to produce a number of highly reactive species that are useful to induce chemical reactions in the solution through the nonlinear absorption processes. When metal ions are present in the solution, they are assumed to readily reduce by ions, radicals, molecules or excited states generated photolytically from the solvent resulting in the formation of zerovalent metal nanoalloys. If two kinds of metal precursors are involved in a reduction process, the alloying process is expected. In this work, irradiation-induced synthesis of AuAg bimetallic nanoparticle at different laser-pulse energies was examined to investigate the formation mechanism in the presence of NH4OH in the initial solution. At a given laser pulse energy (5.8 mJ/pulse), the time evolution of the UV-visible absorption spectra showed that the formation of AuAg nanoalloys most likely begin with the formation of Ag-riched alloy nanoparticles. As the reduction is started, the absorption spectrum of solution was closer to that of pure Ag nanoparticles. This indicates that the reduction rate of Ag is relatively greater than that of Au nanoparticle in the presence of ammonia. The single peak position then shifts to the red region as the irradiation time increases. After 10 min, the peak positions are between pure silver and gold peaks indicating the alloying process occurs at this stage. At low pulse energy (1.0 mJ/pulse), there was an induction time for several minutes before the absorption is detectable, and hence the alloying process is also delayed (after 20 minutes irradiation). While the formation rate of nanoparticles is more pronounced at high laser pulse energy, the formation yield is relatively the same for both laser pulse energies.

  2. Highly Stretchable and Transparent Supercapacitor by Ag-Au Core-Shell Nanowire Network with High Electrochemical Stability.

    PubMed

    Lee, Habeom; Hong, Sukjoon; Lee, Jinhwan; Suh, Young Duk; Kwon, Jinhyeong; Moon, Hyunjin; Kim, Hyeonseok; Yeo, Junyeob; Ko, Seung Hwan

    2016-06-22

    Stretchable and transparent electronics have steadily attracted huge attention in wearable devices. Although Ag nanowire is the one of the most promising candidates for transparent and stretchable electronics, its electrochemical instability has forbidden its application to the development of electrochemical energy devices such as supercapacitors. Here, we introduce a highly stretchable and transparent supercapacitor based on electrochemically stable Ag-Au core-shell nanowire percolation network electrode. We developed a simple solution process to synthesize the Ag-Au core-shell nanowire with excellent electrical conductivity as well as greatly enhanced chemical and electrochemical stabilities compared to pristine Ag nanowire. The proposed core-shell nanowire-based supercapacitor still possesses fine optical transmittance and outstanding mechanical stability up to 60% strain. The Ag-Au core-shell nanowire can be a strong candidate for future wearable electrochemical energy devices. PMID:27285849

  3. 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.

  4. 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

  5. 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.

  6. First principles investigation of the diffusion of interstitial Cu, Ag and Au in ZnTe

    NASA Astrophysics Data System (ADS)

    Chen, Li An; Zhu, Xing Feng; Chen, Ling Fu

    2015-07-01

    The diffusion is of great significance in many applications when the impurities are employed to tune the semiconductor's electrical or optical properties. It is necessary to understand how dopant defects diffuse in semiconductors. Using first-principles calculations, we consider interstitial diffusion mechanisms and calculate the migration barrier energies of interstitial Cu, Ag and Au atoms in II-VI compounds ZnTe. We find that the relative size of dopant and bulk atoms is an important factor which affects the diffusion behavior. The high symmetry Tc site, which is tetrahedrally coordinated by four cation atoms, is the global minimum energy location for Ag and Au interstitials. The size of Cu adatom is small, so Cu is more stable when it locates at the Ta site which is tetrahedrally coordinated by four anion atoms. But the global minimum energy location for Cu interstitials is M site which is of smaller space than Ta. Cu adatoms show an asymmetric curve of energy diffusion barrier with two energetically distinct extremum in the pathway. Ag diffuses along nearly straight line paths along [111] or equivalent directions. Diffusion for Cu or Au deviates from the straight line paths along <111> avoiding high symmetric sites.

  7. Porous Au-Ag Alloy Particles Inlaid AgCl Membranes As Versatile Plasmonic Catalytic Interfaces with Simultaneous, in Situ SERS Monitoring.

    PubMed

    Cao, Qi; Yuan, Kaiping; Liu, Qinghe; Liang, Chongyun; Wang, Xiang; Cheng, Yi-Feng; Li, Qingqing; Wang, Min; Che, Renchao

    2015-08-26

    We present a novel porous Au-Ag alloy particles inlaid AgCl membrane as plasmonic catalytic interfaces with real-time, in situ surface-enhanced Raman spectroscopy (SERS) monitoring. The Au-Ag alloy particles inlaid AgCl membranes were obtained via a facile two-step, air-exposed, and room-temperature immersion reaction with appropriate annealing process. Owing to the designed integration of semiconductor component AgCl and noble metal Au-Ag particles, both the catalytic reduction and visible-light-driven photocatalytic activities toward organic contaminants were attained. Specifically, the efficiencies of about 94% of 4-nitrophenol (4-NP, 5 × 10(-5) M) reduction after 8 min of reaction, and degradation of rhodamine 6G (R6G, 10(-5) M) after 12 min of visible light irradiation were demonstrated. Moreover, efficiencies of above 85% of conversion of 4-NP to 4-aminophenol (4-AP) and 90% of R6G degradation were achieved as well after 6 cycles of reactions, by which robust recyclability was confirmed. Further, with distinct SERS signals generated simultaneously from the surfaces of Au-Ag particles under laser excitation, in situ SERS monitoring of the process of catalytic reactions with superior sensitivity and linearity has been realized. Overall, the capability of the Au-Ag particles inlaid AgCl membranes to provide SERS monitored catalytic and visible-light-driven photocatalytic conversion of organic pollutants, along with their mild and cost-effective fabrication method, would make sense for in-depth understanding of the mechanisms of (photo)catalytic reactions, and also future development of potable, multifunctional and integrated catalytic and sensing devices. PMID:26263301

  8. Dendrite characteristics in directionally solidified Pb-8 pct Au and Pb-3 pct Pd alloys

    NASA Technical Reports Server (NTRS)

    Tewari, S. N.

    1986-01-01

    The dendritic microstructure and solute compression profiles for Pb-8 pct Au and Pb-3 pct Pd alloy samples are examined. Two groups of models, the minimum undercooled dendrite tip model of Burden and Hunt (1974) and Laxmanan (1974, 1984) and marginal stability at the dendrite tip models of Trivedi (1980) and Laxmanan (1974) are used to predict growth behavior of the alloy samples. The experimentally observed dendrite tip radius, primary arm spacing, and liquid composition at the dendrite tip are compared with theoretical predictions. It is observed that the modified minimum undercooling dendrite tip model and both of the marginal stability models accurately predict dendritic behavior. It is concluded that quantitative comparison of the primary arm spacing measurements can not form the basis for distinguishing among the various dendrite growth models in a positive temperature gradient.

  9. Dendrite characteristics in directionally solidified Pb-8 pct Au and Pb-3 pct Pd alloys

    NASA Technical Reports Server (NTRS)

    Tewari, S. N.

    1986-01-01

    An investigation of Pb-8 pct Au and Pb-3 pct Pd alloy specimens which have been partially directionally solidified and then quenched is performed in order to characterize their dendritic microstructural details and solute composition profiles. A controlled sectioning technique is employed to measure dendrite tip radii. It is found that most of the observed behavior is predicted quite well by a modification of the Burden and Hunt (1974) model proposed by Laxmanan (1984), in addition to the models based on the marginal stability approach. Results indicate that quantitative comparison of the primary arm spacing measurements can not form the basis of distinguishing among the various dendrite growth models in a positive temperature gradient.

  10. Configuration of microbially synthesized Pd-Au nanoparticles studied by STEM-based techniques

    NASA Astrophysics Data System (ADS)

    Tran, D. T.; Jones, I. P.; Preece, J. A.; Johnston, R. L.; Deplanche, K.; Macaskie, L. E.

    2012-02-01

    Bimetallic Pd-Au particles synthesized using Desulfovibrio desulfuricans bacteria are characterized using scanning transmission electron microscopy (STEM) with a high-angle annular dark field (HAADF) detector combined with energy dispersive x-ray (EDX) silicon drift detector (SDD) elemental mapping and plasmon electron energy-loss spectroscopy (EELS). When combined with EDX, theoretical considerations or EELS, the atomic-number contrast (Z-contrast) provided by HAADF-STEM is effective in characterizing the compositional configuration of the bimetallic nanoparticles. Homogeneous mixing and complex segregations have been found for different particles in this work. The EELS study has also found different behaviours corresponding to surface plasmon resonances in different regions of a single particle due to its heterogeneity and anisotropy. HAADF-STEM tomography has been performed to obtain three-dimensional (3D) visualization of the nanoparticles.

  11. The adsorption of ethylene on Au/Pd(100) alloy surfaces

    NASA Astrophysics Data System (ADS)

    Li, Zhenjun; Thuening, Theodore; Tysoe, Wilfred T.

    2016-04-01

    The surface chemistry of ethylene is explored on model Au/Pd(100) alloy surfaces using a combination of temperature-programmed desorption and reflection-absorption infrared spectroscopy. The heat of adsorption of ethylene on the model alloy surface is found to increase monotonically with increasing palladium coverage in the alloy, from ~ 33 kJ/mol for a completely gold-covered surface to ~ 80 kJ/mol as the gold coverage decreases to zero. A large change in heat of adsorption is found for palladium coverages between 0 and ~ 0.35 monolayers, where previous studies have shown that the surface comprises exclusively isolated palladium sites. The heat of adsorption changes more slowly for higher palladium coverages, when palladium-palladium bridge sites appear. Vinyl species are identified for palladium coverages above ~ 0.8 ML from a vibrational mode at ~ 1120 cm- 1, which disappears when the sample is heated to ~ 250 K, due to vinyl decomposition.

  12. Surface properties of clean and Au or Pd covered hematite (α-Fe(2)O(3)) (0001).

    PubMed

    Kiejna, Adam; Pabisiak, Tomasz

    2012-03-01

    The structure and electronic properties of different terminations of the α-Fe(2)O(3)(0001) surface were studied with spin-polarized density functional theory (DFT) and the DFT + U method accounting for the effect of strong on-site Coulomb correlations. The results for lattice relaxation, electronic and magnetic properties are presented and discussed. Though the DFT and DFT + U methods provide qualitatively very similar surface geometries they differ very much in the prediction of the electronic and magnetic properties, and the surface energetics of the clean α-Fe(2)O(3)(0001). The most stable single iron terminated (0001) surface and the oxygen-rich termination were chosen to study Au and Pd atom adsorption. The results show that both Au and Pd bind strongly to hematite surfaces and induce large changes in their geometry. The DFT + U bonding is weaker by 0.3-0.6 eV than DFT on the iron terminated surface and about 2 eV stronger on the oxygen terminated one. The binding is stronger for Pd than Au and for both adsorbates is distinctly stronger at the oxygen than at the iron terminated surface. On the iron terminated surface the adsorption binding energy per adatom increases both with Au and Pd coverage, whereas for the oxygen terminated one the opposite trend is observed. PMID:22274998

  13. Highly sensitive electrochemiluminescenc assay of acetylcholinesterase activity based on dual biomarkers using Pd-Au nanowires as immobilization platform.

    PubMed

    Ye, Cui; Wang, Min-Qiang; Zhong, Xia; Chen, Shihong; Chai, Yaqin; Yuan, Ruo

    2016-05-15

    One-dimensional Pd-Au nanowires (Pd-Au NWs) were prepared and applied to fabricate an electrochemiluminescence (ECL) biosensor for the detection of acetylcholinesterase (AChE) activity. Compared with single-component of Pd or Au, the bimetallic nanocomposite of Pd-Au NWs offers a larger surface area for the immobilization of enzyme, and displays superior electrocatalytic activity and efficient electron transport capacity. In the presence of AChE and choline oxidase (ChOx), acetylcholine (ATCl) is hydrolyzed by AChE to generate thiocholine, then thiocholine is catalyzed by ChOx to produce H2O2 in situ, which serves as the coreactant to effectively enhance the ECL intensity in luminol-ECL system. The detection principle is based on the inhibited AChE and reactivated AChE as dual biomarkers, in which AChE was inhibited by organophosphorus (OP) agents, and then reactivated by obidoxime. Such dual biomarkers method can achieve credible evaluation for AChE activity via providing AChE activity before and after reactivation. The liner range for AChE activity detection was from 0.025 U L(-1) to 25 KU L(-1) with a low detection limit down to 0.0083 U L(-1). PMID:26686921

  14. In situ synchrotron study of Au-Pd nanoporous alloy formation by single-source precursor thermolysis

    NASA Astrophysics Data System (ADS)

    Shubin, Yury; Plyusnin, Pavel; Sharafutdinov, Marat

    2012-10-01

    We have successfully prepared a face-centered cubic Au-Pd nanoporous structure (NPS) in a one-pot reaction under thermal decomposition of single-source precursor [Pd(NH3)4][AuCl4]2. The precursor employed contains both desired metals ‘mixed’ on the molecular level, thus providing its significant advantages for obtaining alloys. The observation using a high-resolution transmission electron microscope has shown that the nanostructure was composed of interconnected polycrystalline ligaments with an average diameter of 14 ± 3 nm. The measurements made by energy-dispersive x-ray analysis and powder x-ray diffraction (XRD) confirm that the nanostructure consists of Au0.67Pd0.33 alloy. In situ real-time synchrotron XRD was used to study the formation mechanism for Au-Pd alloy NPS. We provide the correlation of control parameters (such as temperature, rate of increase of temperature and gas atmosphere) with the microstructure and phase behavior of bimetallic products. Under reducing conditions (H2 atmosphere) the first step is the formation of alloy nanowires. Finally, bimetallic alloy 3D nanostructure is formed after the complete decomposition of the precursor (100 °C).

  15. AuPd/polyaniline as the anode in an ethylene glycol microfluidic fuel cell operated at room temperature.

    PubMed

    Arjona, N; Palacios, A; Moreno-Zuria, A; Guerra-Balcázar, M; Ledesma-García, J; Arriaga, L G

    2014-08-01

    AuPd/polyaniline was used for the first time, for ethylene glycol (EG) electrooxidation in a novel microfluidic fuel cell (MFC) operated at room temperature. The device exhibits high electrocatalytic performance and stability for the conversion of cheap and fully available EG as fuel. PMID:24923468

  16. A green approach to ethyl acetate: quantitative conversion of ethanol through direct dehydrogenation in a Pd-Ag membrane reactor.

    PubMed

    Zeng, Gaofeng; Chen, Tao; He, Lipeng; Pinnau, Ingo; Lai, Zhiping; Huang, Kuo-Wei

    2012-12-01

    Pincers do the trick: The conversion of ethanol to ethyl acetate and hydrogen was achieved using a pincer-Ru catalyst in a Pd-Ag membrane reactor. Near quantitative conversions and yields could be achieved without the need for acid or base promoters or hydrogen acceptors (see scheme). PMID:23136053

  17. Green Synthesis of Ag and Pd Nanospheres, Nanowires, and Nanorods Using Vitamin B2: Catalytic Polymerisation of Aniline and Pyrrole

    EPA Science Inventory

    For the first time, we report green chemistry approach using vitamin B2 in the synthesis of silver (Ag) and palladium (Pd), nanospheres, nanowires and nanorods at room temperature without using any harmful reducing agents, such as sodium borohydride (NaBH4) or hydroxylamine hydro...

  18. 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

  19. 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

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

    PubMed

    Wang, Long-De; Zhang, Tong; Zhang, Xiao-Yang; Song, Yuan-Jun; Li, Ruo-Zhou; Zhu, Sheng-Qing

    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

  1. Effect of Pd Surface Roughness on the Bonding Process and High Temperature Reliability of Au Ball Bonds

    NASA Astrophysics Data System (ADS)

    Huang, Y.; Kim, H. J.; McCracken, M.; Viswanathan, G.; Pon, F.; Mayer, M.; Zhou, Y. N.

    2011-06-01

    A 0.3- μm-thick electrolytic Pd layer was plated on 1 μm of electroless Ni on 1 mm-thick polished and roughened Cu substrates with roughness values ( R a) of 0.08 μm and 0.5 μm, respectively. The rough substrates were produced with sand-blasting. Au wire bonding on the Ni/Pd surface was optimized, and the electrical reliability was investigated under a high temperature storage test (HTST) during 800 h at 250°C by measuring the ball bond contact resistance, R c. The average value of R c of optimized ball bonds on the rough substrate was 1.96 mΩ which was about 40.0% higher than that on the smooth substrate. The initial bondability increased for the rougher surface, so that only half of the original ultrasonic level was required, but the reliability was not affected by surface roughness. For both substrate types, HTST caused bond healing, reducing the average R c by about 21% and 27%, respectively. Au diffusion into the Pd layer was observed in scanning transmission electron microscopy/ energy dispersive spectroscopy (STEM-EDS) line-scan analysis after HTST. It is considered that diffusion of Au or interdiffusion between Au and Pd can provide chemically strong bonding during HTST. This is supported by the R c decrease measured as the aging time increased. Cu migration was indicated in the STEM-EDS analysis, but its effect on reliability can be ignored. Au and Pd tend to form a complete solid solution at the interface and can provide reliable interconnection for high temperature (250°C) applications.

  2. 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

  3. Investigation of factors influencing the catalytic performance of CO oxidation over Au-Ag/SBA-15 catalyst

    NASA Astrophysics Data System (ADS)

    Qu, Zhenping; Ke, Guozhou; Wang, Yi; Liu, Mengwei; Jiang, Tingting; Gao, Jinsuo

    2013-07-01

    Au-Ag bimetallic nanoparticles (NPs) supported on SBA-15 have been prepared by a two-step method and characterized by ICP-AES, XRD, UV-vis, TG-DTG, XPS and TEM. Au-Ag/SBA-15 bimetallic catalyst with a low metal loading of 1.26 wt.% exhibited high catalytic performance for low temperature CO oxidation, which was governed by Au/Ag molar ratio and the pretreatment conditions (calcination and reduction). The Au-Ag/SBA-15 with an actual Au/Ag molar ratio of 5.4/1 showed the highest catalytic activity for CO oxidation (T100 = 20 °C), and it has also been found that catalytic activity was strongly related with the calcination and reduction temperature of the bimetallic catalyst. The initial CO conversion was increased with the calcination temperature and then decreased above 500 °C. It was necessary to activate the bimetallic catalyst and completely remove the amine groups in the catalyst at 500 °C for the high activity of CO oxidation. The severe sintering of Au-Ag bimetallic NPs at 700 °C resulted in an obvious loss of activity. H2 reduction following the calcination played an important role in the enhancement of catalytic activity for CO oxidation. The best catalytic performance was obtained in the activation temperature range of 500-600 °C, and then decreased with a further increase of reduction temperature to 700 °C. The reduction treatment induced the surface redistribution of gold and silver. The formation of a closer bulk value of the surface Au/Ag molar ratio after reduction at 500-600 °C and a more random alloy resulted in the improvement in activity. However, the surface enrichment of Ag NPs and the severe aggregation of particles after high temperature reduction (>600 °C) caused the activity decrease.

  4. Phase Evolution in the Pd-Ag-CuO Air Braze Filler Metal Alloy System

    SciTech Connect

    Darsell, Jens T.; Weil, K. Scott

    2006-08-01

    Palladium was added as a ternary component to a series of copper oxide-silver alloys in an effort to increase the use temperature of these materials for potential ceramic air brazing applications. Phase equilibria in the ternary Pd-Ag-CuO system were investigated via differential scanning calorimetry (DSC) and a series of quenching experiments. Presented here are the latest findings on this system and a construction of the corresponding ternary phase diagram for low-to-moderate additions of palladium. The analysis included samples with higher palladium additions than were studied in the past, as well as an analysis of the composition-temperature trends in the Ag-CuO miscibility gap with palladium addition. It was found that the addition of palladium increases the solidus and liquidus and caused three phase zones to appear as expected by the phase rule. Furthermore, the palladium additions cause the miscibility gap boundary extending from the former binary eutectic to shift to lower silver-to-copper ratios.

  5. Green Synthesis of Ag and Pd Nanospheres, Nanowires, and Nanorods Using Vitamin B 2 : Catalytic Polymerisation of Aniline and Pyrrole

    DOE PAGESBeta

    Nadagouda, Mallikarjuna N.; Varma, Rajender S.

    2008-01-01

    Formore » the first time, we report green chemistry approach using vitamin B 2 in the synthesis of silver (Ag) and palladium (Pd), nanospheres, nanowires, and nanorods at room temperature without using any harmful reducing agents, such as sodium borohydride ( NaBH 4 ) or hydroxylamine hydrochloride and any special capping or dispersing agent. Vitamin B 2 was used as reducing agent as well as capping agent due to its high-water solubility, biodegradability, and low-toxicity compared with other reducing agents. The average particle size of nanoprticle was found to be Ag (average size 6.1 ± 0.1 nm) and Pd (average size 4.1 ± 0.1 nm) nanoparticles in ethylene glycol and Ag (average size 5.9 ± 0.1 nm, and average size 6.1 ± 0.1) nanoparticles in acetic acid and NMP, respectively. The formation of noble multiple shape nanostructures and their self assembly were dependent on the solvent employed for the preparation. When water was used as solvent media, Ag and Pd nanoparticles started to self-assemble into rod-like structures and in isopropanol Ag and Pd nanoparticles yielded wire-like structures with a thickness in the range of 10 to 20 nm and several hundred microns in length. In acetone and acetonitrile medium, the Ag and Pd nanoparticles are self-assembled into a regular pattern making nanorod structures with thicknesses ranging from 100 to 200 nm and lengths of a few microns. The so-synthesized nanostructures were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, and UV spectroscopy. The ensuing Ag and Pd nanoparticles catalyzed the reactions of aniline and pyrrole to generate polyaniline and polypyrrole nanofibers and may find various technological and biological applications. This single-step greener approach is general and can be extended to other noble metals and transition metal oxides.« less

  6. Tuning the electronic properties of the golden buckyball by endohedral doping: M@Au16(-) (M=Ag,Zn, In)

    SciTech Connect

    Wang, Leiming; Pal, R.; Huang, Wei; Zeng, Xiao Cheng; Wang, Lai S.

    2009-02-07

    The golden Au16 cage is doped systematically with an external atom of different valence electrons:Ag, Zn, and In. The electronic and structural properties of the doped clusters, MAu16 (M=Ag,Zn, In), are investigated by photoelectron spectroscopy and theoretical calculations. It is observed that the characteristic spectral features of Au16, reflecting its near tetrahedral (Td) symmetry, are retained in the photoelectron spectra of MAu16, suggesting endohedral structures with little distortion from the parent Au16 cage for the doped clusters. Density functional calculations show that the endohedral structures of M@Au16 with Td symmetry are low-lying structures, which give simulated photoelectron spectra in good agreement with the experiment. It is found that the dopant atom does not significantly perturb the electronic and atomic structures of Au16, but simply donate its valence electrons to the parent Au16 cage, resulting in a closed-shell 18-electron system for Ag@Au16, a 19-electron system for Zn@Au16 with a large energy gap,and a 20-electron system for In@Au16. The current work shows that the electronic properties of the golden buckyball can be systematically tuned through doping.

  7. Effect of Ni and Pd Addition on Mechanical, Thermodynamic, and Electronic Properties of AuSn4-Based Intermetallics: A Density Functional Investigation

    NASA Astrophysics Data System (ADS)

    Tian, Yali; Zhou, Wei; Wu, Ping

    2016-05-01

    The effects of Ni and Pd addition on the mechanical, thermodynamic, and electronic properties of AuSn4-based intermetallic compounds (IMCs) have been investigated by first-principles calculations to reveal the essence of Au embrittlement. Three kinds of doped (namely Ni-doped, Pd-doped, and Ni/Pd-codoped) IMCs are considered in this work. The polycrystalline elastic properties are deduced from single-crystal elastic constants. It is found that the doped systems together with nondoped AuSn4 are all ductile phases. For Ni-doped AuSn4, the modulus, hardness, brittleness, Debye temperature, and minimum thermal conductivity increase with the Ni fraction, but this is not the case for the Pd-doped material, since Au0.75Pd0.25Sn4 is the more brittle phase. For Au0.5Pd0.25Ni0.25Sn4, the mechanical, thermodynamic, and electronic properties are similar to those of Au0.5Pd0.5Sn4.

  8. Effect of Ni and Pd Addition on Mechanical, Thermodynamic, and Electronic Properties of AuSn4-Based Intermetallics: A Density Functional Investigation

    NASA Astrophysics Data System (ADS)

    Tian, Yali; Zhou, Wei; Wu, Ping

    2016-08-01

    The effects of Ni and Pd addition on the mechanical, thermodynamic, and electronic properties of AuSn4-based intermetallic compounds (IMCs) have been investigated by first-principles calculations to reveal the essence of Au embrittlement. Three kinds of doped (namely Ni-doped, Pd-doped, and Ni/Pd-codoped) IMCs are considered in this work. The polycrystalline elastic properties are deduced from single-crystal elastic constants. It is found that the doped systems together with nondoped AuSn4 are all ductile phases. For Ni-doped AuSn4, the modulus, hardness, brittleness, Debye temperature, and minimum thermal conductivity increase with the Ni fraction, but this is not the case for the Pd-doped material, since Au0.75Pd0.25Sn4 is the more brittle phase. For Au0.5Pd0.25Ni0.25Sn4, the mechanical, thermodynamic, and electronic properties are similar to those of Au0.5Pd0.5Sn4.

  9. An Alternative Preparation of 1-(N,N-Dimethylaminomethyl)-1′-(diphenylphosphanyl)ferrocene: Synthesis and Structural Characterization of AuI and PdII Complexes with this Hybrid Ligand

    PubMed Central

    Štěpnička, Petr; Zábranský, Martin; Císařová, Ivana

    2012-01-01

    1-(N,N-Dimethylaminomethyl)-1′-(diphenylphosphanyl)ferrocene (1) was synthesized in good yield by lithiation of 1-bromo-1′-(diphenylphosphanyl)ferrocene and subsequent reaction with Eschenmoser's salt (dimethylmethylideneammonium iodide). Making use of an easily accessible, nontoxic starting material, this procedure represents a convenient alternative to the original synthetic protocol based on stepwise lithiation/functionalization of 1,1′-bis(tributylstannyl)ferrocene and reductive amination [M. E. Wright, Organometallics 1990, 9, 853–856]. Compound 1 has typical hybrid-donor properties. When reacted with [AuCl(tht)] (tht=tetrahydrothiophene), it afforded the expected AuI phosphane complex [AuCl(1-κP)] (2). An attempted removal of the chloride ligand from 2 with AgClO4 produced an ill-defined material formulated as Au(1)ClO4. The uncoordinated amine substituent reacted with traces of hydrogen chloride formed by slow decomposition typically occurring in solution. In this manner, complexes [AuCl(Ph2PfcCH2NHMe2)]Cl (3, fc=ferrocene-1,1′-diyl) and [AuCl(Ph2PfcCH2NHMe2)]ClO4 (4) were isolated from crystallizations experiments with 2 and Au(1)ClO4, respectively. On a larger scale, complex 3 was prepared easily from 2 and hydrogen chloride. The course of reactions between [PdCl2(cod)] (cod=cycloocta-1,5-diene) and 1 were found to depend on the ligand-to-metal ratio. Whereas the reaction with two equivalents of 1 afforded bis(phosphane) complex trans-[PdCl2(1-κP)2] (5), that of a Pd:P ratio 1:1 produced ligand-bridged dimer [(μ-1)PdCl2]2 (6). With hydrogen chloride, complex 6 reacted to afford zwitterionic complex [PdCl3(1H-κP)] (7), which was also formed when ligand 1 and [PdCl2(cod)] were allowed to react slowly by liquid-phase diffusion of their chloroform solutions. The compounds were characterized by spectroscopic methods (multinuclear NMR and ESI–MS), and the molecular structures of complex 2–4, 6⋅2CHCl3 and 7⋅1.5CHCl3 were determined by single

  10. A facile and controllable strategy to synthesize Au-Ag alloy nanoparticles within polyelectrolyte multilayer nanoreactors upon thermal reduction.

    PubMed

    Shang, Li; Jin, Lihua; Guo, Shaojun; Zhai, Junfeng; Dong, Shaojun

    2010-05-01

    A new synthesis strategy has been developed for the preparation of bimetallic gold-silver (Au-Ag) alloy nanoparticles by the virtue of polyelectrolyte multilayer (PEM) nanoreactors. By controlling the assembly conditions, gold and silver ions can be effectively loaded onto the PEM composed of polyethylenimine (PEI) and poly(acrylic acid) (PAA) simultaneously. Upon further thermal treatment, Au-Ag alloy nanoparticles with sizes of ca. 3.8 nm formed in the PEM, which were characterized in detail by UV-vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and energy-dispersive X-ray (EDX) analysis. Appearance of a single plasmon band in the visible region and lack of apparent core-shell structures in the TEM images confirm the formation of homogeneous Au-Ag alloy nanoparticles. In addition, the surface plasmon absorption band of the Au-Ag alloy nanoparticles shows linear blue-shift with increasing Ag content, which also supported the formation of alloy nanoparticles. Several key parameters of the present strategy have been investigated, which showed that pH of both the assembly solution and gold salt solution and the choice of polymers for constructing PEM, as well as the reduction approach, all played an important role in successfully synthesizing bimetallic Au-Ag nanoparticles. The formation mechanism of alloy nanoparticles has also been discussed based on the spectral evolution during the thermal reduction. PMID:20017511

  11. 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.

  12. 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.

  13. Hydrothermal ethanol conversion on Ag, Cu, Au/TiO2

    NASA Astrophysics Data System (ADS)

    Mai, Do Tkhyui; Mikhalenko, I. I.; Pylinina, A. I.

    2014-10-01

    The effect UV irradiation and silver, copper, and gold ions (M z+) supported on titania (anatase) have on the activity of M/TiO2 samples in ethanol conversion at 150-400°C is examined. After UV irradiation, the yields of acetaldehyde and ethylene increase for TiO2 and Ag/TiO2 samples, while the activity of Cu2+/TiO2 decreases. The activation energy of ethanol dehydration declines in the order TiO2 > Au3+ > Cu2+ > Ag+ and correlates linearly with a reduction in the radius of M z+ in crystal. The number of acidic sites on a M/TiO2 surface titrated via pyridine adsorption grows upon the introduction of M. Unlike Cu2+/TiO2, these sites are not activated after the irradiation of TiO2, Ag+/TiO2, and Au3+/TiO2. According to IR spectral data on adsorbed pyridine, all samples contain Lewis and Brönsted acidic sites.

  14. 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.

  15. 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.

  16. 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

  17. 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. PMID:25691287

  18. Developing an aqueous approach for synthesizing Au and M@Au (M = Pd, CuPt) hybrid nanostars with plasmonic properties.

    PubMed

    Du, Jingshan; Yu, Junjie; Xiong, Yalin; Lin, Zhuoqing; Zhang, Hui; Yang, Deren

    2015-01-14

    Anisotropic Au nanoparticles show unique localized surface plasmon resonance (LSPR) properties, which make them attractive in optical, sensing, and biomedical applications. In this contribution, we report a general and facile strategy towards aqueous synthesis of Au and M@Au (M = Pd, CuPt) hybrid nanostars by reducing HAuCl4 with ethanolamine in the presence of cetyltrimethylammonium bromide (CTAB). According to electron microscopic observations and spectral monitoring, we found that the layered epitaxial growth mode (i.e., the Frank-van der Merwe mechanism) contributes to the enlargement of the core, while the random attachment of Au nanoclusters onto the cores accounts for the formation of the branches. Both of them are indispensable to the formation of the nanostars. The LSPR properties of the Au nanoparticles have been well investigated with morphology control via the precursor amount and growth temperature. The Au nanostars showed improved surface-enhanced Raman spectroscopy (SERS) performance for rhodamine 6G due to their sharp edges and tips, which were therefore confirmed as good SERS substrates to detect trace amounts of molecules. PMID:25420730

  19. Novel electrochemical redox-active species: one-step synthesis of polyaniline derivative-Au/Pd and its application for multiplexed immunoassay

    NASA Astrophysics Data System (ADS)

    Wang, Liyuan; Feng, Feng; Ma, Zhanfang

    2015-11-01

    Electrochemical redox-active species play crucial role in electrochemically multiplexed immunoassays. A one-pot method for synthesizing four kinds of new electrochemical redox-active species was reported using HAuCl4 and Na2PdCl4 as dual oxidating agents and aniline derivatives as monomers. The synthesized polyaniline derivative-Au/Pd composites, namely poly(N-methyl-o-benzenediamine)-Au/Pd, poly(N-phenyl-o-phenylenediamine)-Au/Pd, poly(N-phenyl-p-phenylenediamine)-Au/Pd and poly(3,3’,5,5’-tetramethylbenzidine)-Au/Pd, exhibited electrochemical redox activity at -0.65 V, -0.3 V, 0.12 V, and 0.5 V, respectively. Meanwhile, these composites showed high H2O2 electrocatalytic activity because of the presence of Au/Pd. The as-prepared composites were used as electrochemical immunoprobes in simultaneous detection of four tumor biomarkers (carcinoembryonic antigen (CEA), carbohydrate antigen 19-9 (CA199), carbohydrate antigen 72-4 (CA724), and alpha fetoprotein (AFP)). This immunoassay shed light on potential applications in simultaneous gastric cancer (related biomarkers: CEA, CA199, CA724) and liver cancer diagnosis (related biomarkers: CEA, CA199, AFP). The present strategy to the synthesize redox species could be easily extended to other polymers such as polypyrrole derivatives and polythiophene derivatives. This would be of great significance in the electrochemical detection of more analytes.

  20. Novel electrochemical redox-active species: one-step synthesis of polyaniline derivative-Au/Pd and its application for multiplexed immunoassay

    PubMed Central

    Wang, Liyuan; Feng, Feng; Ma, Zhanfang

    2015-01-01

    Electrochemical redox-active species play crucial role in electrochemically multiplexed immunoassays. A one-pot method for synthesizing four kinds of new electrochemical redox-active species was reported using HAuCl4 and Na2PdCl4 as dual oxidating agents and aniline derivatives as monomers. The synthesized polyaniline derivative-Au/Pd composites, namely poly(N-methyl-o-benzenediamine)-Au/Pd, poly(N-phenyl-o-phenylenediamine)-Au/Pd, poly(N-phenyl-p-phenylenediamine)-Au/Pd and poly(3,3’,5,5’-tetramethylbenzidine)-Au/Pd, exhibited electrochemical redox activity at −0.65 V, −0.3 V, 0.12 V, and 0.5 V, respectively. Meanwhile, these composites showed high H2O2 electrocatalytic activity because of the presence of Au/Pd. The as-prepared composites were used as electrochemical immunoprobes in simultaneous detection of four tumor biomarkers (carcinoembryonic antigen (CEA), carbohydrate antigen 19-9 (CA199), carbohydrate antigen 72-4 (CA724), and alpha fetoprotein (AFP)). This immunoassay shed light on potential applications in simultaneous gastric cancer (related biomarkers: CEA, CA199, CA724) and liver cancer diagnosis (related biomarkers: CEA, CA199, AFP). The present strategy to the synthesize redox species could be easily extended to other polymers such as polypyrrole derivatives and polythiophene derivatives. This would be of great significance in the electrochemical detection of more analytes. PMID:26577799

  1. Novel PdAgCu ternary alloy as promising materials for hydrogen separation membranes: Synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Tarditi, Ana M.; Cornaglia, Laura M.

    2011-01-01

    The use of the sequential electroless plating method allowed us to obtain the PdAgCu ternary alloy on top of dense stainless steel (SS) 316 L disks. The XRD analysis indicated that initially the nucleation of the two phases of the alloy (FCC and BCC) takes place, but the FCC/BCC ratio increases with the annealing time at 500 °C in H 2 stream. After 162 h, the film contained only the FCC phase, which presents promising properties to be applied in the synthesis of hydrogen selective membranes. SEM cross-section results showed that a dense, continuous, defect-free film was deposited on top of the SS support, and the EDS data indicated that no significant gradient was present on the thickness of the film. XPS and LEIS allowed us to determine that Cu and Ag surface segregation takes place after annealing up to 500 °C/5 days. In the top-most surface layer, Ag enrichment takes place as determined by ARXPS experiments which can be the result of the lower surface tension of Ag compared to that of Cu and Pd. Increasing the annealing temperature results in an increase of the Ag surface segregation while the Cu concentration in the top-most surface layer decreases.

  2. Anti p and anti Lambda production in Si + Au collisions at the AGS

    NASA Technical Reports Server (NTRS)

    Wu, Yue-Dong

    1996-01-01

    (anti (ital p)) and (anti (Lambda)) production in central Si + Au collisions has been measured by E589 at the BNL-AGS. Preliminary (ital m)(sub (perpendicular)) spectra are presented for (anti (ital p))'s and (anti (Lambda))'s. The (ital dn/dy) distribution for (anti (ital p))'s is also presented. Based on the (anti (ital p)) and (anti (Lambda)) measurements, (anti (Lambda))/(anti (ital p)) ratios are calculated in the rapidity range of 1.1-1.5.

  3. In situ synthesis and nonlinear optical properties of Au:Ag nanocomposite polymer films

    NASA Astrophysics Data System (ADS)

    Karthikeyan, B.; Anija, M.; Philip, Reji

    2006-01-01

    We report a simple in situ synthesis procedure for Au:Ag nanocomposite polymer (NCP) films using polyvinyl alcohol as the reducing agent. Optical measurements show absorption bands of varying strengths around 530 and 410 nm. The presence of nanoparticles is confirmed from Transmission Electron Microscopy (TEM). Nonlinear optical response is studied using 7 ns laser pulses, for near-resonant and off-resonant excitation wavelengths (532 and 1064 nm, respectively). Samples exhibit saturable as well as induced absorption. These materials have the potential to be used as saturable absorbers and optical limiters.

  4. Dirac and Weyl Semimetal in XYBi (X = Ba, Eu; Y = Cu, Ag and Au).

    PubMed

    Du, Yongping; Wan, Bo; Wang, Di; Sheng, Li; Duan, Chun-Gang; Wan, Xiangang

    2015-01-01

    Weyl and Dirac semimetals recently stimulate intense research activities due to their novel properties. Combining first-principles calculations and effective model analysis, we predict that nonmagnetic compounds BaYBi (Y = Au, Ag and Cu) are Dirac semimetals. As for the magnetic compound EuYBi, although the time reversal symmetry is broken, their long-range magnetic ordering cannot split the Dirac point into pairs of Weyl points. However, we propose that partially substitute Eu ions by Ba ions will realize the Weyl semimetal. PMID:26399742

  5. 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

  6. 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.

  7. A novel glucose biosensor platform based on Ag@AuNPs modified graphene oxide nanocomposite and SERS application.

    PubMed

    Gupta, Vinod Kumar; Atar, Necip; Yola, Mehmet Lütfi; Eryılmaz, Merve; Torul, Hilal; Tamer, Uğur; Boyacı, Ismail Hakkı; Ustündağ, Zafer

    2013-09-15

    This study represents a novel template demonstration of a glucose biosensor based on mercaptophenyl boronic acid (MBA) terminated Ag@AuNPs/graphene oxide (Ag@AuNPs-GO) nanomaterials. The nanocomposites were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) method. The TEM image shows that Ag@AuNPs in the nanocomposite is in the range of diameters of 10-20 nm. The nanocomposite was used for the determination of glucose through the complexation between boronic acid and diol groups of glucose. Thus, a novel glucose biosensor was further fabricated by immobilizing glucose oxidase (GOD) into MBA terminated Ag@AuNPs-GO nanocomposite film (MBA-Ag@AuNPs-GO). The linearity range of glucose was obtained as 2-6mM with detection limit of 0.33 mM. The developed biosensor was also applied successfully for the determination of glucose in blood samples. The concentration value of glucose in blood samples was calculated to be 1.97±0.002 mM from measurements repeated for six times. PMID:23816220

  8. 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

  9. Fabrication a new modified electrochemical sensor based on Au-Pd bimetallic nanoparticle decorated graphene for citalopram determination.

    PubMed

    Daneshvar, Leili; Rounaghi, Gholam Hossein; Es'haghi, Zarrin; Chamsaz, Mahmoud; Tarahomi, Somayeh

    2016-12-01

    This paper proposes a simple approach for sensing of citalopram (CTL) using gold-palladium bimetallic nanoparticles (Au-PdNPs) decorated graphene modified gold electrode. Au-PdNPs were deposited at the surface of a graphene modified gold electrode with simple electrodeposition method. The morphology and the electrochemical properties of the modified electrode were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), energy dispersion spectroscopy (EDS), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and square wave voltammetry (SWV). The novel sensor exhibited an excellent catalytic activity towards the oxidation of CTL. The oxidation peak current of CTL, was linear in the range of 0.5-50μM with a detection limit 0.049μM with respect to concentration of citalopram. The proposed sensor was successfully applied for determination of CTL tablet and human plasma samples with satisfactory results. PMID:27612758

  10. Amperometric biosensor of SnO2 thin film modified by Pd, In and Ag nanostructure synthesized by CSP method

    NASA Astrophysics Data System (ADS)

    Hassan, Marwa Abdul Muhsien; Hateef, Areej Adnan; Majeed, Aseel Mustafa Abdul; Al-Jabiry, Ali Jasim Mohammed; Jameel, Sabah; Hussian, Haidar Abdul Razaq Abdul

    2013-10-01

    Palladium, Indium and Silver-doped SnO2 thin film was deposited by chemical spray pyrolysis on ITO and porous silicon substrates to be a fast MgSO4·7H2O amperometric biosensor. The prepared SnO2 films were doped by dipping in palladium chloride PdCl2, indium chloride, InCl3 and silver nitrides AgNO3 dissolved in ethanol C2H5OH. The structural and optical properties of the prepared films were studied. The sensitivity behaviors of SnO2, SnO2: Pd, SnO2: In and SnO2: Ag based on the amperometric biosensor to MgSO4·7H2O salts were investigated at room temperature with different doping.

  11. Synthesis of Ag/Pd nanoparticles via reactive micelles as templates and its application to electroless copper deposition.

    PubMed

    Yang, Chia-Cheng; Wan, Chi-Chao; Wang, Yung-Yun

    2004-11-15

    Ag/Pd nanoparticles have been synthesized with a reactive alcohol-type surfactant, sodium dodecyl sulfate (SDS), without the presence of an external reducing agent. Both UV-vis absorption spectra and X-ray diffraction patterns for the bimetallic and physical mixtures of individual nanoparticles revealed the formation of a bimetallic structure. Based on this method, an ordered 3D grapelike nanostructure was formed, possibly due to transformation of the liquid crystal phase of the micelles. Data from the energy-dispersive X-ray analysis show that the composition of bimetallic nanoparticle is approximately equal to the feeing solution. Furthermore, the Ag/Pd nanoparticles exhibit distinct catalyst for electroless copper deposition and may be a substitute for the conventional palladium system, which is expensive and unstable in operation. PMID:15464808

  12. Permo Triassic unconformity-related Au-Pd mineralisation, South Devon, UK: new insights and the European perspective

    NASA Astrophysics Data System (ADS)

    Shepherd, Tom J.; Bouch, Jon E.; Gunn, Andrew G.; McKervey, John A.; Naden, Jonathan; Scrivener, Richard C.; Styles, Michael T.; Large, Duncan E.

    2005-07-01

    An integrated mineralogical-geochemical study of unconformity-related Au-Pd occurrences within and around the Permo Triassic basins of southwest England, UK, has confirmed the importance of low temperature (86±13°C), hydrothermal carbonate veins as hosts for the mineralisation. Fluid inclusion data for the carbonate gangue, supported by stable isotope (13C and 18O) and radiogenic (87Sr/86Sr) data, have identified three principal fluids: (1) a reducing calcic brine [>25 wt% salinity, <0.5 NaCl/(NaCl+CaCl2)] originating in the sub-unconformity basement and an expression of advanced mineral fluid interaction; (2) an oxidising sodic brine [~16 wt% salinity, >0.9 NaCl/(NaCl+CaCl2)] originating in the post-unconformity red beds under evaporitic conditions, and (3) an oxygenated, low salinity groundwater (<3 wt% salinity). The sodic brine is reasoned to be the parent metalliferous fluid and to have acquired its enrichment in Au and Pd by the leaching of immature sediments and intra-rift volcanic rocks within the local Permo Triassic basins. Metal precipitation is linked to the destabilisation of Au and Pd chloride complexes by either mixing with calcic brines, dilution by groundwaters or interaction with reduced lithologies. This explains the diversity of mineralised settings below and above the unconformity and their affinity with red bed brines. The paucity of sulphide minerals, the development of selenides (as ore minerals and as mineral inclusion in gold grains), the presence of rhodochrosite and manganoan calcites (up to 2.5 wt% Mn in calcite) and the co-precipitation of hematite and manganese oxides are consistent with the overall high oxidation state of the ore fluids. A genetic model is proposed linking Permo Triassic red beds, the mixing of oxidising and reducing brines, and the development of unconformity-related precious metal mineralisation. Comparison with other European Permo Triassic basins reveals striking similarities in geological setting, mineralogy

  13. Highly-branched mesoporous Au-Pd-Pt trimetallic nanoflowers blooming on reduced graphene oxide as an oxygen reduction electrocatalyst.

    PubMed

    Huang, Liang; Han, Yujie; Dong, Shaojun

    2016-07-01

    Herein, we develop a one-pot, two surfactant-assisted synthesis of highly-branched mesoporous Au-Pd-Pt trimetallic nanoflowers blooming on rGO with superior electrochemical performance for the ORR. Similarly to the interaction between Pluronic F127 and hexadecylpyridinium chloride (HDPC), this method may be extended to other nonionic/ionic surfactants to synthesize all-metal branched porous nanoparticles, and shows promising applications in electrochemistry and catalysis. PMID:27306642

  14. In situ measurements of change in work function of Pt, Pd and Au surfaces during desorption of oxygen by using photoemission yield spectrometer in air

    NASA Astrophysics Data System (ADS)

    Yamashita, Daisuke; Ishizaki, Atsushi

    2016-02-01

    We investigated the change in work function of Pt, Pd and Au surfaces during desorption of oxygen by using a photoemission yield spectrometer with an open counter. Oxygen coverage was formed by UV/ozone treatment, and then continuous change in work function with exposure to air was observed at various temperatures. Work function of Pt, Pd and Au surfaces decreased during desorption of oxygen, and finally returned to the initial value of untreated surfaces. Furthermore, temperature dependence on the change in work function was found. These characteristics were explained using chemical kinetics scheme. The exponential decay of work function was well reproduced by the first-order reaction rate equation, and it was confirmed that the order of rate constant, kr, is kr(Au) < kr(Pd) < kr(Pt). The activation energy was estimated to be 36, 38 and 28 kJ/mol for Pt, Pd, Au, respectively.

  15. Pd-Cu(2)O and Ag-Cu(2)O hybrid concave nanomaterials for an effective synergistic catalyst.

    PubMed

    Li, Lingling; Chen, Xiaobin; Wu, Yuen; Wang, Dingsheng; Peng, Qing; Zhou, Gang; Li, Yadong

    2013-10-11

    Palladium and silver salts were combined with Cu2 O octadecahedra in concave heterostructures. The formation of concave faces involved selective oxidative etching of Cu2 O on the {100} faces and in situ growth of Pd/Ag on different sites. The structures showed superior catalytic activities to both single domains and their mixtures in a model Sonogashira-type organic reaction. PMID:24038721

  16. Fermi surface study of ScAu{sub 2}(Al, In) and ScPd{sub 2}(Sn, Pb) compounds

    SciTech Connect

    Reddy, P. V. Sreenivasa; Kanchana, V.; Vaitheeswaran, G.

    2015-06-24

    A detailed study on the electronic structure and Fermi surface (FS) of superconducting Heusler compounds ScAu{sub 2}(Al, In) and ScPd{sub 2}(Sn, Pb) has been carried out using first principles electronic structure calculations. The spin orbit coupling is found to play a major role in understanding the band structure and FS. Analysis of the data shows the importance of spin orbit coupling effect in the above compounds. The bands which cross Fermi level (EF) are found to be dominated by the Sc d{sub t2g}-states. The calculated total density of states are in good agreement with the experimentally reported value for ScPd{sub 2}Sn. Under compression we find a change in the Fermi surface topology of ScPd{sub 2}Sn at V/V{sub 0} = 0.95 (pressure of≈15 GPa), which is explained using the band structure calculations.

  17. Study of the state of Ag and Pd in silver-palladium catalysts on a titanium dioxide substrate by IR spectroscopy of adsorbed CO

    NASA Astrophysics Data System (ADS)

    Kovalenko, N. A.; Sen'ko, T. L.; Petkevich, T. S.; Egiazarov, Yu. G.

    2007-01-01

    We have used IR spectroscopy of adsorbed CO to study the effect of the method for preparation of silver-palladium catalysts on a TiO2 substrate and exposure to an oxidizing or reducing gaseous atmosphere on the state of Ag and Pd centers. We have shown that as a result of the metal-support interaction, the reducibility of the Ag and Pd particles is increased, which leads to a change in their adsorption and catalytic properties.

  18. Biosynthesis of Pd-Au alloys on carbon fiber paper: Towards an eco-friendly solution for catalysts fabrication

    NASA Astrophysics Data System (ADS)

    Zhuang, Zechao; Wang, Feifeng; Naidu, Ravendra; Chen, Zuliang

    2015-09-01

    Bimetallic nanomaterials with enhanced activity and stability have been extensively studied as emerging catalysts for hydrogen evolution reaction (HER). Expensive and environmentally unfriendly chemical synthesis routes inhibit their large-scale applications. In this work, we developed a facile and green synthesis of Pd-Au alloy nanoparticles (NPs) dispersed on carbon fiber paper (CFP) by plant-mediated bioreduction coupled with self-assembly. Engineering the morphology and composition of bimetallic catalysts synthesized by plant extracts on complex substrate is achieved. The resulting NPs are uniform in shape and have a spherical morphology with an average diameter of ∼180 nm, in which the molar ratio of Au/Pd is near 75:25 and the catalysts loading is about 0.5 mg cm-2. The Pd-Au/CFP hybrid electrode exhibits an excellent HER performance with a Tafel slope of 47 mV dec-1 and an exchange current density of 0.256 mA cm-2. Electrochemical stability tests through long-term potential cycles and potentiostatic electrolysis further confirm the high durability of the electrode. This development offers an efficient and eco-friendly catalysts synthesis route for constructing water-splitting cells and other electrocatalytic devices.

  19. Determination of redox reaction rates and orders by in situ liquid cell electron microscopy of Pd and Au solution growth

    SciTech Connect

    Sutter, Eli A.; Sutter, Peter W.

    2014-11-19

    In-situ liquid cell transmission and scanning transmission electron microscopy (TEM/STEM) experiments are important as they provide direct insight into processes in liquids, such as solution growth of nanoparticles among others. In liquid cell TEM/STEM redox reaction experiments the hydrated electrons e⁻aq created by the electron beam are responsible for the reduction of metal-ion complexes. Here we investigate the rate equation of redox reactions involving reduction by e⁻aq generated by the electron beam during in-situ liquid TEM/STEM. Specifically we consider the growth of Pd on Au seeds in aqueous solutions containing Pd-chloro complexes. From the quantification of the rate of Pd deposition at different electron beam currents and as a function of distance from a stationary, nanometer-sized exciting beam, we determine that the reaction is first order with respect to the concentration of hydrated electrons, [e⁻aq]. In addition, by comparing Pd- and Au-deposition, we further demonstrate that measurements of the local deposition rate on nanoparticles in the solution via real-time imaging can be used to measure not only [e⁻aq] but also the rate of reduction of a metal-ion complex to zero-valent metal atoms in solution.

  20. Study on deposition technique and properties of Pd/Ag alloy film sensor supported on ceramic substrate

    NASA Astrophysics Data System (ADS)

    Geng, Z. T.; He, Q.; Jin, C. G.

    2016-07-01

    Developing high-quality hydrogen sensitive material is the core part of hydrogen sensor, whose performance is determined by the sensitive response, reproducibility and recovery of hydrogen material etc. In order to overcome the defects of hydrogen embrittlement in previous hydrogen sensor which were based on the pure palladium, sliver as the second component added to the palladium was studied. Using photochemical etching technology to produce a bent metal mask, the mask is put on the ceramic substrate. Firstly, the thin film of Ta2O5 as a transition layer grew on the ceramic substrate. Then, a series of Pd/Ag alloy film sensors were prepared, and each performance characterization of Pd/Ag alloy film was studied. Testing results indicated that the thin film had a good linear output performance at 0∼⃒30% hydrogen concentration range, and demonstrates a high responsiveness and good repeatability. With temperature increasing, the strength of the responsive signal of the Pd/Ag alloy film decreases and its responsive time was also shortened.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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

  6. Half sandwich structures of MCF6- (M = Ag and Au): An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Sun, Zhang; Tang, Zichao; Gao, Zhen

    2013-01-01

    The metal-hexafluorobenzene anionic complexes of [MC6F6]- (M = Ag and Au) were produced from the reactions between metal cluster generated by laser ablation and the hexafluorobenzene seeded in argon carrier gas, and were studied by photoelectron spectroscopy (PES) and density functional theory (DFT). The adiabatic electron affinities (EAs) of these corresponding complexes are measured from the experimental PE spectra at 193 nm photon energy. Also, the calculated EAs and the calculated density of states (DOS) spectra of these complexes in the ground state are conducted, which are in good agreement with their experimental PE spectra. The most possible structures of the anions [AgC6F6]- and [AuC6F6]- are the half-sandwich structures with C6v symmetry, in which the metal atom is above the center of the C6F6 plane. Furthermore, the molecular orbital (MO) analysis of these species indicates that the additional electron of the anions binds on the metal.

  7. 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.

  8. Enhanced Selectivity to H2 Formation in Decomposition of HCOOH on the Ag19@Pd60 Core-Shell Nanocluster from First-Principles.

    PubMed

    Cho, Jinwon; Lee, Sangheon; Han, Jonghee; Yoon, Sung Pil; Nam, Suk Woo; Choi, Sun Hee; Hong, Seong-Ahn; Lee, Kwan-Young; Ham, Hyung Chul

    2015-10-01

    In this study, using spin-polarized density functional theory calculation we examined the origin of enhanced catalytic activity toward H2 production from HCOOH in Ag19@Pd60 core-shell nanoclusters (a 79-atom truncated octahedral cluster models). First, we find that the Pd monolayer shell on the Ag core can greatly enhance the selectivity to H2 formation via HCOOH decomposition compared to the pure Pd79 cluster by substantially reducing the binding energy of key intermediate HCOO and in turn the barrier for dehydrogenation. This activity enhancement is related to the modification of d states in the Pd monolayer shell by the strong ligand effect between Ag core and Pd shell, rather than the tensile strain effect by Ag core. In particular, the absence of dz2-r2 density of states near the Fermi level in the Pd monolayer shell (which originated from the substantial charge transfer from Ag to Pd) is the main reason for the increased H2 production from HCOOH decomposition. PMID:26726494

  9. 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.

  10. An ultrasensitive, uniform and large-area surface-enhanced Raman scattering substrate based on Ag or Ag/Au nanoparticles decorated Si nanocone arrays

    NASA Astrophysics Data System (ADS)

    Zhang, P. P.; Gao, J.; Sun, X. H.

    2015-01-01

    Large-area and highly ordered Si nanocone arrays decorated with Ag or Au/Ag nanoparticles have been fabricated via a mask-free lithography with reaction ion etching, followed by metal deposition process. Ultrasensitive surface enhanced Raman scattering signals with an enhancement factor of 1012 were achieved even at the concentration of the Rhodamine 6G as low as 10-15 M. The surface-enhanced Raman spectroscopy (SERS) substrate was also applied on the detection of Sudan I dye and the Raman signals were substantially enhanced as well. The stability of the SERS substrate can be significantly improved by covering Ag nanoparticles with Au thin layer, which maintain a high SERS performance even after one month storage. This nanofabrication process appears to be a feasible approach to prepare uniform and reproducible SERS-active substrates with high sensitivity and stability for practical SERS applications.

  11. Nucleation-mediated synthesis and enhanced catalytic properties of Au-Pd bimetallic tripods and bipyramids with twinned structures and high-energy facets.

    PubMed

    Zhang, Lei; Chen, Qiaoli; Wang, Xue; Jiang, Zhiyuan

    2016-02-01

    The Au-Pd alloy has been proved to be an excellent catalyst in many applications, such as the electro-oxidation of formic acid, CO oxidation and oxidation of alcohols to aldehydes. However, most of the research has been focused on the shape-controlled Au-Pd alloy NCs with a single-crystal structure. Due to the existence of high-energy atoms on the twin defects, twinned structures usually will further increase their catalytic activities. It is necessary to develop a method to prepare the Au-Pd alloy with twinned structures and investigate their catalytic properties. Herein, we successfully synthesized Au-Pd alloy tripods and bipyramids with twinned structures by the cooperation of cetyltrimethyl ammonium chloride (CTAC) and cetyltrimethyl ammonium bromide (CTAB). The tripods contain one twin plane, while the bipyramids consist of a fivefold-twinned structure. In addition, the tripods and bipyramids are both exposed by high-energy facets. We proposed that the tripods and bipyramids are evolved from bipyramid seeds and fivefold twinned seeds, respectively. The as-prepared Au-Pd tripods and bipyramids performed better activity for electrocatalytic oxidation of formic acid compared to the cubic Au-Pd nanoparticles. PMID:26763593

  12. Polymer monolithic capillary microextraction on-line coupled with inductively coupled plasma-mass spectrometry for the determination of trace Au and Pd in biological samples

    NASA Astrophysics Data System (ADS)

    Liu, Xiaolan; He, Man; Chen, Beibei; Hu, Bin

    2014-11-01

    A novel method based on on-line polymer monolithic capillary microextraction (CME)-inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace Au and Pd in biological samples. For this purpose, poly(glycidyl methacrylate-ethylene dimethacrylate) monolith was prepared and functionalized with mercapto groups. The prepared monolith exhibited good selectivity to Au and Pd, and good resistance to strong acid with a long life span. Factors affecting the extraction efficiency of CME, such as sample acidity, sample flow rate, eluent conditions and coexisting ion interference were investigated in detail. Under the optimal conditions, the limits of detection (LODs, 3σ) were 5.9 ng L- 1 for Au and 8.3 ng L- 1 for Pd, and the relative standard deviations (RSDs, c = 50 ng L -1, n = 7) were 6.5% for Au and 1.1% for Pd, respectively. The developed method was successfully applied to the determination of Au and Pd in human urine and serum samples with the recovery in the range of 84-118% for spiked samples. The developed on-line polymer monolithic CME-ICP-MS method has the advantages of rapidity, simplicity, low sample/reagent consumption, high sensitivity and is suitable for the determination of trace Au and Pd in biological samples with limited amount available and complex matrix.

  13. Catalytic and peroxidase-like activity of carbon based-AuPd bimetallic nanocomposite produced using carbon dots as the reductant.

    PubMed

    Yang, Liuqing; Liu, Xiaoying; Lu, Qiujun; Huang, Na; Liu, Meiling; Zhang, Youyu; Yao, Shouzhuo

    2016-08-01

    In this report, carbon-based AuPd bimetallic nanocomposite (AuPd/C NC) was synthesized using carbon dots (C-dots) as the reducing agent and stabilizer by a simple green sequential reduction strategy, without adding other agents. The as synthesized AuPd/C NC showed good catalytic activity and peroxidase-like property. The structure and morphology of these nanoparticles were clearly characterized by UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The AuPd/C NC catalyst exhibits noticeably higher catalytic activity than Pd and Au nanoparticles in catalysis reduction of 4-nitrophenol (4-NP). Moreover, based on the high peroxidase-like property of AuPd/C NC, a new colorimetric detection method for hydrogen peroxide (H2O2) has been designed using 3,3',5,5'-tetramethyl-benzidine (TMB) as the substrate, which provides a simple and sensitive means to detect H2O2 in wide linear range of 5 μM-500 μM and 500 μM-4 mM with low detection limit of 1.6 μM (S/N = 3). Therefore, the facile synthesis strategy for bimetallic nanoparticles by the mild reductant of carbon dot will provide some new thoughts for preparing of carbon-based metal nanomaterials and expand their application in catalysis and analytical chemistry areas. PMID:27265901

  14. Electron configuration and charge state of electrically active Cu, Ag and Au ions in ZnSe

    NASA Astrophysics Data System (ADS)

    Nedeoglo, N. D.; Sirkeli, V. P.; Nedeoglo, D. D.; Laiho, R.; Lähderanta, E.

    2006-08-01

    The Hall effect, electrical conductivity and electron mobility are investigated at temperatures between 55 and 500 K in n-ZnSe crystals doped with Cu, Ag or Au. The presence of a small amount of Cu atoms leads to an inversion of the sign of the Hall coefficient at temperatures above 300 K. Anomalous temperature dependence of the electron mobility is observed in the samples with low Cu concentration (<0.3 at.% in the melt). Different characters of the temperature dependences of kinetic coefficients are found for n-ZnSe doped with Ag and Au. These curves are typical for crystals having several donor levels at different energetic depths. Immediately after doping, silver behaves like a usual compensating acceptor impurity while gold shows amphoteric properties. We propose a model that explains the anomalies of the temperature dependences of the kinetic coefficients in Cu-doped crystals and the lack of the anomalies in Ag-doped and Au-doped crystals. In accordance with this model and our experimental data, copper in n-ZnSe has two charge states, CuZn+ (d10) and CuZn2+ (d9), and two acceptor levels near the valence band. Silver and gold exist in single-charged states AgZn+ and AuZn+ with d10 electron configuration forming single energy levels near the valence band. Au atoms form mainly interstitial Aui donors at low doping concentrations and substitutional AuZn and AuZn-based acceptors at high doping concentrations. Time stimulation of the amphoteric properties of Ag is discussed.

  15. 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

  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. Au@Ag nanorods based electrochemical immunoassay for immunoglobulin G with signal enhancement using carbon nanofibers-polyamidoamine dendrimer nanocomposite.

    PubMed

    Ma, Lina; Ning, Danlei; Zhang, Hongfang; Zheng, Jianbin

    2015-06-15

    Au@Ag nanorods (Au@AgNRs) was utilized to construct a novel sandwich-type electrochemical immunosensor for the detection of immunoglobulin G (IgG). The sensor was prepared by immoblizing capture antibodies on the amine-terminated nanocomposite of carbon nanofibers-polyamidoamine dendrimer (CNFs-PAMAM), whilst the trace tag was prepared by loading anti-human IgG on Au@AgNRs. The "built-in" Ag layer on Au nanorods was characterized by UV-vis extinction spectra, transmission electron microscopy and energy dispersive spectroscopy. The results of cyclic voltammetry indicated that modifying CNFs-PAMAM nanocomposite on glassy carbon electrode enabled 177 times of peak current increase of Ag in the bimetallic nanorods. The peak current was quantitatively related with the concentration of the target protein IgG via the formation of immunocomplex. After the parameter optimization, the oxidative peak current of silver was proportional to the concentration of IgG in a wide linear range of six orders of magnitude with a low detection limit of 0.5 fg mL(-1). Besides, this sensor showed acceptable reproducibility and stability, and thus the strategy reported here has great promise for extension to the other disease biomarkers. PMID:25569874

  18. 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

  19. 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

  20. Fabrication of Au@Ag core/shell nanoparticles decorated TiO2 hollow structure for efficient light-harvesting in dye-sensitized solar cells.

    PubMed

    Yun, Juyoung; Hwang, Sun Hye; Jang, Jyongsik

    2015-01-28

    Improving the light-harvesting properties of photoanodes is promising way to enhance the power conversion efficiency (PCE) of dye-sensitized solar cells (DSSCs). We synthesized Au@Ag core/shell nanoparticles decorated TiO2 hollow nanoparticles (Au@Ag/TiO2 HNPs) via sol-gel reaction and chemical deposition. The Au@Ag/TiO2 HNPs exhibited multifunctions from Au@Ag core/shell NPs (Au@Ag CSNPs) and TiO2 hollow nanoparticles (TiO2 HNPs). These Au@Ag CSNPs exhibited strong and broadened localized surface plasmon resonance (LSPR), together with a large specific surface area of 129 m(2) g(-1), light scattering effect, and facile oxidation-reduction reaction of electrolyte from TiO2 HNPs, which resulted in enhancement of the light harvesting. The optimum PCE of η = 9.7% was achieved for the DSSCs using photoanode materials based on TiO2 HNPs containing Au@Ag/TiO2 HNPs (0.2 wt % Au@Ag CSNPs with respect to TiO2 HNPs), which outperformed by 24% enhancement that of conventional photoanodes formed using P25 (η = 7.8%). PMID:25562329

  1. Isothermal nucleation and growth kinetics of Pd/Ag alloy phase via in-situ time-resolved high-temperature x-ray diffraction (HTXRD) analysis

    SciTech Connect

    Ayturk, Mahmut Engin; Payzant, E Andrew; Speakman, Scott A; Ma, Yi Hua

    2008-01-01

    Among several different approaches to form Pd/Ag alloys for hydrogen separation applications, ex-situ studies carried by conventional X-ray point scanning detectors might fail to reveal the key aspects of the phase transformation between Pd and Ag metals. In this respect, in-situ time-resolved high temperature X-ray diffraction (HTXRD) was employed to study the Pd/Ag alloy phase nucleation and growth kinetics. By the use of linear position sensitive detectors, advanced optics and profile fitting with the use of JADE-6.5 software, isothermal phase evolution of the Pd/Ag alloy at 500 C, 550 C and 600 C under hydrogen atmosphere were quantified to elucidate the mechanistic details of the Pd/Ag alloy phase nucleation and growth pattern. Analysis of the HTXRD data by the Avrami model indicated that the nucleation of the Pd/Ag alloy phase was instantaneous where the growth mechanism was through diffusion-controlled one-dimensional thickening of the Pd/Ag alloy layer. The value of the Avrami exponent, n, was found to increase with temperature with the values of 0.34, 0.39 and 0.67 at 500oC, 550oC and 600oC, respectively. In addition, parabolic rate law analysis suggested that the nucleation of the Pd/Ag alloy phase was through a heterogeneous nucleation mode, in which the nucleation sites were defined as the non-equilibrium defects. The cross-sectional SEI micrographs indicated that the Pd/Ag alloy phase growth was strongly dependent upon the deposition morphology of the as-synthesized Pd and Ag layers formed by the electroless plating. Based on the Avrami model and the parabolic rate law, the estimated activation energies for the phase transformation were 236.5 and 185.6 kJ/mol and in excellent agreement with the literature values (183-239.5 kJ/mol).

  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. PMID:24383549

  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. Controlled preparation of Au/Ag/SnO2 core-shell nanoparticles using a photochemical method and applications in LSPR based sensing

    NASA Astrophysics Data System (ADS)

    Zhou, Na; Ye, Chen; Polavarapu, Lakshminarayana; Xu, Qing-Hua

    2015-05-01

    A photochemical method for the controlled preparation of core-shell Au/Ag/SnO2 nanorods (NRs) and nanospheres (NSs) has been developed based on photo-induced electron transfer processes in the plasmonic metal-semiconductor system. Au/AgNR/SnO2 and Au/AgNS/SnO2 were prepared by the UV irradiation of a mixture of mesoporous SnO2 coated AuNRs, or AuNSs, and AgNO3, in which AgNO3 was reduced by electrons transferred from the photo-excited mesoporous SnO2 (semiconductor) to the gold (metal). This method allows precise control over the composition and optical properties of the obtained nanoparticles. The LSPR refractive index sensitivity of the obtained Au/AgNR/SnO2 nanoparticles has been optimized to obtain a refractive index sensitivity of ~442 nm RIU-1. The optimized nanoparticles were subsequently chosen for the LSPR based sensing of glutathione (GSH) with the limit of detection of ~7.5 × 10-7 M. This photochemical method allows the controlled preparation of various Au/Ag/SnO2 nanoparticles to adjust their LSPR to suit various applications.A photochemical method for the controlled preparation of core-shell Au/Ag/SnO2 nanorods (NRs) and nanospheres (NSs) has been developed based on photo-induced electron transfer processes in the plasmonic metal-semiconductor system. Au/AgNR/SnO2 and Au/AgNS/SnO2 were prepared by the UV irradiation of a mixture of mesoporous SnO2 coated AuNRs, or AuNSs, and AgNO3, in which AgNO3 was reduced by electrons transferred from the photo-excited mesoporous SnO2 (semiconductor) to the gold (metal). This method allows precise control over the composition and optical properties of the obtained nanoparticles. The LSPR refractive index sensitivity of the obtained Au/AgNR/SnO2 nanoparticles has been optimized to obtain a refractive index sensitivity of ~442 nm RIU-1. The optimized nanoparticles were subsequently chosen for the LSPR based sensing of glutathione (GSH) with the limit of detection of ~7.5 × 10-7 M. This photochemical method allows

  5. A theoretical DFT-based and experimental study of the transmetalation step in Au/Pd-mediated cross-coupling reactions.

    PubMed

    Hansmann, Max M; Pernpointner, Markus; Döpp, René; Hashmi, A Stephen K

    2013-11-01

    In this work a combined theoretical and experimental investigation of the cross-coupling reaction involving two metallic reaction centers, namely gold and palladium, is described. One metal center (Au) hereby is rather inert towards change in its oxidation state, whereas Pd undergoes oxidative insertion and reductive elimination steps. Detailed mechanistic and energetic studies of each individual step, with the focus on the key transmetalation step are presented and compared for different substrates and ligands on the catalytic Pd center. Different aryl halides (Cl, Br, I) and aryl triflates were investigated. Hereby the nature of the counteranion X turned out to be crucial. In the case of X=Cl and L=PMe3 the oxidative addition is rate-determining, whereas in the case of X=I the transmetalation step becomes rate-determining in the Au/Pd-cross-coupling mechanism. A variety of Au-Pd transmetalation reaction scenarios are discussed in detail, favoring a transition state with short intermetallic Au-Pd contacts. Furthermore, without a halide counteranion the transmetalation from gold(I) to palladium(II) is highly endothermic, which confirms our experimental findings that the coupling does not occur with aryl triflates and similar weakly coordinating counteranions--a conclusion that is essential in designing new Au-Pd catalytic cycles. In combination with experimental work, this corrects a previous report in the literature claiming a successful coupling potentially catalytic in both metals with weakly coordinating counteranions. PMID:24115258

  6. CO₂ electroreduction at bare and Cu-decorated Pd pseudomorphic layers: catalyst tuning by controlled and indirect supporting onto Au(111).

    PubMed

    Januszewska, Aneta; Jurczakowski, Rafal; Kulesza, Pawel J

    2014-12-01

    We report here the results of electrochemical studies on CO2 electroreduction at multilayered catalyst composed of the monatomic layer of copper covering palladium overlayers (0.8-10 monolayers) deposited on the well-defined Au(111) surface. These multilayered systems were obtained by successive underpotential deposition steps: Pd on Au(111) as well as Cu on Pd/Au(111). Low index orientation of Au substrate was chosen to compare Pd overlayers with bulk Pd(111), which is known to reduce CO2 to CO adsorbates in acidic solutions. The process of CO2 electroreduction was studied by using classical transient electrochemical methods. Catalytic activity of bare Pd layers was investigated in acidic and neutral solutions. In the latter case, much higher activity of Pd overlayers was observed. The results showed that the palladium layer thickness significantly changed the catalytic activities of both bare Pd overlayers and the one Cu monolayer covered electrodes toward CO2 electroreduction. Results show that catalytic activity can be finely tuned by using the multilayered near-surface-alloy approach. PMID:25350872

  7. 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/.

  8. Nucleation-mediated synthesis and enhanced catalytic properties of Au-Pd bimetallic tripods and bipyramids with twinned structures and high-energy facets

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Chen, Qiaoli; Wang, Xue; Jiang, Zhiyuan

    2016-01-01

    The Au-Pd alloy has been proved to be an excellent catalyst in many applications, such as the electro-oxidation of formic acid, CO oxidation and oxidation of alcohols to aldehydes. However, most of the research has been focused on the shape-controlled Au-Pd alloy NCs with a single-crystal structure. Due to the existence of high-energy atoms on the twin defects, twinned structures usually will further increase their catalytic activities. It is necessary to develop a method to prepare the Au-Pd alloy with twinned structures and investigate their catalytic properties. Herein, we successfully synthesized Au-Pd alloy tripods and bipyramids with twinned structures by the cooperation of cetyltrimethyl ammonium chloride (CTAC) and cetyltrimethyl ammonium bromide (CTAB). The tripods contain one twin plane, while the bipyramids consist of a fivefold-twinned structure. In addition, the tripods and bipyramids are both exposed by high-energy facets. We proposed that the tripods and bipyramids are evolved from bipyramid seeds and fivefold twinned seeds, respectively. The as-prepared Au-Pd tripods and bipyramids performed better activity for electrocatalytic oxidation of formic acid compared to the cubic Au-Pd nanoparticles.The Au-Pd alloy has been proved to be an excellent catalyst in many applications, such as the electro-oxidation of formic acid, CO oxidation and oxidation of alcohols to aldehydes. However, most of the research has been focused on the shape-controlled Au-Pd alloy NCs with a single-crystal structure. Due to the existence of high-energy atoms on the twin defects, twinned structures usually will further increase their catalytic activities. It is necessary to develop a method to prepare the Au-Pd alloy with twinned structures and investigate their catalytic properties. Herein, we successfully synthesized Au-Pd alloy tripods and bipyramids with twinned structures by the cooperation of cetyltrimethyl ammonium chloride (CTAC) and cetyltrimethyl ammonium bromide (CTAB

  9. Determination of redox reaction rates and orders by in situ liquid cell electron microscopy of Pd and Au solution growth

    DOE PAGESBeta

    Sutter, Eli A.; Sutter, Peter W.

    2014-11-19

    In-situ liquid cell transmission and scanning transmission electron microscopy (TEM/STEM) experiments are important as they provide direct insight into processes in liquids, such as solution growth of nanoparticles among others. In liquid cell TEM/STEM redox reaction experiments the hydrated electrons e⁻aq created by the electron beam are responsible for the reduction of metal-ion complexes. Here we investigate the rate equation of redox reactions involving reduction by e⁻aq generated by the electron beam during in-situ liquid TEM/STEM. Specifically we consider the growth of Pd on Au seeds in aqueous solutions containing Pd-chloro complexes. From the quantification of the rate of Pdmore » deposition at different electron beam currents and as a function of distance from a stationary, nanometer-sized exciting beam, we determine that the reaction is first order with respect to the concentration of hydrated electrons, [e⁻aq]. In addition, by comparing Pd- and Au-deposition, we further demonstrate that measurements of the local deposition rate on nanoparticles in the solution via real-time imaging can be used to measure not only [e⁻aq] but also the rate of reduction of a metal-ion complex to zero-valent metal atoms in solution.« less

  10. 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

  11. Facile Synthesis of Ag Nanorods with No Plasmon Resonance Peak in the Visible Region by Using Pd Decahedra of 16 nm in Size as Seeds.

    PubMed

    Luo, Ming; Huang, Hongwen; Choi, Sang-Il; Zhang, Chao; da Silva, Robson Rosa; Peng, Hsin-Chieh; Li, Zhi-Yuan; Liu, Jingyue; He, Zhike; Xia, Younan

    2015-10-27

    This article describes a seed-mediated approach to the synthesis of Ag nanorods with thin diameters and tunable aspect ratios. The success of this method is built upon our recent progress in the synthesis of Pd decahedra as uniform samples, together with controllable sizes. When used as a seed, the Pd decahedron could direct the deposition of Ag atoms along the 5-fold axis to generate a nanorod, with its diameter being determined by the lateral dimension of the seed. We were able to generate Ag nanorods with uniform diameters down to 20 nm. Under the conditions we used for growth, symmetry breaking occurred as the Ag atoms were only deposited along one side of the Pd decahedral seed to generate a Ag nanorod with the Pd seed being positioned at one of its two ends. We also systematically investigated the localized surface plasmon resonance (LSPR) properties of the Ag nanorods. With the transverse mode kept below 400 nm, the longitudinal mode could be readily tuned from the visible to the near-infrared region by varying the aspect ratio. As an important demonstration, we obtained Ag nanorods with no LSPR peak in the visible spectrum (400-800 nm), which are attractive for applications related to the fabrication of touchscreen displays, solar films, and energy-saving smart windows. PMID:26372854

  12. A novel electrochemical immunosensor based on nonenzymatic Ag@Au-Fe3O4 nanoelectrocatalyst for protein biomarker detection.

    PubMed

    Zhang, Hongfang; Ma, Lina; Li, Pengli; Zheng, Jianbin

    2016-11-15

    A hybrid nanostructure of Fe3O4 nanospheres and Ag@Au nanorods prepared by polydopamine coating was utilized as nanoelectrocatalyst to construct a novel sandwich-type electrochemical immunosensor. Ag@Au-Fe3O4 nanohybrid modified electrode exhibited much better electrocatalytic activity toward the reduction of hydrogen peroxide than Fe3O4 nanospheres or Ag@Au nanorods due to the synergetic catalytic effect. The immunosensor was prepared by immobilizing the capture antibodies on the amine-terminated nanocomposite of carbon nanofibers-chitosan, whilst the trace tag was prepared by loading detection antibodies on the Ag@Au-Fe3O4 nanocomposite. After the parameter optimization, the amperometric signal increased linearly with human IgG concentration in the broad range of 0.1pgmL(-1) to 5μgmL(-1) with a detection limit of 50fgmL(-1). Meanwhile, the enzyme-free catalyst based immunosensor also showed acceptable selectivity, reproducibility and stability. PMID:27183286

  13. 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

  14. Dextrin-mediated synthesis of Ag NPs for colorimetric assays of Cu(2+) ion and Au NPs for catalytic activity.

    PubMed

    Bankura, Kalipada; Rana, Dipak; Mollick, Md Masud Rahaman; Pattanayak, Sutanuka; Bhowmick, Biplab; Saha, Nayan Ranjan; Roy, Indranil; Midya, Tarapada; Barman, Gadadhar; Chattopadhyay, Dipankar

    2015-09-01

    A facile one-pot approach for rapid synthesis of silver and gold nanoparticles (Ag NPs and Au NPs) with narrow size distribution and good stability was described by reducing silver nitrate and chloroauric acid with polysaccharide dextrin. Here, dextrin was used as both a reducing and stabilizing agent for synthesis of NPs. The as-synthesized Ag NPs and Au NPs were characterized by UV-visible absorption spectroscopy, transmission electron microscopy (TEM) and X-ray diffraction (XRD). The Ag NPs and Au NPs exhibited an absorption maxima at 404 and 547 nm respectively. TEM images showed NPs in the range of 8-28 nm. The crystallinity of the NPs was measured by XRD analysis. Furthermore, the as-prepared Ag NPs revealed colorimetric sensor property for detection of Cu(2+) ions based on changes in absorbance resulting from metal ion-induced aggregation of NPs or direct deposition of metal ions onto NPs. The as-prepared Au NPs exhibited a notable catalytic activity toward the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4. PMID:26143120

  15. 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.

  16. 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. PMID:27111025

  17. 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

  18. Steering Fluorescence Emission with Metal-Dielectric-Metal Structures of Au, Ag and Al

    PubMed Central

    Dutta Choudhury, Sharmistha; Badugu, Ramachandram; Ray, Krishanu; Lakowicz, Joseph R.

    2014-01-01

    Directional control over fluorescence emission is important for improving the sensitivity of fluorescence based techniques. In recent years, plasmonic and photonic structures have shown great promise in shaping the spectral and spatial distribution of fluorescence, which otherwise is typically isotropic in nature and independent of the observation direction. In this work we have explored the potential of metal-dielectric-metal (MDM) structures composed of Au, Ag or Al in steering the fluorescence emission from various probes emitting in the NIR, Visible or UV/blue region. We show that depending on the optical properties of the metal and the thickness of the dielectric layer, the emission from randomly oriented fluorophores embedded within the MDM substrate is transformed into beaming emission normal to the substrate. Agreement of the observed angular emission patterns with reflectivity calculations reveals that the directional emission is due to the coupling of the fluorescence with the electromagnetic modes supported by the MDM structure. PMID:25126154

  19. 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.

  20. 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) . PMID:27028550

  1. Tailor-made Au@Ag core-shell nanoparticle 2D arrays on protein-coated graphene oxide with assembly enhanced antibacterial activity

    NASA Astrophysics Data System (ADS)

    Wang, Huiqiao; Liu, Jinbin; Wu, Xuan; Tong, Zhonghua; Deng, Zhaoxiang

    2013-05-01

    Water-dispersible two-dimensional (2D) assemblies of Au@Ag core-shell nanoparticles are obtained through a highly selective electroless silver deposition on pre-assembled gold nanoparticles on bovine serum albumin (BSA)-coated graphene oxide (BSA-GO). While neither BSA-GO nor AuNP-decorated BSA-GO shows any antibacterial ability, the silver-coated GO@Au nanosheets (namely GO@Au@Ag) exhibit an enhanced antibacterial activity against Gram-negative Escherichia coli (E. coli) bacteria, superior to unassembled Au@Ag nanoparticles and even ionic Ag. Such an improvement may be attributed to the increased local concentration of silver nanoparticles around a bacterium and a polyvalent interaction with the bacterial surface. In addition, the colloidal stability of this novel nano-antimicrobial against the formation of random nanoparticle aggregates guarantees a minimized activity loss of the Au@Ag nanoparticles. The antibacterial efficacy of GO@Au@Ag is less sensitive to the existence of Cl-, in comparison with silver ions, providing another advantage for wound dressing applications. Our research unambiguously reveals a strong and very specific interaction between the GO@Au@Ag nanoassembly and E. coli, which could be an important clue toward a rational design, synthesis and assembly of innovative and highly active antibacterial nanomaterials.

  2. ARPES study of the surface states from Au/Ag( 1 1 1 ): evolution with coverage and photon energy

    NASA Astrophysics Data System (ADS)

    Palomares, F. J.; Serrano, M.; Ruiz, A.; Soria, F.; Horn, K.; Alonso, M.

    2002-07-01

    The Shockley surface states formed on the (1 1 1) surfaces of noble metals have been extensively studied, but few reports exist on layered thin film systems. We present angle-resolved photoemission (ARPES) results, recorded at normal emission in the photon energy range from 21 to 49 eV, which describe the behavior of these sp-derived surface states for Au layers epitaxially grown on Ag(1 1 1). Growth was performed at room and low temperatures. In both cases, the ARPES spectra are found to evolve from Ag(1 1 1)-like to Au(1 1 1)-like features as the thickness of the Au film increases. In particular, the surface-state binding energy shifts from the Ag(1 1 1) to the bulk Au(1 1 1) position, the shift being already evident at coverages lower than one monolayer. The origin of the changes observed in the surface-state peak as a function of Au coverage and photon energy will be discussed.

  3. Electrocatalytic activity of alkyne-functionalized AgAu alloy nanoparticles for oxygen reduction in alkaline media

    NASA Astrophysics Data System (ADS)

    Hu, Peiguang; Song, Yang; Chen, Limei; Chen, Shaowei

    2015-05-01

    1-Dodecyne-functionalized AgAu alloy nanoparticles were synthesized by chemical reduction of metal salt precursors at varied initial feed ratios. Transmission electron microscopic measurements showed that the nanoparticles were all rather well dispersed with the average core diameter in the narrow range of 3 to 5 nm. X-ray photoelectron spectroscopic studies confirmed the formation of AgAu alloy nanoparticles with the gold concentration ranging from approximately 25 at% to 55 at%. Consistent results were obtained in UV-vis spectroscopic measurements where the nanoparticle surface plasmon resonance red-shifted almost linearly with increasing gold concentrations. The self-assembly of 1-dodecyne ligands on the nanoparticle surface was manifested in infrared spectroscopic measurements. Importantly, the resulting nanoparticles exhibited apparent electrocatalytic activity for oxygen reduction in alkaline media, and the performance was found to show a volcano variation in the Au content in the alloy nanoparticles, with the best performance observed for the samples with ca. 35.5 at% Au. The enhanced catalytic activity, as compared to pure Ag nanoparticles or even commercial Pt/C catalysts, was accounted for by the unique metal-ligand interfacial bonding interactions as well as alloying effects that increased metal-oxygen affinity.1-Dodecyne-functionalized AgAu alloy nanoparticles were synthesized by chemical reduction of metal salt precursors at varied initial feed ratios. Transmission electron microscopic measurements showed that the nanoparticles were all rather well dispersed with the average core diameter in the narrow range of 3 to 5 nm. X-ray photoelectron spectroscopic studies confirmed the formation of AgAu alloy nanoparticles with the gold concentration ranging from approximately 25 at% to 55 at%. Consistent results were obtained in UV-vis spectroscopic measurements where the nanoparticle surface plasmon resonance red-shifted almost linearly with increasing gold

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

    DOE PAGESBeta

    Poudel, Lekhanath N.; De la cruz, Clarina; Payzant, E. Andrew; Koehler, Michael R.; May, Andrew F.; Garlea, Vasile O.; Taylor, Alice E.; Parker, David S.; Cao, Huibo B.; McGuire, Michael A.; et al

    2015-12-15

    The structural and the magnetic properties of CeCu6-xAgx (0 ≤ x ≤ 0.85) and CeCu6-xPdx (0 ≤ x ≤ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu6-xAgx and CeCu6-xPdx as a function of Ag/Pd composition are reported. The end member, CeCu6, undergoes a structural phase transition from an orthorhombic (Pnma) to a monoclinic (P21/c) phase at 240 K. In CeCu6-xAgx, the structural phase transition temperature (Ts) decreases linearly with Ag concentration and extrapolates to zero at xS ≈ 0.1. The structural transitionmore » in CeCu6-xPdx remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu6-xAgx and CeCu6-xPdx, exhibit a magnetic quantum critical point (QCP), at x ≈ 0.2 and x ≈ 0.05, respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ1 0 δ2), where δ1 ~ 0.62, δ2 ~ 0.25, x = 0.125 for CeCu6-xPdx and δ1 ~ 0.64, δ2 ~ 0.3, x = 0.3 for CeCu6-xAgx. As a result, the magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.« less

  5. 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

  6. THERMODYNAMIC PROPERTIES OF THE METALLIC SYSTEM Au(111)-(3×3)R30∘-Pd

    NASA Astrophysics Data System (ADS)

    Chadli, R.; Kheffache, S.; Khater, A.

    2016-02-01

    This work constitutes an analysis of the thermodynamic properties in the ordered metallic surface alloy system Au(111)-(3×3)R30∘-Pd. The equilibrium structural characteristics as well as the thermodynamic functions are examined by the matching method, associated with real space Green’s function formalism, evaluated in the harmonic approximation. Our numerical results, for this metallic system of surface alloy, show in particular a significant dependence between the thermodynamic properties and the coordination number and the values of the force constants.

  7. 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.

  8. Electronic Properties of MoSi2-Type Hf2X Intermetallic Compounds (X=Pd, Ag, Cd)

    NASA Astrophysics Data System (ADS)

    Yaar, I.; Maytal-Beck, S.; Berant, Z.

    2001-11-01

    The Hf z coordinate and the value of the electric field gradient (efg) main component (V zz ), were calculated for three Hf2X compounds (X = Pd, Ag, Cd) on a first-principle basis, using the full potential linear augmented plane wave (LAPW) method. Exchange and correlation effects were treated either by the local spine density approximation (LSDA) or by the more advanced generalized gradient approximation (GGA). The calculated V zz values, in the Hf site, were in very good agreement with available 181Hf TDPAC experimental results.

  9. Investigation of nanostructured Pd-Ag/n-ZnO thin film based Schottky junction for methane sensing

    NASA Astrophysics Data System (ADS)

    Roy, S.; Das, S.; Sarkar, C. K.

    2016-07-01

    Undoped nanocrystalline n-type ZnO thin film was deposited by chemical deposition technique on a thermally oxidized p-Si (~5 Ω cm resistivity and <100> orientation) substrate. Formation of stable zinc oxide thin film was confirmed by two-dimensional X-Ray Diffraction (XRD) and EDX analysis. The average crystallite size of the ZnO sample was evaluated as ~50 nm. The surface was characterized by Field Emission Scanning Electron Microscopy (FESEM) and Atomic Force Microscopy (AFM) that confirm the formation of nanocrystalline (grain size ~50 nm) ZnO thin film with surface roughness of ~100 nm. Good conversion of precursor into ZnO thin film in the chemical deposition method was evident by Fourier Transform Infrared Spectroscopy (FTIR). A small peak at 479 cm-1was observed in the FTIR spectrum confirming the formation of quartzite structure of the ZnO. The band gap (~3.44 eV) of the material was calculated from the optical absorption spectroscopy. To prepare Pd-Ag/n-ZnO Schottky junction, Pd-Ag contacts were taken by electron beam evaporation method. I-V characteristics of the junction were studied at different temperatures in inert and reducing ambient (N2 and N2 + CH4) with turn on voltage of around 0.2 V. The parameters like ideality factor ( η), saturation current ( I 0), series resistance ( Rs), and barrier height ( Φ BO) of the junction were calculated in the temperature range 50-200 °C in N2 as well as in 1 % CH4 + N2 ambient. It was observed that the ideality factor decreases in the temperature range 50-200 °C ( η = 12.34 at 50 °C and η = 1.52 at 200 °C) in N2 ambient and η = 1.18 in N2 +CH4 ambient at 200 °C. Schottky Barrier Height ( Φ BO) of the Pd-Ag/n-ZnO junction was found to increase with temperature. A close observation of Pd-Ag/n-ZnO junction in the presence of methane was performed to appreciate its application as methane sensor. The sensing mechanism was illustrated by a simplified energy band diagram.

  10. Investigation of nanostructured Pd-Ag/n-ZnO thin film based Schottky junction for methane sensing

    NASA Astrophysics Data System (ADS)

    Roy, S.; Das, S.; Sarkar, C. K.

    2016-07-01

    Undoped nanocrystalline n-type ZnO thin film was deposited by chemical deposition technique on a thermally oxidized p-Si (~5 Ω cm resistivity and <100> orientation) substrate. Formation of stable zinc oxide thin film was confirmed by two-dimensional X-Ray Diffraction (XRD) and EDX analysis. The average crystallite size of the ZnO sample was evaluated as ~50 nm. The surface was characterized by Field Emission Scanning Electron Microscopy (FESEM) and Atomic Force Microscopy (AFM) that confirm the formation of nanocrystalline (grain size ~50 nm) ZnO thin film with surface roughness of ~100 nm. Good conversion of precursor into ZnO thin film in the chemical deposition method was evident by Fourier Transform Infrared Spectroscopy (FTIR). A small peak at 479 cm-1was observed in the FTIR spectrum confirming the formation of quartzite structure of the ZnO. The band gap (~3.44 eV) of the material was calculated from the optical absorption spectroscopy. To prepare Pd-Ag/n-ZnO Schottky junction, Pd-Ag contacts were taken by electron beam evaporation method. I-V characteristics of the junction were studied at different temperatures in inert and reducing ambient (N2 and N2 + CH4) with turn on voltage of around 0.2 V. The parameters like ideality factor (η), saturation current (I 0), series resistance (Rs), and barrier height (Φ BO) of the junction were calculated in the temperature range 50-200 °C in N2 as well as in 1 % CH4 + N2 ambient. It was observed that the ideality factor decreases in the temperature range 50-200 °C (η = 12.34 at 50 °C and η = 1.52 at 200 °C) in N2 ambient and η = 1.18 in N2 +CH4 ambient at 200 °C. Schottky Barrier Height (Φ BO) of the Pd-Ag/n-ZnO junction was found to increase with temperature. A close observation of Pd-Ag/n-ZnO junction in the presence of methane was performed to appreciate its application as methane sensor. The sensing mechanism was illustrated by a simplified energy band diagram.

  11. Integration of Kinetic Control and Lattice Mismatch To Synthesize Pd@AuCu Core-Shell Planar Tetrapods with Size-Dependent Optical Properties.

    PubMed

    Meng, Min; Fang, Zhicheng; Zhang, Chao; Su, Hongyang; He, Rong; Zhang, Renpeng; Li, Hongliang; Li, Zhi-Yuan; Wu, Xiaojun; Ma, Chao; Zeng, Jie

    2016-05-11

    Planar nanocrystals with multiple branches exhibit unique localized surface plasmon resonance properties and great promise in optical applications. Here, we report an aqueous synthesis of Pd@AuCu core-shell planar tetrapods through preferential overgrowth on Pd cubic seeds. The large lattice mismatch between the Pd core and the AuCu shell is the key to induce the formation of branches under sluggish reduction kinetics. Meanwhile, the capping effect of cetyltrimethylammonium chloride on the {100} facets of Pd cubes with an aspect ratio of 1.2 can determine the growth direction of AuCu branches to form a planar structure. Through simply varying the amounts of Pd cubic seeds, the sizes of products can be well-controlled in the range from 33 to 70 nm. With the manipulation of sizes, the peak position of in-plane dipole resonance can be adjusted from visible to near-infrared region. Due to the presence of tips and edges in the branches, planar tetrapods exhibited excellent surface-enhanced Raman scattering performance with an enhancement factor up to 9.0 × 10(3) for 70 nm Pd@AuCu planar tetrapods. PMID:27074129

  12. Sensitive electrochemical sensors for simultaneous determination of ascorbic acid, dopamine, and uric acid based on Au@Pd-reduced graphene oxide nanocomposites.

    PubMed

    Jiang, Jingjing; Du, Xuezhong

    2014-10-01

    Sensitive electrochemical sensors were fabricated with reduced graphene oxide-supported Au@Pd (Au@Pd-RGO) nanocomposites by one-step synthesis for individual and simultaneous determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA) with low detection limits and wide concentration ranges. From the Au@Pd-RGO-modified electrodes, well-separated oxidation peaks and enhanced peak currents of AA, DA, and UA were observed owing to the superior conductivity of RGO and the excellent catalytic activity of Au@Pd nanoparticles. For individual detection, the linear responses of AA, DA, and UA were in the concentration ranges of 0.1-1000, 0.01-100, and 0.02-500 μM with detection limits of 0.02, 0.002, and 0.005 μM (S/N = 3), respectively. For simultaneous detection by synchronous change of the concentrations of AA, DA, and UA, the linear response ranges were 1-800, 0.1-100, and 0.1-350 μM with detection limits of 0.28, 0.024, and 0.02 μM (S/N = 3), respectively. The fabricated sensors were further applied to the detection of AA, DA, and UA in urine samples. The Au@Pd-RGO nanocomposites have promising applications in highly sensitive and selective electrochemical sensing. PMID:25137352

  13. Electrochemical immunosensor for detecting typical bladder cancer biomarker based on reduced graphene oxide-tetraethylene pentamine and trimetallic AuPdPt nanoparticles.

    PubMed

    Ma, Hongmin; Zhang, Xiaoyue; Li, Xiaojian; Li, Rongxia; Du, Bin; Wei, Qin

    2015-10-01

    A highly sensitive electrochemical immunosensor for detection of typical bladder cancer biomarker-nuclear matrix protein 22 (NMP22) was developed by using reduced graphene oxide-tetraethylene pentamine (rGO-TEPA) and trimetallic AuPdPt nanoparticles (NPs). rGO-TEPA was used as the ideal material for signal amplification and AuPdPt NPs immobilization due to its excellent conductivity and large surface area. An effective platform was constructed for antibodies anchoring by using AuPdPt NPs, which kept the antibodies' high stability and bioactivity. Moreover, AuPdPt NPs could accelerate the electron transfer and enhance the signal response, which assisted by the synergistic effect of the three different metals (Au, Pd and Pt). The proposed immunosensor showed satisfied performance such as simple fabrication, low detection limits (0.01 U/mL), wide linear range (from 0.040 to 20 U/mL), short analysis time (2 min), high stability and selectivity in the detection of NMP22. Furthermore, the proposed immunosensor was employed to test real urine samples with satisfactory results. PMID:26078131

  14. Temperature, pressure, and size dependence of Pd-H interaction in size selected Pd-Ag and Pd-Cu alloy nanoparticles: In-situ X-ray diffraction studies

    SciTech Connect

    Sengar, Saurabh K.; Mehta, B. R.; Kulriya, P. K.

    2014-03-21

    In this study, in-situ X-ray diffraction has been carried out to investigate the effect of temperature and pressure on hydrogen induced lattice parameter variation in size selected Pd-Ag and Pd-Cu alloy nanoparticles. The nanoparticles of three different mobility equivalent diameters (20, 40, and 60 nm) having a narrow size distribution were prepared by gas phase synthesis method. In the present range of temperature (350 K to 250 K) and pressure (10{sup −4} to 100 millibars), no α (H/Pd ≤ 0.03) ↔ β (H/Pd ≥ 0.54) phase transition is observed. At temperature higher than 300 °C or pressure lower than 25 millibars, there is a large difference in the rate at which lattice constant varies as a function of pressure and temperature. Further, the lattice variation with temperature and pressure is also observed to depend upon the nanoparticle size. At lower temperature or higher pressure, size of the nanoparticle seems to be relatively less important. These results are explained on the basis of the relative dominance of physical absorption and diffusion of H in Pd alloy nanoparticles at different temperature and pressure. In the present study, absence of α ↔ β phase transition points towards the advantage of using Pd-alloy nanoparticles in applications requiring long term and repeated hydrogen cycling.

  15. Total structure determination of surface doping [Ag46Au24(SR)32](BPh4)2 nanocluster and its structure-related catalytic property

    PubMed Central

    Wang, Shuxin; Jin, Shan; Yang, Sha; Chen, Shuang; Song, Yongbo; Zhang, Jun; Zhu, Manzhou

    2015-01-01

    The structure effect is widely present in the catalysis of alloy systems. However, the surface structure of this system is still ambiguous because of the limitations of the current surface characterization tools. We reported the x-ray crystallographic structure of the first and the largest AgAu alloy nanocluster with a doping shell formulated as [Ag46Au24(SR)32](BPh4)2. This nanocluster consists of an achiral bimetallic Ag2@Au18@Ag20 core protected by a chiral Ag24Au6(SR)32 shell. The catalysis experiments further revealed that the surface structure affects the selectivity of products significantly. This is the first case to find the structure effect in atomically precise alloy nanoclusters. Our work will benefit the basic understanding of bimetal distribution, as well as the structure-related catalytic property of alloy nanoclusters at the atomic level. PMID:26601236

  16. Bi-SERS sensing and enhancement by Au-Ag bimetallic non-alloyed nanoparticles on amorphous and crystalline silicon substrate.

    PubMed

    Tan, Chee Leong; Lee, Soo Kyung; Lee, Yong Tak

    2015-03-01

    We have demonstrated Au-Ag bimetallic non-alloy nanoparticles (BNNPs) on thin a-Si film and c-Si substrate for high SERS enhancement, low cost, high sensitivity and reproducible SERS substrate with bi-SERS sensing properties where two different SERS peak for Au NPs and Ag NPs are observed on single SERS substrate. The isolated Au-Ag bimetallic NPs, with uniform size and spacing distribution, are suitable for uniform high density hotspot SERS enhancement. The SERS enhancement factor of Au-Ag BNNPs is 2.9 times higher compared to Ag NPs on similar substrates due to the increase of the localized surface plasmon resonance effect. However there is a decrement of SERS peak intensity at specific wavenumbers when the surrounding refractive index increases due to out-phase hybridization of Au NPs. The distinct changes of the two different SERS peaks on single Au-Ag BNNPs SERS substrate due to Au and Ag NPs independently show possible application for bi-molecular sensing. PMID:25836846

  17. 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.

  18. Shape transformation of bimetallic Au–Pd core–shell nanocubes to multilayered Au–Pd–Au core–shell hexagonal platelets

    SciTech Connect

    Bhattarai, Nabraj; Prozorov, Tanya

    2015-11-05

    Transformation of metallic or bimetallic (BM) nanoparticles (NPs) from one shape to another desired shape is of importance to nanoscience and nanotechnology, where new morphologies of NPs lead to enhancement of their exploitable properties. In this report, we present the shape transformation of Au octahedral NPs to Au–Pd core–shell nanocubes, followed by their transformation to nanostars and finally to multilayered Au–Pd–Au core–shell hexagonal platelets in the presence of T30 DNA. The weaker binding affinity of T30 DNA directs the growth to favor the formation of lower energy {111} facets, changing the morphology from nanocubes to nanostar. The nanostars, exhibiting unusual intermediate morphologies, are comprised two sets of shell layers and have Au core, Pd intermediate shell, and Au outer shell. Similarly, the hexagonal platelets, which also have Au core and inner Pd shell, are encased in an external gold shell. As a result, the formation of multilayered Au–Pd–Au core–shell hexagonal platelets from Au–Pd core–shell nanocubes via the multilayered nanostars is monitored using scanning/transmission electron microscopy analysis.

  19. Shape transformation of bimetallic Au–Pd core–shell nanocubes to multilayered Au–Pd–Au core–shell hexagonal platelets

    DOE PAGESBeta

    Bhattarai, Nabraj; Prozorov, Tanya

    2015-11-05

    Transformation of metallic or bimetallic (BM) nanoparticles (NPs) from one shape to another desired shape is of importance to nanoscience and nanotechnology, where new morphologies of NPs lead to enhancement of their exploitable properties. In this report, we present the shape transformation of Au octahedral NPs to Au–Pd core–shell nanocubes, followed by their transformation to nanostars and finally to multilayered Au–Pd–Au core–shell hexagonal platelets in the presence of T30 DNA. The weaker binding affinity of T30 DNA directs the growth to favor the formation of lower energy {111} facets, changing the morphology from nanocubes to nanostar. The nanostars, exhibiting unusualmore » intermediate morphologies, are comprised two sets of shell layers and have Au core, Pd intermediate shell, and Au outer shell. Similarly, the hexagonal platelets, which also have Au core and inner Pd shell, are encased in an external gold shell. As a result, the formation of multilayered Au–Pd–Au core–shell hexagonal platelets from Au–Pd core–shell nanocubes via the multilayered nanostars is monitored using scanning/transmission electron microscopy analysis.« less

  20. Electron transport properties and spin modulation effect analysis for C60, Au@C60 and Ag@C60

    NASA Astrophysics Data System (ADS)

    Wang, Fangyuan; Li, Guiqin

    2016-04-01

    The electron transport properties of C60, Au@C60 and Ag@C60 junctions between Au electrodes are investigated with density functional theory and the first-principle nonequilibrium Greens function. Density of states and transmission possibility as functions of energy are examined, and current-voltage characteristics of all these models are calculated with and without spin correction. With spin correction, we find a spin-current difference in Au@C60 as large as an order of magnitude. It may be used to obtain high-purity arbitrary spin current. By comparing the calculation results with and without spin correction, we attribute this spin difference to the spin resonance between transmission electrons and the valence electron of endohedral Au atom.

  1. 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

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  4. 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.

  5. Development of Pd-Ag Compostie Membrane for Separation of Hydrogen at Elevated Temperature

    SciTech Connect

    Shamsuddin Ilias

    2009-02-28

    Pd-based membrane reactor offers the possibility of combining reaction and separation in a single operation at high temperatures to overcome the equilibrium limitations experienced in conventional reactor configurations. In this project to develop a defect-free and hermally-stable Pd-film on microporous stainless steel (MPSS) support for H2-separation and membrane reactor applications, the electroless plating process was revisited with an aim to improve the membrane morphology. Specifically, this study includes; (a) an improvement f activation step using Pulse Laser Deposition (PLD), (b) development of a novel surfactant induced electroless plating (SIEP) for depositing robust Pd-film on microporous support, and (c) application of Pd-membrane as membrane reactor in steam methanol reforming (SMR) reactions.

  6. 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

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

    SciTech Connect

    Poudel, Lekhanath N.; De la cruz, Clarina; Payzant, E. Andrew; Koehler, Michael R.; May, Andrew F.; Garlea, Vasile O.; Taylor, Alice E.; Parker, David S.; Cao, Huibo B.; McGuire, Michael A.; Tian, Wei; Matsuda, Masaaki; Jeen, Hyoung Jeen; Lee, Ho Nyung; Hong, Tao; Calder, Stuart A.; Lumsden, Mark D.; Zhou, Haidong; Keppens, Veerle; Mandrus, D.; Christianson, Andrew D.

    2015-12-15

    The structural and the magnetic properties of CeCu6-xAgx (0 ≤ x ≤ 0.85) and CeCu6-xPdx (0 ≤ x ≤ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu6-xAgx and CeCu6-xPdx as a function of Ag/Pd composition are reported. The end member, CeCu6, undergoes a structural phase transition from an orthorhombic (Pnma) to a monoclinic (P21/c) phase at 240 K. In CeCu6-xAgx, the structural phase transition temperature (Ts) decreases linearly with Ag concentration and extrapolates to zero at xS ≈ 0.1. The structural transition in CeCu6-xPdx remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu6-xAgx and CeCu6-xPdx, exhibit a magnetic quantum critical point (QCP), at x ≈ 0.2 and x ≈ 0.05, respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ1 0 δ2), where δ1 ~ 0.62, δ2 ~ 0.25, x = 0.125 for CeCu6-xPdx and δ1 ~ 0.64, δ2 ~ 0.3, x = 0.3 for CeCu6-xAgx. As a result, the magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.

  8. Multiple adsorption of molecular oxygen on small Au/Pd cationic clusters at finite temperature. A van der Waals density functional study

    NASA Astrophysics Data System (ADS)

    Fernández, Eva María; Balbás, Luis Carlos

    2016-06-01

    The adsorption of molecular oxygen on cationic bimetallic palladium/gold clusters, Au n Pdm + (n + m ≤ 5), is studied by means of self-consistent density functional calculations including long range van der Waals non-local interactions. A single O2 molecule is adsorbed preferably on top of Pd sites for m = 0, 1, but bridge or hollow locations between Pd atoms are preferred for m ≥ 2. In the later cases, both the O2 electronic charge and the O-O distance increase as compared with the values for free O2, leading to negatively charged O2 superoxo species which facilitates the CO oxidation. Multiple sequential adsorption of several O2 is considered for the n + m ≤ 3 clusters, which occurs with decreasing adsorption energy, except when severe distortion of the bimetallic support appears. The Gibbs free energy of Au n Pd2 - n + O 2 x complexes with n = 1-2 and x = 1-5 is computed at temperatures 0 K, 50 K, 150 K, and 300 K. We obtain that Pd 2+ (PdAu+) can adsorb 5 (4) oxygen molecules at ambient temperature; however, Au 2+ can adsorb up to three O2 molecules when the temperature is lower than 150 K.

  9. 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

  10. Selective Oxidation of 1,6-Hexanediol to 6-Hydroxycaproic Acid over Reusable Hydrotalcite-Supported Au-Pd Bimetallic Catalysts.

    PubMed

    Tuteja, Jaya; Nishimura, Shun; Choudhary, Hemant; Ebitani, Kohki

    2015-06-01

    Selective oxidation of 1,6-hexanediol into 6-hydroxycaproic acid was achieved over hydrotalcite-supported Au-Pd bimetallic nanoparticles as heterogeneous catalyst using aqueous H2 O2 . N,N-dimethyldodecylamine N-oxide (DDAO) was used as an efficient capping agent. Spectroscopic analyses by UV/Vis, TEM, XPS, and X-ray absorption spectroscopy suggested that interactions between gold and palladium atoms are responsible for the high activity of the reusable Au40 Pd60 -DDAO/HT catalyst. PMID:25990616

  11. Turning the Halide Switch in the Synthesis of Au-Pd Alloy and Core-Shell Nanoicosahedra with Terraced Shells: Performance in Electrochemical and Plasmon-Enhanced Catalysis.

    PubMed

    Hsu, Shih-Cheng; Chuang, Yu-Chun; Sneed, Brian T; Cullen, David A; Chiu, Te-Wei; Kuo, Chun-Hong

    2016-09-14

    Au-Pd nanocrystals are an intriguing system to study the integrated functions of localized surface plasmon resonance (LSPR) and heterogeneous catalysis. Gold is both durable and can harness incident light energy to enhance the catalytic activity of another metal, such as Pd, via the SPR effect in bimetallic nanocrystals. Despite the superior catalytic performance of icosahedral (IH) nanocrystals compared to alternate morphologies, the controlled synthesis of alloy and core-shell IH is still greatly challenged by the disparate reduction rates of metal precursors and lack of continuous epigrowth on multiply twinned boundaries of such surfaces. Herein, we demonstrate a one-step strategy for the controlled growth of monodisperse Au-Pd alloy and core-shell IH with terraced shells by turning an ionic switch between [Br(-)]/[Cl(-)] in the coreduction process. The core-shell IH nanocrystals contain AuPd alloy cores and ultrathin Pd shells (<2 nm). They not only display more than double the activity of the commercial Pd catalysts in ethanol electrooxidation attributed to monatomic step terraces but also show SPR-enhanced conversion of 4-nitrophenol. This strategy holds promise toward the development of alternate bimetallic IH nanocrystals for electrochemical and plasmon-enhanced catalysis. PMID:27575057

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

  13. One-step Solution Processing of Ag, Au and Pd@MXene Hybrids for SERS.

    PubMed

    Satheeshkumar, Elumalai; Makaryan, Taron; Melikyan, Armen; Minassian, Hayk; Gogotsi, Yury; Yoshimura, Masahiro

    2016-01-01

    We report on one-step hybridization of silver, gold and palladium nanoparticles from solution onto exfoliated two-dimensional (2D) Ti3C2 titanium carbide (MXene) nanosheets. The produced hybrid materials can be used as substrates for surface-enhanced Raman spectroscopy (SERS). An approximate analytical approach is also developed for the calculation of the surface plasmon resonance (SPR) frequency of nanoparticles immersed in a medium, near the interface of two dielectric media with different dielectric constants. We obtained a good match with the experimental data for SPR wavelengths, 440 nm and 558 nm, respectively for silver and gold nanoparticles. In the case of palladium, our calculated SPR wavelength for the planar geometry was 160 nm, demonstrating that non-spherical palladium nanoparticles coupled with 2D MXene yield a broad, significanlty red-shifted SPR band with a peak at 230 nm. We propose a possible mechanism of the plasmonic hybridization of nanoparticles with MXene. The as-prepared noble metal nanoparticles on MXene show a highly sensitive SERS detection of methylene blue (MB) with calculated enhancement factors on the order of 10(5). These findings open a pathway for extending visible-range SERS applications of novel 2D hybrid materials in sensors, catalysis, and biomedical applications. PMID:27557838

  14. One-step Solution Processing of Ag, Au and Pd@MXene Hybrids for SERS

    PubMed Central

    Satheeshkumar, Elumalai; Makaryan, Taron; Melikyan, Armen; Minassian, Hayk; Gogotsi, Yury; Yoshimura, Masahiro

    2016-01-01

    We report on one-step hybridization of silver, gold and palladium nanoparticles from solution onto exfoliated two-dimensional (2D) Ti3C2 titanium carbide (MXene) nanosheets. The produced hybrid materials can be used as substrates for surface-enhanced Raman spectroscopy (SERS). An approximate analytical approach is also developed for the calculation of the surface plasmon resonance (SPR) frequency of nanoparticles immersed in a medium, near the interface of two dielectric media with different dielectric constants. We obtained a good match with the experimental data for SPR wavelengths, 440 nm and 558 nm, respectively for silver and gold nanoparticles. In the case of palladium, our calculated SPR wavelength for the planar geometry was 160 nm, demonstrating that non-spherical palladium nanoparticles coupled with 2D MXene yield a broad, significanlty red-shifted SPR band with a peak at 230 nm. We propose a possible mechanism of the plasmonic hybridization of nanoparticles with MXene. The as-prepared noble metal nanoparticles on MXene show a highly sensitive SERS detection of methylene blue (MB) with calculated enhancement factors on the order of 105. These findings open a pathway for extending visible-range SERS applications of novel 2D hybrid materials in sensors, catalysis, and biomedical applications. PMID:27557838

  15. 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.

  16. Sensitive electrochemical detection of copper ions based on the copper(II) ion assisted etching of Au@Ag nanoparticles.

    PubMed

    Wu, Tianxiang; Xu, Teng; Ma, Zhanfang

    2015-12-01

    A new sensitive electrochemical sensor for the detection of copper ions based on the copper ion assisted etching of Au@Ag nanoparticles was developed in this work. Since copper ions could greatly catalyze the etching process of the silver shell of Au@Ag nanoparticles in the presence of thiosulfate solutions, leading to an obvious decrease of the linear sweep voltammetry (LSV) signals of silver, the concentration of the copper ions, therefore, can be measured. Under the optimized conditions, the electrochemical sensor exhibited excellent sensitivity and selectivity for Cu(2+), with wide linear ranges of 1 nM to 100 μM, and the detection limit of 0.3 nM. In addition, this method was successfully applied for the analysis of Cu(2+) in river water and exhibited good analytical performance. PMID:26501137

  17. 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.

  18. Generation and self-organization of bimetallic Pd/Au nanoparticles on SiO2 by sequential sputtering depositions and annealing processes.

    PubMed

    Ruffino, F; Pecora, E F; Grimaldi, M G

    2012-11-01

    PdAu nanoparticles have been grown on SiO2 by room-temperature sequential sputtering depositions. The nucleation and growth kinetics have been determined crossing atomic force and scanning electron microscopy measurements. From these measurements the mechanisms of the nucleation and growth have been determined. In particular: (1) during the deposition of the first metal (Pd), atoms adsorbed on the substrate are readily trapped on the substrate defects, forming stable nuclei which grow further. During the deposition of the second metal (Au), adsorbed atoms are captured by the clusters formed during the first deposition, before they have time to form a stable nucleus of pure second metal on the surface sites. So, the nucleation is mainly controlled by the Pd and the Au atoms are incorporated essentially by direct impingement of the vapour atoms on the already formed particles. (2) fixing the amount of Pd and Au, during post-deposition thermal treatments, a surface diffusion limited ripening of the NPs occurs. Applying the standard ripening growth theory several parameters characterizing the process were determined, in particular, the growth exponent n and the activation energy E(a). n was found to be dependent on temperature and amount of Au deposited. E(a) was found to linearly increase with the amount of Au deposited. Such a dependence is discussed separating E(a) in two terms: one describing the activation energy for atomic surface diffusion (independent on the amount of Au deposited), the other one describing the activation energy for the film clustering process (dependent on the amount of Au deposited). PMID:23421241

  19. Scanning surface-enhanced Raman spectroscopy (SERS) of chemical agent simulants on templated Au-Ag nanowire substrates

    NASA Astrophysics Data System (ADS)

    Hoffmann, J. A.; Miragliotta, J. A.; Wang, J.; Tyagi, P.; Maddanimath, T.; Gracias, D. H.; Papadakis, S. J.

    2009-05-01

    We report the results of scanning micro-Raman spectroscopy obtained on Au-Ag nanowires for a variety of chemical warfare agent simulants. Rough silver segments embedded in gold nanowires showed enhancement of 105 - 107 and allowed unique identification of 3 of 4 chemical agent simulants tested. These results suggest a promising method for detection of compounds significant for security applications, leading to sensors that are compact and selective.

  20. 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

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. 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

    2014-01-01

    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 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. PMID:25098677

  6. Factors affecting the optical properties of Pd-free Au-Pt-based dental alloys.

    PubMed

    Shiraishi, Takanobu; Takuma, Yasuko; Miura, Eri; Tanaka, Yasuhiro; Hisatsune, Kunihiro

    2003-12-01

    The optical properties of experimental Au-Pt-based alloys containing a small amount of In, Sn, and Zn were investigated by spectrophotometric colorimetry to extract factors affecting color of Au-Pt-based high-karat dental alloys. It was found that the optical properties of Au-Pt-based alloys are strongly affected by the number of valence electrons per atom in an alloy, namely, the electron:atom ratio, e/a. That is, by increasing the e/a-value, activities of reflection in the long-wavelength range and absorption in the short-wavelength range in the visible spectrum apparently increased. As a result, the maximum slope of the spectral reflectance curve at the absorption edge, which is located near 515 nm (approximately 2.4 eV), apparently increased with e/a-value. Due to this effect, the b*-coordinate (yellow-blue) in the CIELAB color space considerably increased and the a*-coordinate (red-green) slightly increased with e/a-value. The addition of a third element with a higher number of valence electrons to the binary Au-Pt alloy is, therefore, effective in giving a gold tinge to the parent Au-Pt alloy. This information may be useful in controlling the color of Au-Pt-based dental alloys. PMID:15348493

  7. Carbon nanotube-supported Au-Pd alloy with cooperative effect of metal nanoparticles and organic ketone/quinone groups as a highly efficient catalyst for aerobic oxidation of amines.

    PubMed

    Deng, Weiping; Chen, Jiashu; Kang, Jincan; Zhang, Qinghong; Wang, Ye

    2016-05-21

    Functionalised carbon nanotube (CNT)-supported Au-Pd alloy nanoparticles were highly efficient catalysts for the aerobic oxidation of amines. We achieved the highest turnover frequencies (>1000 h(-1)) for the oxidative homocoupling of benzylamine and the oxidative dehydrogenation of dibenzylamine. We discovered a cooperative effect between Au-Pd nanoparticles and ketone/quinone groups on CNTs. PMID:27125360

  8. 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)"

  9. Cylindrical posts of Ag/SiO₂/Au multi-segment layer patterns for highly efficient surface enhanced Raman scattering.

    PubMed

    Kim, Kyoung Hwan; Baek, Youn-Kyoung; Jeon, Hwan-Jin; Srinivasarao, Mohan; Jung, Hee-Tae

    2012-08-10

    We fabricated a regular array of Ag/SiO₂/Au multi-segment cylindrical nanopatterns to create a highly efficient surface enhanced Raman scattering (SERS) active substrate using an advanced soft-nanoimprint lithographic technique. The SERS spectra results for Rhodamine 6G (R6G) molecules on the Ag/SiO₂/Au multi-segment nanopatterns show that the highly ordered patterns and interlayer thickness are responsible for enhancing the sensitivity and reproducibility, respectively, The multi-segment nanopattern with a silica interlayer generates significant SERS enhancement (~EF = 1.2 x 10⁶) as compared to that of the bimetallic (Ag/Au) nanopatterns without a dielectric gap (~EF = 1.0 x 10⁴). Further precise control of the interlayer distances between the two metals plays an essential role in enhancing SERS performance for detecting low concentrations of analytes such as fluorescent (Rhodamine 6G) and DNA molecules. Therefore, the highly ordered multi-segment patterns provide great sensitivity and reproducibility of SERS based detection, resulting in a high performance of the SERS substrate. PMID:22802161

  10. 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.

  11. DNA biosensor-based on fluorescence detection of E. coli O157:H7 by Au@Ag nanorods.

    PubMed

    Sun, Jiadi; Ji, Jian; Sun, Yanqing; Abdalhai, Mandour H; Zhang, Yinzhi; Sun, Xiulan

    2015-08-15

    A novel DNA sensor for the detection of the Escherichia coli O157:H7 (E. coli O157:H7) eaeA gene was constructed using surface enhanced fluorescence (SEF). The spacing distance dependence nature of Au@Ag nanorods surface enhanced fluorescence was investigated when the cy3-labled single strand DNA(ssDNA) and the stem-loop DNA probe modified on the nanorods was co-hybridized. The result revealed that the fluorescence intensity reached the maximum value with the spacing distance of about 10nm between cy3 and the Au@Ag nanorods surface. Based on this result, a fluorescence "ON/OFF" switch for detecting the eaeA gene of E. coli O157:H7 was constructed. Under optimal conditions, the DNA sensor produced a linear range from 10(-17) to 10(-11) M with a correlation coefficient of 0.9947 and a detection limit of 3.33×10(-18) M, and was also found to be specific in targeting eaeA. The DNA sensor demonstrated a new strategy of combining eaeA recognition and Au@Ag nanorods for fluorescence signal enhancement, and increased sensitivity in the detection of bacterial specific genes. PMID:25829221

  12. 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.

  13. Surface Plasmons and Optical Properties of TiO2/X(X = Au and Ag) Nanostructure Thin Films

    NASA Astrophysics Data System (ADS)

    Zolanvari, A.; Sadeghi, H.; Norouzi, R.; Ranjgar, A.

    2013-09-01

    TiO2/X(X = Au and Ag) nanolayers are fabricated by depositing TiO2 films using rf magnetron sputtering on thin quartz substrates embedded with Au and Ag nanoparticles. Enhancement of light absorption of the nanostructural layers is observed. These plasmonic and non-plasmonic materials are ordered in geometric arrangements with dimensions that are fractions of the wavelength of light. The light absorption enhancement of synthesized structure in comparison to TiO2 is originated from near-field enhancement caused by the plasmonic effect of metallic nanoparticles, which can be demonstrated by the optical absorption spectra. We show that plasmon modes can exist for the infrared region of the optical spectrum. Also, we analyze the optical properties of the metal-insulator films, in order to clarify the role of metal inclusions in the TiO2 dielectric matrix. Optical band gaps of the nanolayer films are calculated by using Tauc's relation, and the n values of optical band gaps with the variation composition are found from 1.80 to 3.69 eV. Band gap narrowing and absorption in the visible spectral region induced by the incorporation of TiO2/X(X=Au and Ag) nanolayers enable the design of nanostructured thin films to be achieved for photocatalysts and solar energy converters.

  14. 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. PMID:25558009

  15. 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

  16. Associations of Pd, U and Ag in the SiC layer of neutron-irradiated TRISO fuel

    SciTech Connect

    Lillo, Thomas; Rooyen, Isabella Van

    2015-05-01

    Knowledge of the associations and composition of fission products in the neutron irradiated SiC layer of high-temperature gas reactor TRISO fuel is important to the understanding of various aspects of fuel performance that presently are not well understood. Recently, advanced characterization techniques have been used to examine fuel particles from the Idaho National Laboratory’s AGR-1 experiment. Nano-sized Ag and Pd precipitates were previously identified in grain boundaries and triple points in the SiC layer of irradiated TRISO nuclear fuel. Continuation of this initial research is reported in this paper and consists of the characterization of a relatively large number of nano-sized precipitates in three areas of the SiC layer of a single irradiated TRISO nuclear fuel particle using standardless EDS analysis on focused ion beam-prepared transmission electron microscopy samples. Composition and distribution analyses of these precipitates, which were located on grain boundaries, triple junctions and intragranular precipitates, revealed low levels, generally <10 atomic %, of palladium, silver and/or uranium with palladium being the most common element found. Palladium by itself, or associated with either silver or uranium, was found throughout the SiC layer. A small number of precipitates on grain boundaries and triple junctions were found to contain only silver or silver in association with palladium while uranium was always associated with palladium but never found by itself or in association with silver. Intergranular precipitates containing uranium were found to have migrated ~23 μm along a radial direction through the 35 μm thick SiC coating during the AGR-1 experiment while silver-containing intergranular precipitates were found at depths up to ~24 μm in the SiC layer. Also, Pd-rich, nano-precipitates (~10 nm in diameter), without evidence for the presence of either Ag or U, were revealed in intragranular regions throughout the SiC layer. Because not all

  17. Associations of Pd, U and Ag in the SiC layer of neutron-irradiated TRISO fuel

    NASA Astrophysics Data System (ADS)

    Lillo, T. M.; van Rooyen, I. J.

    2015-05-01

    Knowledge of the associations and composition of fission products in the neutron irradiated SiC layer of high-temperature gas reactor TRISO fuel is important to the understanding of various aspects of fuel performance that presently are not well understood. Recently, advanced characterization techniques have been used to examine fuel particles from the Idaho National Laboratory's AGR-1 experiment. Nano-sized Ag and Pd precipitates were previously identified in grain boundaries and triple points in the SiC layer of irradiated TRISO nuclear fuel. Continuation of this initial research is reported in this paper and consists of the characterization of a relatively large number of nano-sized precipitates in three areas of the SiC layer of a single irradiated TRISO nuclear fuel particle using standardless EDS analysis on focused ion beam-prepared transmission electron microscopy samples. Composition and distribution analyses of these precipitates, which were located on grain boundaries, triple junctions and intragranular precipitates, revealed low levels, generally <10 atomic %, of palladium, silver and/or uranium with palladium being the most common element found. Palladium by itself, or associated with either silver or uranium, was found throughout the SiC layer. A small number of precipitates on grain boundaries and triple junctions were found to contain only silver or silver in association with palladium while uranium was always associated with palladium but never found by itself or in association with silver. Intergranular precipitates containing uranium were found to have migrated ∼23 μm along a radial direction through the 35 μm thick SiC coating during the AGR-1 experiment while silver-containing intergranular precipitates were found at depths up to ∼24 μm in the SiC layer. Also, Pd-rich, nano-precipitates (∼10 nm in diameter), without evidence for the presence of either Ag or U, were revealed in intragranular regions throughout the SiC layer. Because not

  18. 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.

  19. The mechanism of N-Ag bonding determined tunability of surface-enhanced Raman scattering of pyridine on MAg (M = Cu, Ag, Au) diatomic clusters.

    PubMed

    Chen, Lei; Gao, Yang; Xu, Haoran; Wang, Zhigang; Li, Zhengqiang; Zhang, Rui-Qin

    2014-10-14

    Binary coinage metal clusters can show a significantly different enhancement in surface-enhanced Raman scattering (SERS) from that of pure element clusters, owing to their tunable surface plasmon resonance energies affected by the composition and atomic ordering. Yet, the tunability by composition requires a deep understanding in order to further optimize the SERS-based detection technique. Here, to fill this deficiency, we conducted detailed analyses of the SERS of pyridine adsorbed through N-Ag bonding on the homonuclear diatomic metal cluster Ag2 and heteronuclear diatomic metal clusters of AuAg and CuAg, as well as the involved charge transfer under an intracluster excitation, based on calculations using time-dependent density functional theory with a short-time approximation for the Raman cross-section. We find that although the SERS enhancements for all complexes can reach the order of 10(3)-10(4), the corresponding wavelengths used for SERS excitation are significantly different. Our molecular orbital analysis reveals that the complexes based on heteronuclear metal clusters can produce varied electronic transitions owing to the polarization between different metal atoms, which tune the SERS enhancements with altered optical properties. Our analyses are expected to provide a theoretical basis for exploring the multi-composition SERS substrates applicable for single molecular detection, nanostructure characterization, and biological molecular identification. PMID:25157565

  20. Lattice distortions in layered type arsenides LnTAs 2 ( Ln=La-Nd, Sm, Gd, Tb; T=Ag, Au): Crystal structures, electronic and magnetic properties

    NASA Astrophysics Data System (ADS)

    Rutzinger, D.; Bartsch, C.; Doerr, M.; Rosner, H.; Neu, V.; Doert, Th.; Ruck, M.

    2010-03-01

    The lanthanide coinage-metal diarsenides LnTAs 2 ( Ln=La, Ce-Nd, Sm; T=Ag, Au) have been reinvestigated and their structures have been refined from single crystal X-ray data. Two different distortion variants of the HfCuSi 2 type are found: PrAgAs 2, NdAgAs 2, SmAgAs 2, GdAgAs 2, TbAgAs 2, NdAuAs 2 and SmAuAs 2 crystallize as twofold superstructures in space group Pmcn with the As atoms of their planar layers forming zigzag chains, whereas LaAgAs 2, CeAgAs 2 and PrAuAs 2 adopt a fourfold superstructure (space group Pmca) with cis-trans chains of As atoms. The respective atomic positions can be derived from the HfCuSi 2 type by group-subgroup relations. The compounds with zigzag chains of As atoms exhibit metallic behaviour while those with cis-trans chains are semiconducting as measured on powder pellets. The majority of the compounds including 4 f elements show antiferromagnetic ordering at TN<20 K.

  1. Semiempirical calculation of radiative constants in the spectra of nickel-like ions Kr IX, Sr XI, Y XII, Ru XVII, Pd XIX, and Ag XX

    NASA Astrophysics Data System (ADS)

    Loginov, A. V.

    2015-03-01

    The probabilities of the electric-dipole transitions 3 d 94 p, 3 d 94 f-3 d 10, 3 d 94 s, and 3 d 94 d in the spectra of nickel-like ions Kr IX, Sr XI, Y XII, Ru XVII, Pd XIX, and Ag XX are calculated semiempirically with the use of published energy levels.

  2. 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

  3. Depressing the hydrogenation and decomposition reaction in H2O2 synthesis by supporting AuPD on oxygen functionalized carbon nanofibers

    DOE PAGESBeta

    Villa, Alberto; Freakley, Simon J.; Schiavoni, Marco; Edwards, Jennifer K.; Hammond, Ceri; Wang, Wu; Wang, Di; Prati, Laura; Dimitratos, Nikolaos; Hutchings, Graham J.; et al

    2015-12-03

    In this work, we show that the introduction of acidic oxygen functionalities to the surface of carbon nanofibers serves to depress the hydrogenation and the decomposition of hydrogen peroxide during the direct synthesis of H2O2. Furthermore, the presence of acidic groups enhances the H2O2 productivity in the case of supported AuPd nanoparticles.

  4. Ultrasensitive electrochemical aptasensor for the detection of thrombin based on dual signal amplification strategy of Au@GS and DNA-CoPd NPs conjugates.

    PubMed

    Wang, Yaoguang; Zhang, Yong; Yan, Tao; Fan, Dawei; Du, Bin; Ma, Hongmin; Wei, Qin

    2016-06-15

    In this work, an ultrasensitive electrochemical aptasensor for the detection of thrombin was developed based on Au nanoparticles decorated graphene sheet (Au@GS) and CoPd binary nanoparticles (CoPd NPs). A sulfydryl-labeled thrombin capture probe (Apt1) and a biotin-labeled thrombin reporter probe (Apt2) were designed to achieve a sandwich-type strategy. Au@GS was used as a sensing platform for the facile immobilization of Apt1 through Au-S bond, forming a sensing interface for thrombin. The specific recognition of thrombin induced the attachment of Apt2-CoPd NPs to the electrode. The labeled CoPd NPs showed good catalytic properties toward the reduction of H2O2, resulting in an amperometric signal. The amperometric response was correlated to the thrombin concentration in sample solutions. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) confirmed the successful fabrication of the aptasensor. A linear response to thrombin in the range of 0.01-2.00 ng mL(-1) with a low detection limit (5 pg mL(-1)) was achieved. The proposed aptasensor showed good selectivity, good reproducibility and acceptable stability. This proposed strategy may find many potential applications in the detection of other biomolecules. PMID:26908183

  5. Selective photocatalytic oxidation of benzene for the synthesis of phenol using engineered Au-Pd alloy nanoparticles supported on titanium dioxide.

    PubMed

    Su, Ren; Kesavan, Lokesh; Jensen, Mads M; Tiruvalam, Ramchandra; He, Qian; Dimitratos, Nikolaos; Wendt, Stefan; Glasius, Marianne; Kiely, Christopher J; Hutchings, Graham J; Besenbacher, Flemming

    2014-10-28

    The selectivity of photocatalytic phenol production from the direct oxidation of benzene can be enhanced by fine adjustment of the morphology and composition of Au-Pd metal nanoparticles supported on titanium dioxide thereby suppressing the decomposition of benzene and evolution of phenolic compounds. PMID:25032752

  6. A sensitive electrochemiluminescence immunosensor based on luminophore capped Pd@Au core-shell nanoparticles as signal tracers and ferrocenyl compounds as signal enhancers.

    PubMed

    Liu, Yuting; Wang, Haijun; Xiong, Chengyi; Yuan, Yali; Chai, Yaqin; Yuan, Ruo

    2016-07-15

    In this work, N-(aminobutyl)-N-(ethylisoluminol) (ABEI), an analogue of luminol, is served as both the reductant and luminescence reagent to synthesize ABEI capped Pd@Au core-shell nanoparticles (ABEI-Pd@AuNPs). The nanoparticles not only exhibit inherent electrochemiluminescence (ECL) property, but also possess advantages of noble-metal nanomaterials such as outstanding electronic property, high specific surface area and good biocompatibility. In order to enhance the luminescence efficiency, ferrocene monocarboxylic acid (Fc) as catalyzer is grafted on the surface of ABEI-Pd@AuNPs with the aid of l-cysteine (l-Cys). When the Fc is electrochemically oxidized to ferricinium cation species (Fc(+)), the decomposition of H2O2 which existed in detection solution can be catalyzed by Fc(+) to generate oxygen-related free radicals, resulting effective signal amplification for ABEI-H2O2 system. For potential applications, the Pd@Au core-shell nanoparticles bifunctionalized by ABEI and catalyzer are employed as nano-carriers to immobilize detection antibody (Ab2). Based on sandwiched immunoreactions, a "signal-on" ECL immunosensor is developed for detection of human collagen type IV (Col IV), a potential biomarker associated with diabetic nephropathy. Consequently, the proposed immunosensor provides a wide linear detection ranging from 1pgmL(-1) to 10ngmL(-1) with a relatively low detection limit of 0.3pgmL(-1) (S/N=3). PMID:26985586

  7. Hydrogen FBG sensor using Pd/Ag film with application in propulsion system fuel tank model of aerospace vehicle

    NASA Astrophysics Data System (ADS)

    Saad, Said; Hassine, Lotfi; Elfahem, Wassim

    2014-09-01

    The high efficiency hydrogen fiber Bragg grating (FBG) sensor is presented. The sensitive film was a new alliance of palladium-silver (Pd-Ag). In addition, the titanium (Ti) layer was used as the adhesive layer. The presented sensor showed the resolution of more than 60 pm/1% H2, and a fast response time of 4 s-5 s was guaranteed in the 0.1% H2-4% H2 range. Moreover, the life time of the sensor was investigated. The obtained results showed that the sensor had an enhanced life time. Furthermore, the sensor was applied in the propulsion system fuel tank model of the aerospace vehicle. The obtained results indicated that it is a prevention system against the disaster aerospace due to hydrogen leakage.

  8. Sensitive electrochemical sensors for simultaneous determination of ascorbic acid, dopamine, and uric acid based on Au@Pd-reduced graphene oxide nanocomposites

    NASA Astrophysics Data System (ADS)

    Jiang, Jingjing; Du, Xuezhong

    2014-09-01

    Sensitive electrochemical sensors were fabricated with reduced graphene oxide-supported Au@Pd (Au@Pd-RGO) nanocomposites by one-step synthesis for individual and simultaneous determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA) with low detection limits and wide concentration ranges. From the Au@Pd-RGO-modified electrodes, well-separated oxidation peaks and enhanced peak currents of AA, DA, and UA were observed owing to the superior conductivity of RGO and the excellent catalytic activity of Au@Pd nanoparticles. For individual detection, the linear responses of AA, DA, and UA were in the concentration ranges of 0.1-1000, 0.01-100, and 0.02-500 μM with detection limits of 0.02, 0.002, and 0.005 μM (S/N = 3), respectively. For simultaneous detection by synchronous change of the concentrations of AA, DA, and UA, the linear response ranges were 1-800, 0.1-100, and 0.1-350 μM with detection limits of 0.28, 0.024, and 0.02 μM (S/N = 3), respectively. The fabricated sensors were further applied to the detection of AA, DA, and UA in urine samples. The Au@Pd-RGO nanocomposites have promising applications in highly sensitive and selective electrochemical sensing.Sensitive electrochemical sensors were fabricated with reduced graphene oxide-supported Au@Pd (Au@Pd-RGO) nanocomposites by one-step synthesis for individual and simultaneous determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA) with low detection limits and wide concentration ranges. From the Au@Pd-RGO-modified electrodes, well-separated oxidation peaks and enhanced peak currents of AA, DA, and UA were observed owing to the superior conductivity of RGO and the excellent catalytic activity of Au@Pd nanoparticles. For individual detection, the linear responses of AA, DA, and UA were in the concentration ranges of 0.1-1000, 0.01-100, and 0.02-500 μM with detection limits of 0.02, 0.002, and 0.005 μM (S/N = 3), respectively. For simultaneous detection by synchronous change of the

  9. A colorimetric nitrite detection system with excellent selectivity and high sensitivity based on Ag@Au nanoparticles.

    PubMed

    Li, Tianhua; Li, Yonglong; Zhang, Yujie; Dong, Chen; Shen, Zheyu; Wu, Aiguo

    2015-02-21

    Excessive uptake of NO2(-) is detrimental to human health, but the currently available methods used to sensitively detect this ion in the environment are cumbersome and expensive. In this study, we developed an improved NO2(-) detection system based on a redox etching strategy of CTAB-stabilized Ag-Au core-shell nanoparticles (Ag@AuNPs). The detection mechanism was verified by UV-Vis spectroscopy, TEM and XPS. The detection system produces a color change from purple to colorless in response to an increase of NO2(-) concentration. The selectivity of detection of NO2(-), both with the unaided eye and by measurement of UV-Vis spectra, is excellent in relation to other ions, including Cu(2+), Co(2+), Ni(2+), Cr(3+), Al(3+), Pb(2+), Cd(2+), Ca(2+), Ba(2+), Zn(2+), Mn(2+), Mg(2+), Fe(3+), Hg(2+), Ag(+), K(+), F(-), PO4(3-), C2O4(2-), SO3(2-), CO3(2-), SO4(2-), NO3(-) and CH3-COO(-) (Ac(-)). The limit of detection (LOD) for NO2(-) is 1.0 μM by eye and 0.1 μM by UV-Vis spectroscopy. The LOD by eye is lower than the lowest previously reported value (4.0 μM). There is a good linear relationship between A/A0 and the concentration of NO2(-) from 1.0 to 20.0 μM NO2(-), which permits a quantitative assay. The applicability of our detection system was also verified by analysis of NO2(-) in tap water and lake water. The results demonstrate that our Ag@AuNP-based detection system can be used for the rapid colorimetric detection of NO2(-) in complex environmental samples, with excellent selectivity and high sensitivity. PMID:25564225

  10. New apparatus for DTA at 2000 bar: thermodynamic studies on Au, Ag, Al and HTSC oxides

    NASA Astrophysics Data System (ADS)

    Garnier, V.; Giannini, E.; Hugi, S.; Seeber, B.; Flükiger, R.

    2004-03-01

    A new differential thermal analysis (DTA) device was designed and installed in a hot isostatic pressure (HIP) furnace in order to perform high-pressure thermodynamic investigations up to 2 kbar and 1200 °C. Thermal analysis can be carried out in inert or oxidizing atmosphere up to p(O2) = 400 bar. The calibration of the DTA apparatus under pressure was successfully performed using the melting temperature (Tm) of pure metals (Au, Ag and Al) as standard calibration references. The thermal properties of these metals have been studied under pressure. The values of DgrV (volume variation between liquid and solid at Tm), rgrsm (density of the solid at Tm) and agrm (linear thermal expansion coefficient at Tm) have been extracted. A very good agreement was found with the existing literature and new data were added. This HIP-DTA apparatus is very useful for studying the thermodynamics of those systems where one or more volatile elements are present, such as high TC superconducting oxides. DTA measurements have been performed on Bi,Pb(2223) tapes up to 2 kbar under reduced oxygen partial pressure (p(O2) = 0.07 bar). The reaction leading to the formation of the 2223 phase was found to occur at higher temperatures when applying pressure: the reaction DTA peak shifted by 49 °C at 2 kbar compared to the reaction at 1 bar. This temperature shift is due to the higher stability of the Pb-rich precursor phases under pressure, as the high isostatic pressure prevents Pb from evaporating.

  11. Sensitive determination of dopamine in the presence of uric acid and ascorbic acid using TiO2 nanotubes modified with Pd, Pt and Au nanoparticles.

    PubMed

    Mahshid, Sara; Li, Chengcheng; Mahshid, Sahar Sadat; Askari, Masoud; Dolati, Abolghasem; Yang, Lixia; Luo, Shenglian; Cai, Qingyun

    2011-06-01

    A simple modified TiO(2) nanotubes electrode was fabricated by electrodeposition of Pd, Pt and Au nanoparticles. The TiO(2) nanotubes electrode was prepared using the anodizing method, followed by modifying Pd nanoparticles onto the tubes surface, offering a uniform conductive surface for electrodeposition of Pt and Au. The performance of the modified electrode was characterized by cyclic voltammetry and differential pulse voltammetry methods. The Au/Pt/Pd/TiO(2) NTs modified electrode represented a high sensitivity towards individual detection of dopamine as well as simultaneous detection of dopamine and uric acid using 0.1 M phosphate buffer solution (pH 7.00) as the base solution. In both case, electro-oxidation peak currents of dopamine were linearly related to accumulated concentration over a wide concentration range of 5.0 × 10(-8) to 3.0 × 10(-5) M. However in the same range of dopamine concentration, the sensitivity had a significant loss at Pt/Pd/TiO(2) NTs electrode, suggesting the necessity for Au nanoparticles in modified electrode. The limit of the detection was determined as 3 × 10(-8) M for dopamine at signal-to-noise ratio equal to 3. Furthermore, the Au/Pt/Pd/TiO(2) NTs modified electrode was able to distinguish the oxidation response of dopamine, uric acid and ascorbic acid in mixture solution of different acidity. It was shown that the modified electrode possessed a very good reproducibility and long-term stability. The method was also successfully applied for determination of DA in human urine samples with satisfactory results. PMID:21494708

  12. 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

  13. 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 a