WorldWideScience

Sample records for metals pd au

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

    DEFF Research Database (Denmark)

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

    2012-01-01

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

  2. Surface noble metal modified PdM/C (M = Ru, Pt, Au) as anode catalysts for direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Mao, Han; Huang, Tao; Yu, Aishui

    2016-01-01

    In this article, we studied the surface noble metal modification on Pd nanoparticles, other than the homogeneous or core-shell structure. The surface modification will lead to the uneven constitution within the nanoparticles and thus more obvious optimization effect toward the catalyst brought by the lattice deformation. The surface of the as-prepared Pd nanoparticles was modified with Ru, Pt or Au by a moderate and green approach, respectively. XPS results confirm the interactive electron effects between Pd and the modified noble metal. Electrochemical measurements show that the surface noble metal modified catalysts not only show higher catalytic activity, but also better stability and durability. The PdM/C catalysts all exhibit good dispersion and very little agglomeration after long-term potential cycles toward ethanol oxidation. With only 10% metallic atomic ratio of Au, PdAu/C catalyst shows extraordinary catalytic activity and stability, the peak current reaches 1700 mA mg"−"1 Pd, about 2.5 times that of Pd/C. Moreover, the PdAu/C maintains 40% of the catalytic activity after 4500 potential cycles. - Highlights: • Pd-based catalysts with complicated exposed facets. • Much enhanced electrocatalytic activity and stability with about 10% noble metal M (M = Ru, Pt, Au) on Pd nanoparticles. • The outstanding electrocatalytic performance of PdAu/C towards ethanol oxidation after the Au modification.

  3. Surface noble metal modified PdM/C (M = Ru, Pt, Au) as anode catalysts for direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Han; Huang, Tao, E-mail: huangt@fudan.edu.cn; Yu, Aishui, E-mail: asyu@fudan.edu.cn

    2016-08-15

    In this article, we studied the surface noble metal modification on Pd nanoparticles, other than the homogeneous or core-shell structure. The surface modification will lead to the uneven constitution within the nanoparticles and thus more obvious optimization effect toward the catalyst brought by the lattice deformation. The surface of the as-prepared Pd nanoparticles was modified with Ru, Pt or Au by a moderate and green approach, respectively. XPS results confirm the interactive electron effects between Pd and the modified noble metal. Electrochemical measurements show that the surface noble metal modified catalysts not only show higher catalytic activity, but also better stability and durability. The PdM/C catalysts all exhibit good dispersion and very little agglomeration after long-term potential cycles toward ethanol oxidation. With only 10% metallic atomic ratio of Au, PdAu/C catalyst shows extraordinary catalytic activity and stability, the peak current reaches 1700 mA mg{sup −1} Pd, about 2.5 times that of Pd/C. Moreover, the PdAu/C maintains 40% of the catalytic activity after 4500 potential cycles. - Highlights: • Pd-based catalysts with complicated exposed facets. • Much enhanced electrocatalytic activity and stability with about 10% noble metal M (M = Ru, Pt, Au) on Pd nanoparticles. • The outstanding electrocatalytic performance of PdAu/C towards ethanol oxidation after the Au modification.

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

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

    DEFF Research Database (Denmark)

    Su, Ren; Tiruvalam, Ramchandra; He, Qian

    2012-01-01

    Noble metal nanoparticles (Au, Pd, AuPd alloys) with a narrow size distribution supported on nanocrystalline TiO2 (M/TiO2) have been synthesized via a sol-immobilization route. The effect of metal identity and size on the photocatalytic performance of M/TiO2 has been systematically investigated u...

  6. Determination of Au, Ir, Os, Pd, Pt, Ru in high-purity metals by neutron activation

    International Nuclear Information System (INIS)

    Samadi, A.A.; Fedoroff, M.

    1978-01-01

    This determination was achieved by thermal neutron activation, chemical separations and radioactivity measurements by γ spectrometry. In order to develop chemical separations, some studies on the distillation and ion exchange of platinum group elements were perfomed. The fixation of these elements on an anion exchange resin in a nitrite medium was studied more particularly. This method enables a fully quantitative fixation. The detection limits in these irradiation conditions ranges from 10 -12 g for Ir to 10 -8 g for Pd [fr

  7. Study of Pd-Au/MWCNTs formic acid electrooxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Mikolajczuk, Anna; Borodzinski, Andrzej; Kedzierzawski, Piotr; Lesiak, Beata [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warszawa (Poland); Stobinski, Leszek [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warszawa (Poland); Faculty of Materials Science and Engineering, Warsaw University of Technology, ul. Woloska 141, 02-507 Warsaw (Poland); Koever, Laszlo; Toth, Jozsef [Institute of Nuclear Research, Hungarian Academy of Sciences (ATOMKI), P. O. Box 51, 4001 Debrecen (Hungary); Lin, Hong-Ming [Department of Materials Engineering, Tatung University, 40, Chungshan N. Rd., 3rd Sec, 104, Taipei (China)

    2010-12-15

    The Pd-Au multiwall carbon nanotubes (MWCNTs) supported catalyst exhibits higher power density in direct formic acid fuel cell (DFAFC) than similar Pd/MWCNTs catalyst. The Pd-Au/MWCNTs catalyst also exhibits higher activity and is more stable in electrooxidation reaction of formic acid during cyclic voltammetry (CV) measurements. After preparation by polyol method, the catalyst was subjected to two type of treatments: (I) annealing at 250 C in 100% of Ar, (II) reducing in 5% of H{sub 2} in Ar atmosphere at 200 C. It was observed that the catalyst after treatment I was completely inactive, whereas after treatment II exhibited high activity. In order to explain this effect the catalysts were characterized by electron spectroscopy methods. The higher initial catalytic activity of Pd-Au/MWCNTs catalyst than Pd/MWCNTs catalyst in reaction of formic acid electrooxidation was attributed to electronic effect of gold in Pd-Au solution, and larger content of small Au nanoparticles of 1 nm size. The catalytic inactivity of Pd-Au/MWCNTs catalysts annealed in argon is attributed to carbon amorphous overlayer covering of Pd oxide shell on the metallic nanoparticles. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

    Science.gov (United States)

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

    2003-03-01

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

  9. Hollow Au@Pd and Au@Pt core-shell nanoparticles as electrocatalysts for ethanol oxidation reactions

    KAUST Repository

    Song, Hyon Min; Anjum, Dalaver H.; Sougrat, Rachid; Hedhili, Mohamed N.; Khashab, Niveen M.

    2012-01-01

    that individual metals may not catalyze. Here, preparation of hollow Au@Pd and Au@Pt core-shell nanoparticles (NPs) and their use as electrocatalysts are reported. Galvanic displacement with Ag NPs is used to obtain hollow NPs, and higher reduction potential of Au

  10. Toward hybrid Au nanorods @ M (Au, Ag, Pd and Pt) core-shell heterostructures for ultrasensitive SERS probes

    Science.gov (United States)

    Xie, Xiaobin; Gao, Guanhui; Kang, Shendong; Lei, Yanhua; Pan, Zhengyin; Shibayama, Tamaki; Cai, Lintao

    2017-06-01

    Being able to precisely control the morphologies of noble metallic nanostructures is of essential significance for promoting the surface-enhanced Raman scattering (SERS) effect. Herein, we demonstrate an overgrowth strategy for synthesizing Au @ M (M = Au, Ag, Pd, Pt) core-shell heterogeneous nanocrystals with an orientated structural evolution and highly improved properties by using Au nanorods as seeds. With the same reaction condition system applied, we obtain four well-designed heterostructures with diverse shapes, including Au concave nanocuboids (Au CNs), Au @ Ag crystalizing face central cube nanopeanuts, Au @ Pd porous nanocuboids and Au @ Pt nanotrepangs. Subsequently, the exact overgrowth mechanism of the above heterostructural building blocks is further analysed via the systematic optimiziation of a series of fabrications. Remarkably, the well-defined Au CNs and Au @ Ag nanopeanuts both exhibit highly promoted SERS activity. We expect to be able to supply a facile strategy for the fabrication of multimetallic heterogeneous nanostructures, exploring the high SERS effect and catalytic activities.

  11. A comprehensive comparative DFT study on adsorption and reactions involved in vinyl acetate synthesis from acetoxylation of ethylene on pure Pd(100) and Pd-Au(100): Elucidating the role of Au

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yanping [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Dong, Xiuqin [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University (China); Zhang, Minhua, E-mail: mhzhangtj@163.com [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China)

    2016-11-30

    Highlights: • Addition of Au into Pd increases the electron density of Pd d-band. • Addition of Au impairs adsorption of species in both Samanos and Moiseev mechanisms. • Addition of Au is kinetically unfavorable for Samonos mechanism. • Addition of Au hinders Moiseev mechanism without considering surface Os and OHs. • Addition of Au facilitates Moiseev mechanism with the effect of surface Os and OHs. - Abstract: Firstly, with DFT, electronic properties of Pd(100) and Pd-Au(100) were examined and it was found that addition of Au into Pd increases the electron density of Pd d-band. Besides, adsorption of relevant species involved in Samanos mechanism and Moiseev mechanism on Pd(100) and Pd-Au(100) was investigated and it was discovered that addition of Au impairs adsorption of species on metal surfaces. Finally, activation energies of all the reactions on Pd(100) and Pd-Au(100) were compared. Our calculations suggested that the rate-limiting step of the Samanos pathway on Pd(100) and Pd-Au(100) is the dehydrogenation of hydrogenated vinyl acetate. The rate-limiting step of the Moiseev pathway on Pd(100) is the coupling of vinyl with acetate, while that on Pd-Au(100) is the dehydrogenation of ethylene. The activation energies that are only involved in the Samanos mechanism become higher on Pd-Au(100) than on pure Pd(100), suggesting that alloying of Au is kinetically unfavorable for Samonos mechanism. Alloying of Au changes the rate-limiting step of Moiseev pathway, and Moiseev mechanism is preferred on Pd-Au(100).

  12. Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

    International Nuclear Information System (INIS)

    Zhou, Juan; Chen, Huan; Chen, Quanyuan; Huang, Zhaolu

    2016-01-01

    Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N 2 adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H 2 chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d 5/2 shifted to higher positions while that of Au 4f 7/2 had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest catalytic activity

  13. Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Juan [School of the Environment, Donghua University, Shanghai 201620 (China); Chen, Huan, E-mail: hchen404@njust.edu.cn [Key Laboratory of Jiangsu Province for Chemical Pollution Control and Resources Reuse, School of Environmental & Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Chen, Quanyuan; Huang, Zhaolu [School of the Environment, Donghua University, Shanghai 201620 (China)

    2016-11-30

    Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N{sub 2} adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H{sub 2} chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d{sub 5/2} shifted to higher positions while that of Au 4f{sub 7/2} had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest

  14. Synthesis of Pd-Au bimetallic nanocrystals via controlled overgrowth.

    Science.gov (United States)

    Lim, Byungkwon; Kobayashi, Hirokazu; Yu, Taekyung; Wang, Jinguo; Kim, Moon J; Li, Zhi-Yuan; Rycenga, Matthew; Xia, Younan

    2010-03-03

    This paper describes the synthesis of Pd-Au bimetallic nanocrystals with controlled morphologies via a one-step seeded-growth method. Two different reducing agents, namely, L-ascorbic acid and citric acid, were utilized for the reduction of HAuCl(4) in an aqueous solution to control the overgrowth of Au on cubic Pd seeds. When L-ascorbic acid was used as the reducing agent, conformal overgrowth of Au on the Pd nanocubes led to the formation of Pd-Au nanocrystals with a core-shell structure. On the contrary, localized overgrowth of Au was observed when citric acid was used as the reducing agent, producing Pd-Au bimetallic dimers. Through this morphological control, we were able to tune the localized surface plasmon resonance peaks of Pd-Au bimetallic nanostructures in the visible region.

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    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...

  16. Hollow Au@Pd and Au@Pt core-shell nanoparticles as electrocatalysts for ethanol oxidation reactions

    KAUST Repository

    Song, Hyon Min

    2012-09-27

    Hybrid alloys among gold, palladium and platinum become a new category of catalysts primarily due to their enhanced catalytic effects. Enhancement means not only their effectiveness, but also their uniqueness as catalysts for the reactions that individual metals may not catalyze. Here, preparation of hollow Au@Pd and Au@Pt core-shell nanoparticles (NPs) and their use as electrocatalysts are reported. Galvanic displacement with Ag NPs is used to obtain hollow NPs, and higher reduction potential of Au compared to Ag, Pd, and Pt helps to produce hollow Au cores first, followed by Pd or Pt shell growth. Continuous and highly crystalline shell growth was observed in Au@Pd core-shell NPs, but the sporadic and porous-like structure was observed in Au@Pt core-shell NPs. Along with hollow core-shell NPs, hollow porous Pt and hollow Au NPs are also prepared from Ag seed NPs. Twin boundaries which are typically observed in large size (>20 nm) Au NPs were not observed in hollow Au NPs. This absence is believed to be due to the role of the hollows, which significantly reduce the strain energy of edges where the two lattice planes meet. In ethanol oxidation reactions in alkaline medium, hollow Au@Pd core-shell NPs show highest current density in forward scan. Hollow Au@Pt core-shell NPs maintain better catalytic activities than metallic Pt, which is thought to be due to the better crystallinity of Pt shells as well as the alloy effect of Au cores. © 2012 The Royal Society of Chemistry.

  17. A Novel Ultraviolet Irradiation Technique for Fabrication of Polyacrylamide-metal (M = Au, Pd) Nanocomposites at Room Temperature

    International Nuclear Information System (INIS)

    Zhou, Y.; Hao, L.Y.; Zhu, Y.R.; Hu, Y.; Chen, Z.Y.

    2001-01-01

    Polyacrylamide (PAM)-metal (M = gold, palladium) nanocomposites with metal nanoparticles homogeneously dispersed in the polymer matrix have been prepared via a novel ultraviolet irradiation technique at room temperature, which is based on the simultaneous occurrence of photo-reduction formation of the colloidal metal particles and photo-polymerization of the acrylamide (AM) monomer. The UV-vis absorption spectra and TEM were employed to characterize the M-PAM nanocomposites by different irradiation times. The average sizes of the colloidal gold and palladium particles dispersed in the nanocomposites were calculated by XRD patterns and TEM images. The present method may be extended to prepare other metal-polymer hybrid nanocomposite materials

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

    International Nuclear Information System (INIS)

    Villa S, G.

    2006-01-01

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

  19. Alloying Au surface with Pd reduces the intrinsic activity in catalyzing CO oxidation

    KAUST Repository

    Qian, Kun; Luo, Liangfeng; Jiang, Zhiquan; Huang, Weixin

    2016-01-01

    were evaluated. The formation of Au-Pd alloy particles was identified. The Au-Pd alloy particles exhibit enhanced dispersions on SiO2 than Au particles. Charge transfer from Pd to Au within Au-Pd alloy particles. Isolated Pd atoms dominate the surface

  20. High-temperature stability of Au/Pd/Cu and Au/Pd(P)/Cu surface finishes

    Science.gov (United States)

    Ho, C. E.; Hsieh, W. Z.; Lee, P. T.; Huang, Y. H.; Kuo, T. T.

    2018-03-01

    Thermal reliability of Au/Pd/Cu and Au/Pd(4-6 wt.% P)/Cu trilayers in the isothermal annealing at 180 °C were investigated by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and transmission electron microscopy (TEM). The pure Pd film possessed a nanocrystalline structure with numerous grain boundaries, thereby facilitating the interdiffusion between Au and Cu. Out-diffusion of Cu through Pd and Au grain boundaries yielded a significant amount of Cu oxides (CuO and Cu2O) over the Au surface and gave rise to void formation in the Cu film. By contrast, the Pd(P) film was amorphous and served as a good diffusion barrier against Cu diffusion. The results of this study indicated that amorphous Pd(P) possessed better oxidation resistance and thermal reliability than crystalline Pd.

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

    Science.gov (United States)

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

  2. Alloying Au surface with Pd reduces the intrinsic activity in catalyzing CO oxidation

    KAUST Repository

    Qian, Kun

    2016-03-30

    © 2016. Various Au-Pd/SiO2 catalysts with a fixed Au loading but different Au:Pd molar ratios were prepared via deposition-precipitation method followed by H2 reduction. The structures were characterized and the catalytic activities in CO oxidation were evaluated. The formation of Au-Pd alloy particles was identified. The Au-Pd alloy particles exhibit enhanced dispersions on SiO2 than Au particles. Charge transfer from Pd to Au within Au-Pd alloy particles. Isolated Pd atoms dominate the surface of Au-Pd alloy particles with large Au:Pd molar ratios while contiguous Pd atoms dominate the surface of Au-Pd alloy particles with small Au:Pd molar ratios. Few synergetic effect of Au-Pd alloy occurs on catalyzing CO oxidation under employed reaction conditions. Alloying Au with Pd reduces the intrinsic activity in catalyzing CO oxidation, and contiguous Pd atoms on the Au-Pd alloy particles are capable of catalyzing CO oxidation while isolated Pd atoms are not. These results advance the fundamental understandings of Au-Pd alloy surfaces in catalyzing CO oxidation.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  4. Hydrogen evolution on Au(111) covered with submonolayers of Pd

    DEFF Research Database (Denmark)

    Björketun, Mårten; Karlberg, Gustav; Rossmeisl, Jan

    2011-01-01

    A theoretical investigation of electrochemical hydrogen evolution on Au(111) covered with submonolayers of Pd is presented. The size and shape of monoatomically high Pd islands formed on the Au(111) surface are determined using Monte Carlo simulations, for Pd coverages varying from 0.02 to 0.95 ML....... The energetics of adsorption and desorption of hydrogen on/from different types of sites on the Pd-Au(111) surface are assessed by means of density functional theory calculations combined with thermodynamic modeling. Based on the density functional and Monte Carlo data, the hydrogen evolution activity...... is evaluated with a micro-kinetic model. The analysis reproduces measured Pd-coverage-dependent activities for Pd submonolayers exceeding similar to 0.15 ML and enables the relative contributions from different types of electrocatalytically active sites to be determined. Finally, the implications of surface...

  5. 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.

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Villa S, G

    2006-07-01

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

  7. Synthesis of Au-Pd Nanoflowers Through Nanocluster Assembly

    Energy Technology Data Exchange (ETDEWEB)

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

    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.

  8. Synthesis and Catalytic Properties of Au Pd Nanoflowers

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Jianguang [Department of Chemistry, Duke University; Wilson, Adria [Duke University; Howe, Jane Y [ORNL; Chi, Miaofang [ORNL; Wiley, Benjamin J [Duke University

    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.

  9. Synthesis and catalytic properties of Au-Pd nanoflowers.

    Science.gov (United States)

    Xu, Jianguang; Wilson, Adria R; Rathmell, Aaron R; Howe, Jane; Chi, Miaofang; Wiley, Benjamin J

    2011-08-23

    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. © 2011 American Chemical Society

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

    Science.gov (United States)

    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.

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    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......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...

  12. Hydrogen adsorption on bimetallic PdAu(111) surface alloys

    DEFF Research Database (Denmark)

    Takehiro, Naoki; Liu, Ping; Bergbreiter, Andreas

    2014-01-01

    The adsorption of hydrogen on structurally well defined PdAu-Pd(111) monolayer surface alloys was investigated in a combined experimental and theoretical study, aiming at a quantitative understanding of the adsorption and desorption properties of individual PdAu nanostructures. Combining...... the structural information obtained by high resolution scanning tunneling microscopy (STM), in particular on the abundance of specific adsorption ensembles at different Pd surface concentrations, with information on the adsorption properties derived from temperature programmed desorption (TPD) spectroscopy...... and high resolution electron energy loss spectroscopy (HREELS) provides conclusions on the minimum ensemble size for dissociative adsorption of hydrogen and on the adsorption energies on different sites active for adsorption. Density functional theory (DFT) based calculations give detailed insight...

  13. Thermal induced structural transformation of bimetallic AuPd nanoparticles

    International Nuclear Information System (INIS)

    Bruma, A; Li, Z Y

    2014-01-01

    High Angle Annular Dark Field Scanning Transmission Electron Microscope (HAADF-STEM) has been employed for the study of thermal effects of structural transformation of AuPd nanoparticles produced by physical vapour deposition. Depending on the duration of annealing at a temperature of 500 K, atomic resolved imaging analysis reveals the formation of various structure morphologies from the ordered L1 2 superlattice to the core-shell structure. The effects of Pd-oxides are also discussed

  14. Manipulating the optical properties of symmetrically branched Au/Pd nanocrystals through interior design.

    Science.gov (United States)

    DeSantis, Christopher J; Skrabalak, Sara E

    2014-05-25

    Au/Pd octopods with hollow, cubic interiors and Oh symmetry were synthesized for the first time by etching core@shell Pd@Au/Pd octopods to selectively remove their Pd interiors. Integration of multiple architectural features - in this case branching symmetry, composition, and interior design - into one nanostructure provides design strategies to new plasmonic colloids.

  15. Synthesis of ultrathin face-centered-cubic Au@Pt and Au@Pd core-shell nanoplates from hexagonal-close-packed Au square sheets

    KAUST Repository

    Fan, Zhanxi; Zhu, Yihan; Huang, Xiao; Han, Yu; Wang, Qingxiao; Liu, Qing; Huang, Ying; Gan, Chee Lip; Zhang, Hua

    2015-01-01

    @Pd rhombic nanoplates, respectively. We believe that these findings will shed new light on the synthesis of novel noble bimetallic nanostructures. Phase change: Ultrathin Au@Pt and Au@Pd core-shell nanoplates were prepared from Au square sheets. A phase

  16. Synthesis of ultrathin face-centered-cubic Au@Pt and Au@Pd core-shell nanoplates from hexagonal-close-packed Au square sheets

    KAUST Repository

    Fan, Zhanxi

    2015-03-17

    The synthesis of ultrathin face-centered-cubic (fcc) Au@Pt rhombic nanoplates is reported through the epitaxial growth of Pt on hexagonal-close-packed (hcp) Au square sheets (AuSSs). The Pt-layer growth results in a hcp-to-fcc phase transformation of the AuSSs under ambient conditions. Interestingly, the obtained fcc Au@Pt rhombic nanoplates demonstrate a unique (101)f orientation with the same atomic arrangement extending from the Au core to the Pt shell. Importantly, this method can be extended to the epitaxial growth of Pd on hcp AuSSs, resulting in the unprecedented formation of fcc Au@Pd rhombic nanoplates with (101)f orientation. Additionally, a small amount of fcc (100)f-oriented Au@Pt and Au@Pd square nanoplates are obtained with the Au@Pt and Au@Pd rhombic nanoplates, respectively. We believe that these findings will shed new light on the synthesis of novel noble bimetallic nanostructures. Phase change: Ultrathin Au@Pt and Au@Pd core-shell nanoplates were prepared from Au square sheets. A phase transformation from hexagonal close-packed (hcp) to face-centered cubic (fcc) is observed upon coating the hcp Au square sheets with Pt or Pd under ambient conditions. The prepared fcc Au@Pt and Au@Pd rhombic nanoplates demonstrate unique (101)f orientation (picture shows a typical fcc Au@Pt rhombic nanoplate). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Efficient Synthesis of MCu (M = Pd, Pt, and Au) Aerogels with Accelerated Gelation Kinetics and their High Electrocatalytic Activity.

    Science.gov (United States)

    Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang; Song, Junhua; Xia, Haibing; Du, Dan; Lin, Yuehe

    2016-10-01

    To accelerate hydrogel formation and further simplify the synthetic procedure, a series of MCu (M = Pd, Pt, and Au) bimetallic aerogels is synthesized from the in situ reduction of metal precursors through enhancement of the gelation kinetics at elevated temperature. Moreover, the resultant PdCu aerogel with ultrathin nanowire networks exhibits excellent electrocatalytic performance toward ethanol oxidation, holding promise in fuel-cell applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Pd-Au/C catalysts with different alloying degrees for ethanol oxidation in alkaline media

    International Nuclear Information System (INIS)

    Qin, Yuan-Hang; Li, Yunfeng; Lv, Ren-Liang; Wang, Tie-Lin; Wang, Wei-Guo; Wang, Cun-Wen

    2014-01-01

    High alloyed Pd-Au/C catalyst is prepared through a rate-limiting strategy in water/ethylene glycol solution. Pd/C and low alloyed Pd-Au/C catalysts are prepared with trisodium citrate and sodium borohydride as stabilizing and reducing agents, respectively. Transmission electron microscopy (TEM) shows that the synthesized Pd(Au) particles are well dispersed on the catalysts. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) show that the high alloyed Pd-Au/C catalyst presents a relatively homogenous structure while the low alloyed Pd-Au/C catalyst presents a Pd-rich shell/Au-rich core structure. Electrochemical characterization shows that the low alloyed Pd-Au/C catalyst exhibits the best catalytic activity for ethanol oxidation reaction (EOR) in alkaline media, which could be attributed to its relatively large exposed Pd surface area as compared with the high alloyed Pd-Au/C catalyst due to its Pd-rich shell structure and its enhanced adsorption of OH ads as compared with Pd/C catalyst due to its core-shell structure

  19. Synthesis and crystal structure of a new Cu3Au-type ternary phase in the Au-In-Pd system: distribution of atoms over crystallographic positions.

    Science.gov (United States)

    Ptashkina, Evgeniya A; Kabanova, Elizaveta G; Tursina, Anna I; Yatsenko, Alexandr V; Kuznetsov, Victor N

    2018-03-01

    A new Cu 3 Au-type ternary phase (τ phase) is found in the AuPd-rich part of the Au-In-Pd system. It has a broad homogeneity range based on extensive (Pd,Au) and (In,Au) replacement, with the composition varying between Au 17.7 In 25.3 Pd 57.0 and Au 50.8 In 16.2 Pd 33.0 . The occupancies of the crystallographic positions were studied by single-crystal X-ray diffraction for three samples of different composition. The sites with m-3m symmetry are occupied by atoms with a smaller scattering power than the atoms located on 4/mmm sites. Two extreme structure models were refined. Within the first, the occupation type changes from (Au,In,Pd) 3 (Pd,In) to (Au,Pd) 3 (In,Pd,Au) with an increase in the Au gross content. For the second model, the occupation type (Au,In,Pd) 3 (Pd,Au) remains essentially unchanged for all Au concentrations. Although the diffraction data do not allow the choice of one of these models, the latter model, where Au substitutes In on 4/mmm sites, seems to be preferable, since it agrees with the fact that the homogeneity range of the τ phase is inclined to the Au corner and provides the same occupation type for all the studied samples of different compositions.

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

    Science.gov (United States)

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

    2016-01-01

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

  1. Ethanol electro-oxidation in an alkaline medium using Pd/C, Au/C and PdAu/C electrocatalysts prepared by electron beam irradiation

    International Nuclear Information System (INIS)

    Geraldes, Adriana Napoleão; Furtunato da Silva, Dionisio; Pino, Eddy Segura; Martins da Silva, Júlio César; Brambilla de Souza, Rodrigo Fernando; Hammer, Peter; Spinacé, Estevam Vitório; Neto, Almir Oliveira; Linardi, Marcelo; Coelho dos Santos, Mauro

    2013-01-01

    Carbon-supported Pd, Au and bimetallic PdAu (Pd:Au 90:10, 50:50 and 30:70 atomic ratios) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their catalytic activities toward ethanol electro-oxidation were evaluated in an alkaline medium using electrochemical techniques, in situ attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR) analysis and a single alkaline direct ethanol fuel cell (ADEFC). EDX analyses showed that the actual Pd:Au atomic ratios were very similar to the nominal ones. X-ray diffractograms of PdAu/C electrocatalysts evidenced the presence of Pd-rich (fcc) and Au-rich (fcc) phases. TEM analysis showed a homogeneous dispersion of nanoparticles on the carbon support, with an average size in the range of 3–5 nm and broad size distributions. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments revealed the superior ambient activity toward ethanol electro-oxidation of PdAu/C electrocatalysts with Pd:Au ratios of 90:10 and 50:50. In situ ATR-FTIR spectroscopy measurements have shown that the mechanism for ethanol electro-oxidation is dependent on catalyst composition, leading to different reaction products, such as acetaldehyde and acetate, depending on the number of electrons transferred. Experiments on a single ADEFC were conducted between 50 and 90 °C, and the best performance of 44 mW cm −2 in 2.0 mol L −1 ethanol was obtained at 85 °C for the Pd:Au 90:10 catalysts. This superior performance is most likely associated with enhancement of ethanol adsorption on Pd, oxidation of the intermediates, the presence of gold oxide-hydroxyl species, low mean particle diameters and better distribution of particles on the support

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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 (H 2 O 2 ) has been designed using 3,3′,5,5′-tetramethyl-benzidine (TMB) as the substrate, which provides a simple and sensitive means to detect H 2 O 2 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. - Highlights: • Carbon-based AuPd bimetallic nanocomposite was synthesized using carbon dots. • The green sequential reduction strategy synthesis method is simple, green, convenient and effective. • The as synthesized AuPd/C NC showed good catalytic activity and peroxidase-like activity. • The AuPd/C NC exhibits noticeably higher catalytic activity in reduction of 4-nitrophenol. • A new colorimetric detection method for hydrogen peroxide based on AuPd/C NC was proposed.

  3. Critical Factors Controlling Pd and Pt Potential in Porphyry Cu–Au Deposits: Evidence from the Balkan Peninsula

    Directory of Open Access Journals (Sweden)

    Demetrios G. Eliopoulos

    2014-03-01

    Full Text Available Porphyry Cu–Au–Pd±Pt deposits are significant Au resources, but their Pd and Pt potential is still unknown. Elevated Pd, Pt (hundreds of ppb and Au contents are associated with typical stockwork magnetite-bornite-chalcopyrite assemblages, at the central parts of certain porphyry deposits. Unexpected high grade Cu–(Pd+Pt (up to 6 ppm mineralization with high Pd/Pt ratios at the Elatsite porphyry deposit, which is found in a spatial association with the Chelopech epithermal deposit (Bulgaria and the Skouries porphyry deposit, may have formed during late stages of an evolved hydrothermal system. Estimated Pd, Pt and Au potential for porphyry deposits is consistent with literature model calculations demonstrating the capacity of aqueous vapor and brine to scavenge sufficient quantities of Pt and Pd, and could contribute to the global platinum-group element (PGE production. Critical requirements controlling potential of porphyry deposits may be from the metals contained in magma (metasomatized asthenospheric mantle wedge as indicated by significant Cr, Co, Ni and Re contents. The Cr content may be an indicator for the mantle input.

  4. Hysteresis-free nanoplasmonic pd-au alloy hydrogen sensors

    DEFF Research Database (Denmark)

    Wadell, Carl; Nugroho, Ferry Anggoro Ardy; Lidström, Emil

    2015-01-01

    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....

  5. Preparation and electric and photoelectric properties of thin deposits of Fe, Co, Ni, Cu, Ag, Au and Pd

    International Nuclear Information System (INIS)

    Heras, J.M.; Albano, E.V.; Asensio, M.C.; Viscido, L.

    1984-01-01

    The physics chemical properties of desordered metallic thin films of Fe, Co, Ni, Pd, Ag, Cu and Au are of great interest for its catalitic activity and for its application in radiation absorption of solar cells and micro electronic devices. This work has the purpose of reporting the experimental results obtained by evaporated films of these metals, which present desordered characteristics, small crystal size and high surface-volume rate. (A.C.A.S.) [pt

  6. Synthesis of AuPd alloyed nanoparticles via room-temperature electron reduction with argon glow discharge as electron source.

    Science.gov (United States)

    Yang, Manman; Wang, Zongyuan; Wang, Wei; Liu, Chang-Jun

    2014-01-01

    Argon glow discharge has been employed as a cheap, environmentally friendly, and convenient electron source for simultaneous reduction of HAuCl4 and PdCl2 on the anodic aluminum oxide (AAO) substrate. The thermal imaging confirms that the synthesis is operated at room temperature. The reduction is conducted with a short time (30 min) under the pressure of approximately 100 Pa. This room-temperature electron reduction operates in a dry way and requires neither hydrogen nor extra heating nor chemical reducing agent. The analyses using X-ray photoelectron spectroscopy (XPS) confirm all the metallic ions have been reduced. The characterization with X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) shows that AuPd alloyed nanoparticles are formed. There also exist some highly dispersed Au and Pd monometallic particles that cannot be detected by XRD and transmission electron microscopy (TEM) because of their small particle sizes. The observed AuPd alloyed nanoparticles are spherical with an average size of 14 nm. No core-shell structure can be observed. The room-temperature electron reduction can be operated in a larger scale. It is an easy way for the synthesis of AuPd alloyed nanoparticles.

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

    Energy Technology Data Exchange (ETDEWEB)

    Shendage, Suresh S., E-mail: sureshsshendage@gmail.com; Singh, Abilash S.; Nagarkar, Jayashree M., E-mail: jm.nagarkar@ictmumbai.edu.in

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Shiraishi, Takanobu [Department of Dental and Biomedical Materials Science, Unit of Basic Medical Sciences, Graduate School of Biomedical Sciences, Nagasaki University, 1-7-1 Sakamoto, Nagasaki 852-8588 (Japan)]. E-mail: siraisi@nagasaki-u.ac.jp; Takuma, Yasuko [Department of Dental and Biomedical Materials Science, Unit of Basic Medical Sciences, Graduate School of Biomedical Sciences, Nagasaki University, 1-7-1 Sakamoto, Nagasaki 852-8588 (Japan); Miura, Eri [Department of Dental and Biomedical Materials Science, Unit of Basic Medical Sciences, Graduate School of Biomedical Sciences, Nagasaki University, 1-7-1 Sakamoto, Nagasaki 852-8588 (Japan); Fujita, Takeshi [Department of Dental and Biomedical Materials Science, Unit of Basic Medical Sciences, Graduate School of Biomedical Sciences, Nagasaki University, 1-7-1 Sakamoto, Nagasaki 852-8588 (Japan); Hisatsune, Kunihiro [Department of Dental and Biomedical Materials Science, Unit of Basic Medical Sciences, Graduate School of Biomedical Sciences, Nagasaki University, 1-7-1 Sakamoto, Nagasaki 852-8588 (Japan)

    2007-06-15

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

  10. Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)-electrodes: Effects of the heteroatomic junction on the reaction paths

    Science.gov (United States)

    Schulte, E.; Belletti, G.; Arce, M.; Quaino, P.

    2018-05-01

    The seek for materials to enhance the oxygen reduction reaction (orr) rate is a highly relevant topic due to its implication in fuel cell devices. Herein, the orr on bimetallic electrocatalysts based on Au-M (M = Pt, Pd) has been studied computationally, by performing density functional theory calculations. Bimetallic (1 0 0) electrode surfaces with two different Au:M ratios were proposed, and two possible pathways, associative and dissociative, were considered for the orr. Changes in the electronic properties of these materials with respect to the pure metals were acknowledged to gain understanding in the overall reactivity trend. The effect of the bimetallic junction on the stability of the intermediates O2 and OOH was also evaluated by means of geometrical and energetic parameters; being the intermediates preferably adsorbed on Pt/Pd atoms, but presenting in some cases higher adsorption energies compared with bare metals. Finally, the kinetics of the Osbnd O bond breaking in O2∗ and OOH∗ adsorbed intermediates in the bimetallic materials and the influence of the Au-M junction were studied by means of the nudge elastic-band method. A barrierless process for the scission of O2∗ was found in Au-M for the higher M ratios. Surprisingly, for Au-M with lower M ratios, the barriers were much lower than for pure Au surfaces, suggesting a highly reactive surface towards the orr. The Osbnd O scission of the OOH∗ was found to be a barrierless process in Ausbnd Pt systems and nearly barrierless in all Ausbnd Pd systems, implying that the reduction ofO2 in these systems proceeds via the full reduction of O2 to H2O , avoiding H2O2 formation.

  11. Precipitation hardening of a Cu-free Au-Ag-Pd-In dental alloy

    Energy Technology Data Exchange (ETDEWEB)

    Seol, Hyo-Joung [Department of Dental Materials, College of Dentistry and Research Institute for Oral Biotechnology, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of); Son, Kuk-Hyeon [Department of Dental Materials, College of Dentistry and Research Institute for Oral Biotechnology, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of); Yu, Chin-Ho [Department of Dental Materials, College of Dentistry and Research Institute for Oral Biotechnology, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of); Kwon, Yong Hoon [Department of Dental Materials, College of Dentistry and Research Institute for Oral Biotechnology, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of); Kim, Hyung-Il [Department of Dental Materials, College of Dentistry and Research Institute for Oral Biotechnology, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of)]. E-mail: hilkim@pusan.ac.kr

    2005-10-27

    The hardening mechanism and related microstructural changes of the Cu-free dental casting alloy composed of Au-Ag-Pd-In was examined by means of hardness test, X-ray diffraction (XRD), scanning electron microscopic (SEM) observations and electron probe microanalysis (EPMA). The Au-Ag-Pd-In alloy showed apparent age-hardenability. In the SEM photograph, three phases were observed in the solution-treated specimen, that is, the Au-Ag based phase with small amounts of In and Pd as matrix, the InPd phase as particle-like structures, and the Pd-rich phase as lamellar precipitates. By aging the specimen, the very fine Pd-rich inter-granular precipitates grew toward the grain interior as lamellar structure, and finally the coarsened Pd-rich precipitates covered a large part of the Au-Ag based matrix. The hardness increase in the early stage of the age-hardening process was assumed to be caused by the diffusion and aggregation of Pd atoms from the Au-Ag based matrix. The hardness decrease in the later stage of age-hardening process was caused by coarsening of the lamellar precipitates composed of the Pd-rich phase.

  12. Precipitation hardening of a Cu-free Au-Ag-Pd-In dental alloy

    International Nuclear Information System (INIS)

    Seol, Hyo-Joung; Son, Kuk-Hyeon; Yu, Chin-Ho; Kwon, Yong Hoon; Kim, Hyung-Il

    2005-01-01

    The hardening mechanism and related microstructural changes of the Cu-free dental casting alloy composed of Au-Ag-Pd-In was examined by means of hardness test, X-ray diffraction (XRD), scanning electron microscopic (SEM) observations and electron probe microanalysis (EPMA). The Au-Ag-Pd-In alloy showed apparent age-hardenability. In the SEM photograph, three phases were observed in the solution-treated specimen, that is, the Au-Ag based phase with small amounts of In and Pd as matrix, the InPd phase as particle-like structures, and the Pd-rich phase as lamellar precipitates. By aging the specimen, the very fine Pd-rich inter-granular precipitates grew toward the grain interior as lamellar structure, and finally the coarsened Pd-rich precipitates covered a large part of the Au-Ag based matrix. The hardness increase in the early stage of the age-hardening process was assumed to be caused by the diffusion and aggregation of Pd atoms from the Au-Ag based matrix. The hardness decrease in the later stage of age-hardening process was caused by coarsening of the lamellar precipitates composed of the Pd-rich phase

  13. [Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents

    International Nuclear Information System (INIS)

    1991-01-01

    Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III)

  14. [Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents

    Energy Technology Data Exchange (ETDEWEB)

    1991-12-31

    Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

  15. (Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents)

    Energy Technology Data Exchange (ETDEWEB)

    1991-01-01

    Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

  16. Catalytic activity of bimetallic AuPd alloys supported MgO and MnO2 nanostructures and their role in selective aerobic oxidation of alcohols

    Directory of Open Access Journals (Sweden)

    Hamed Alshammari

    2017-10-01

    Full Text Available The use of metal oxides as supports for gold and palladium (Au-Pd nano alloys constitutes new horizons to improve catalysts materials for very important reactions. From the literatures, Pd-based bimetallic nanostructures have great properties and active catalytic performance. In this study, nanostructures of magnesium oxide (MgO and manganese dioxide (MnO₂ were synthesised and utilized as supports for Au-Pd nanoparticle catalysts. Gold and palladium were deposited on these supports using sol-immobilisation method. The MgO and MnO2 supported Au-Pd catalysts were evaluated for the oxidation of benzyl alcohol and 1-octanol, respectively. These catalysts were found to be more selective, active and reusable than the corresponding monometallic Au and Pd catalysts. The effect of base supports on the disproportionation reaction during the oxidation process was investigated. The results show that MgO stopped the disproportionation reaction for both aromatic and aliphatic alcohols while MnO₂ stopped it in the case of benzyl alcohol only. The outcomes of this work shed light on the selective aerobic oxidation of alcohols using bimetallic Au-Pd nanoalloys and pave the way to a complete investigation of more basic metal oxides for various aliphatic alcohols.

  17. The Role of Mg(OH)2 in the So-Called "Base-Free" Oxidation of Glycerol with AuPd Catalysts.

    Science.gov (United States)

    Fu, Jile; He, Qian; Miedziak, Peter J; Brett, Gemma L; Huang, Xiaoyang; Pattisson, Samuel; Douthwaite, Mark; Hutchings, Graham J

    2018-02-16

    Mg(OH) 2 - and Mg(OH) 2 -containing materials can provide excellent performance as supports for AuPd nanoparticles for the oxidation of glycerol in the absence of base, which is considered to be a result of additional basic sites on the surface of the support. However, its influence on the reaction solution is not generally discussed. In this paper, we examine the relationship between the basic Mg(OH) 2 support and AuPd nanoparticles in detail using four types of catalyst. For these reactions, the physical interaction between Mg(OH) 2 and AuPd was adjusted. It was found that the activity of the AuPd nanoparticles increased with the amount of Mg(OH) 2 added under base-free conditions, regardless of its interaction with the noble metals. In order to investigate how Mg(OH) 2 affected the glycerol oxidation, detailed information about the performance of AuPd/Mg(OH) 2 , physically mixed (AuPd/C+Mg(OH) 2 ) and (AuPd/C+NaHCO 3 ) was obtained and compared. Furthermore, NaOH and Mg(OH) 2 were added during the reaction using AuPd/C. All these results indicate that the distinctive and outstanding performance of Mg(OH) 2 supported catalysts in base-free condition is in fact directly related to its ability to affect the pH during the reaction and as such, assists with the initial activation of the primary alcohol, which is considered to be the rate determining step in the reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Physical Properties Of Some Pd-Au-Ag Ternary Alloys: A Md Study

    International Nuclear Information System (INIS)

    Aydin, G.

    2010-01-01

    Mechanical properties of palladium (Pd), gold (Au) and silver (Ag) and their ternary alloys in the following concentrations (Au 5 0Ag 2 5Pd 2 5, Au 4 0Ag 2 0Pd 4 0) are studied by using by using molecular dynamics with Quantum Sutton-Chen (Q-SC) potential. Cell constants, densities, enthalpies, elastic constants and heat capacities are investigated. Calculations are performed in the solid phase. Rafii-Tabar combination rules are used and it is showed that these combination rules are valid for ternary alloys also. Additionally, temperature dependence of mechanical properties of alloys are investigated.

  19. Corrosion of Dental Au-Ag-Cu-Pd Alloys in 0.9 % Sodium Chloride Solution

    International Nuclear Information System (INIS)

    Chiba, Atsushi; Kusayanagi, Yukiharu

    2005-01-01

    Two Au-Ag-Cu-Pd dental casting alloys (Au:12% and 20%) used. The test solutions used 0.9 % NaCl solution (isotonic sodium chloride solution), 0.9 % NaCl solution containing 1 % lactic acid, and 0.9 % NaCl solution containing 1 % lactic acid and 0.1 mol dm -3 Na 2 S. The surface of two samples in three sample solutions was not natural discoloration during one year. The alloy containing 12 % gold was easily alloyed and the composition was uniform comparing with the alloy containing 20 % gold. The rest potentials have not a little effect after three months. The kinds of metals could not definitely from the oxidation and reduction waves of metal on the cyclic voltammograms. The dissolutions of gold and palladium were 12 % Au sample in the 0.9 % NaCl solution containing 1 % lactic acid and 0.1 mol dm -3 Na 2 S. The pH of solution had an affect on dissolution of copper, and sulfur ion had an affect on dissolution of silver. The copper dissolved amount from 20 % gold sample was about 26 times comparing with that of 12 % gold sample in the 0.9 % solution containing 1 % lactic acid. Corrosion products were silver chloride and copper chloride in NaCl solution, and silver sulfide and copper sulfide in NaCl solution containing Na 2 S

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

    Science.gov (United States)

    Sutter, Eli A; Sutter, Peter W

    2014-12-03

    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]. 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 zerovalent metal atoms in solution.

  1. Au and Pd nanoparticles supported on CeO{sub 2}, TiO{sub 2}, and Mn{sub 2}O{sub 3} oxides

    Energy Technology Data Exchange (ETDEWEB)

    Nascente, P.A.P., E-mail: nascente@ufscar.br [Federal University of Sao Carlos, Department of Materials Engineering, Sao Carlos, SP (Brazil); Maluf, S.S.; Afonso, C.R.M. [Federal University of Sao Carlos, Department of Materials Engineering, Sao Carlos, SP (Brazil); Landers, R. [State University of Campinas, Institute of Physics, Department of Applied Physics, Campinas, SP (Brazil); Pinheiro, A.N.; Leite, E.R. [Federal University of Sao Carlos, Department of Chemistry, Sao Carlos, SP (Brazil)

    2014-10-01

    Highlights: • CeO{sub 2}, TiO{sub 2}, and Mn{sub 2}O{sub 3} supported Au and Pd nanoparticles. • Additions of 0.5 wt% of Au and Pd onto CeO{sub 2}, TiO{sub 2}, and Mn{sub 2}O{sub 3} supports. • Characterization by XRD, XPS, EDS, TEM, HRTEM, STEM, and EFTEM. - Abstract: Gold and palladium nanoparticles were incorporated on CeO{sub 2}, TiO{sub 2}, and Mn{sub 2}O{sub 3} 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/Mn{sub 2}O{sub 3} due to an overlap with the Mn 3p spectrum. The XPS Au 4f spectra for Au/CeO{sub 2} and Au/TiO{sub 2} present negative chemical shifts that could be attributed to particle-size-related properties. The XPS Pd 3d spectra indicate that for both CeO{sub 2} and TiO{sub 2} substrates, the Pd NPs were in the metallic state, while for the Mn{sub 2}O{sub 3} 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 CeO{sub 2} NPS, formation of Au NPs for the TiO{sub 2} support, and homogeneous distribution of Au clusters for the Mn{sub 2}O{sub 3} support. The addition of Pd yielded a homogeneous dispersion throughout the CeO{sub 2} and TiO{sub 2}, but caused the formation of Pd clusters for the Mn{sub 2}O

  2. Fabrication of Au-Pd Core-shell Nanoparticles using Au Thin-Film Dewetting at High Temperature and Chemical Synthesis Methods

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Min-Gyu; Lee, Hye-Jung; Oh, Yong-Jun [Hanbat National Univ., Daejeon (Korea, Republic of)

    2016-07-15

    Au-Pd bimetallic nanoparticles (NPs) have received a lot of attention in the fields of catalysts and hydrogen sensors. In this study, Au-Pd core-shell NP arrays were successfully fabricated using two steps: formation of the ordered array of Au NPs cores via solid-state dewetting of a Au thin film on a topographic silica substrate, and Pd shell formation via chemical synthesis using two different surfactants (CTAB and CTAC). Using the CTAB surfactant in particular, a 2-D composite structure comprised of an ordered array of Au-Pd NPs, with smaller Pd NPs on the nanoscopic gaps between the Au-Pd NPs, could be formed. This structure is expected to have potential application in resistance-base hydrogen sensors.

  3. Preparation and Characterization of Au/Pd Modified-TiO2 Photocatalysts for Phenol and Toluene Degradation under Visible Light—The Effect of Calcination Temperature

    Directory of Open Access Journals (Sweden)

    Anna Cybula

    2014-01-01

    Full Text Available Rutile loaded with Au/Pd nanoparticles was prepared using a water-in-oil microemulsion system of water/AOT/cyclohexane followed by calcination. The effect of calcination temperature (from 350 to 700°C on the structure of Au/Pd nanoparticles deposited at rutile matrix and the photocatalytic properties of Au/Pd-TiO2 was investigated in two model reactions (toluene degradation in gas phase and phenol degradation in aqueous phase. Toluene was irradiated over Au/Pd-TiO2 using light emitting diodes (LEDs, λmax⁡ = 415 nm. The sample 0.5 mol% Pd/TiO2 exhibited the highest activity under visible light irradiation in gas and aqueous phase reaction among all photocatalysts calcined at 350°C, while the sample modified only with gold nanoparticles showed the lowest activity. The Au/Pd-TiO2 sample calcinated at 350°C possesses the highest photocatalytic activity when degrading phenol under visible light, which is 14 times higher than that of the one calcinated at 450°C. It was observed that increasing temperature from 350 to 700°C during calcination step caused segregation of metals and finally resulted in photoactivity drop.

  4. Equilibrium, kinetics and mechanism of Au3+, Pd2+ and Ag+ ions adsorption from aqueous solutions by graphene oxide functionalized persimmon tannin.

    Science.gov (United States)

    Wang, Zhongmin; Li, Xiaojuan; Liang, Haijun; Ning, Jingliang; Zhou, Zhide; Li, Guiyin

    2017-10-01

    In this study, a novel bio-adsorbent (PT-GO) was prepared by functionalization persimmon tannin (PT) with graphene oxide (GO) and the effective adsorption behaviors of Au 3+ , Pd 2+ and Ag + ions from aqueous solution was investigated. The PT-GO was characterized by Fourier transform infrared spectrometer (FTIR), scanning electronic microscope (SEM), thermogravimetric analysis (TGA) and Zeta potential. Many influence factors such as pH value, bio-adsorbent dosage, initial concentration of metal ions and contact time were optimized. The maximum adsorption capacity for Au 3+ , Pd 2+ and Ag + was 1325.09mg/g, 797.66mg/g and 421.01mg/g, respectively. The equilibrium isotherm for the adsorption of Au 3+ and Ag + on PT-GO were found to obey the Langmuir model, while the Freundlich model fitted better for Pd 2+ . The adsorption process of Au 3+ , Pd 2+ presented relatively fast adsorption kinetics with pseudo-second-order equation as the best fitting model, while the pseudo-first-order kinetic model was suitable for describing the adsorption of Ag + . Combination of ion exchange, electrostatic interaction and physical adsorption was the mechanism for adsorption of Au 3+ , Pd 2+ and Ag + onto PT-GO bio-adsorbent. Therefore, the PT-GO bio-adsorbent would be an ideal adsorbent for removal of precious metal ions and broaden the potential applications of persimmon tannin in environmental research. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Xiu, Fu-Rong, E-mail: xiu_chem@hotmail.com [College of Ecological Environment and Urban Construction, Fujian University of Technology, Fuzhou 350108 (China); Qi, Yingying [College of Ecological Environment and Urban Construction, Fujian University of Technology, Fuzhou 350108 (China); Zhang, Fu-Shen [Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Liuqing [Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081 (China); Liu, Xiaoying [College of Science, Science and Technological Innovation Platform, Hunan Agricultural University, Hunan, Changsha 410128 (China); Lu, Qiujun; Huang, Na [Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081 (China); Liu, Meiling, E-mail: liumeilingww@126.com [Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081 (China); Zhang, Youyu; Yao, Shouzhuo [Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081 (China)

    2016-08-03

    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 (H{sub 2}O{sub 2}) has been designed using 3,3′,5,5′-tetramethyl-benzidine (TMB) as the substrate, which provides a simple and sensitive means to detect H{sub 2}O{sub 2} 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. - Highlights: • Carbon-based AuPd bimetallic nanocomposite was synthesized using carbon dots. • The green sequential reduction strategy synthesis method is simple, green, convenient and effective. • The as synthesized AuPd/C NC showed good catalytic activity and peroxidase-like activity. • The AuPd/C NC exhibits noticeably higher catalytic activity in reduction of 4-nitrophenol. • A new colorimetric detection method for hydrogen peroxide based on AuPd/C NC was proposed.

  8. Direct atomic imaging and density functional theory study of the Au24Pd1 cluster catalyst.

    Science.gov (United States)

    Bruma, A; Negreiros, F R; Xie, S; Tsukuda, T; Johnston, R L; Fortunelli, A; Li, Z Y

    2013-10-21

    In this study we report a direct, atomic-resolution imaging of calcined Au24Pd1 clusters supported on multiwall carbon nanotubes by employing aberration-corrected scanning transmission electron microscopy. Using gold atoms as mass standards, we confirm the cluster size to be 25 ± 2, in agreement with the Au24Pd1(SR)18 precursor used in the synthesis. Concurrently, a Density-Functional/Basin-Hopping computational algorithm is employed to locate the low-energy configurations of free Au24Pd1 cluster. Cage structures surrounding a single core atom are found to be favored, with a slight preference for Pd to occupy the core site. The cluster shows a tendency toward elongated arrangements, consistent with experimental data. The degree of electron transfer from the Pd dopant to Au is quantified through a Löwdin charge analysis, suggesting that Pd may act as an electron promoter to the surrounding Au atoms when they are involved in catalytic reactions.

  9. Behaviour of Au(I,III) cyanides on anion exchangers in the presence of Pd compounds

    International Nuclear Information System (INIS)

    Knothe, M.

    1985-01-01

    The behaviour of low concentrations of [Au(I)(CN) 2 ] - and [Au(III)(CN) 4 ] - in the presence of [Pd(NH 3 ) 4 ](NO 3 ) 2 when adsorbed by anionites has been studied with the aid of labelled Au compounds. The adsorption rate of Au decreased with increasing ageing of the feed solution, which was due to the conversion of gold cyanides into species not capable of being adsorbed. This conversion proceeded at a considerably lower rate when the cyanides of gold had been fixed on the ionite. Au(I) cyanides were always converted at a higher rate than Au(III) cyanides. Thus, an effective separation of Au cyanides by anionites is possible only in the Au(III) system. (author)

  10. Evolution of Ternary AuAgPd Nanoparticles by the Control of Temperature, Thickness, and Tri-Layer

    Directory of Open Access Journals (Sweden)

    Sundar Kunwar

    2017-11-01

    Full Text Available Metallic alloy nanoparticles (NPs possess great potential to enhance the optical, electronic, chemical, and magnetic properties for various applications by the control of morphology and elemental composition. This work presents the fabrication of ternary AuAgPd alloy nanostructures on sapphire (0001 via the solid-state dewetting of sputter-deposited tri-metallic layers. Based on the systematic control of temperature, thickness, and deposition order of tri-layers, the composite AuAgPd alloy nanoparticles (NPs with various shape, size, and density are demonstrated. The metallic tri-layers exhibit various stages of dewetting based on the increasing growth temperatures between 400 and 900 °C at 15 nm tri-layer film thickness. Specifically, the nucleation of tiny voids and hillocks, void coalescence, the growth and isolated nanoparticle formation, and the shape transformation with Ag sublimation are observed. With the reduced film thickness (6 nm, tiny alloy NPs with improved structural uniformity and spatial arrangement are obtained due to enhanced dewetting. The growth trend of alloy NPs is drastically altered by changing the deposition order of metallic tri-layers. The overall evolution is governed by the surface diffusion and inter-mixing of metallic atoms, Rayleigh-like instability, surface and interface energy minimization, and equilibrium state of the system. The UV-VIS-NIR reflectance spectra reveal the formation of an absorption band and reflectance maxima at specific wavelengths based on the morphology and composition of AuAgPd alloy NPs. In addition, Raman spectra analysis shows the modulation of intensity and peak position of natural vibration modes of sapphire (0001.

  11. 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

    KAUST Repository

    Huang, Jianfeng

    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. © 2013 American Chemical Society.

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

    Science.gov (United States)

    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

  13. First-principles investigations of O2 dissociation on low-coordinated Pd ensembles over stepped Au surfaces

    International Nuclear Information System (INIS)

    Yuan, D.W.; Liu, Z.R.; Xu, Y.

    2012-01-01

    The adsorption and dissociation of O 2 on Pd monomer or trimer incorporated into Au(322) and Au(321) surfaces are systematically investigated by first-principles calculations and nudged-elastic-band simulations. We found that the contiguous low-coordinated Pd ensembles alloyed into step edges of Au surfaces are required for O 2 dissociation with an enhanced adsorption energy (∼−1.00 eV). The dissociative barrier of O 2 is mainly related to the size of Pd ensembles, and the activation energy is about 1.00 eV on Pd trimers. However, the Pd monomer is less active for the adsorption and dissociation of O 2 . Additionally, the O spillover from Pd to Au sites only occurs at elevated temperature, and the diffusion processes are highly endothermic. The calculated results indicate that the Pd-modified Au step edge with a contiguous Pd ensemble is the reactive center for supplying atomic oxygen on Pd-doped Au catalysts. -- Highlights: ► Our results reveal the mechanism of O 2 dissociation on Pd-decorated stepped Au surfaces. ► The adsorption energy of O 2 is related to both coordination numbers and geometrical arrangements of Pd atoms alloyed into Au surface. ► The Pd-modified Au step with a contiguous Pd ensemble is the reactive center for O 2 dissociation. ► Our results are important for understanding the catalytic properties of Pd-modified nanoporous gold, especially for those catalytic reactions related to O 2 activation.

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. AuPd Bimetallic Nanocrystals Embedded in Magnetic Halloysite Nanotubes: Facile Synthesis and Catalytic Reduction of Nitroaromatic Compounds

    Directory of Open Access Journals (Sweden)

    Lei Jia

    2017-10-01

    Full Text Available In this research, a facile and effective approach was developed for the preparation of well-designed AuPd alloyed catalysts supported on magnetic halloysite nanotubes (HNTs@Fe3O4@AuPd. The microstructure and the magnetic properties of HNTs@Fe3O4@AuPd were confirmed by transmission electron microscopy (TEM, high resolution TEM (HRTEM, energy-dispersive X-ray spectroscopy (EDS, and vibrating sample magnetometry (VSM analyses. The catalysts, fabricated by a cheap, environmentally friendly, and simple surfactant-free formation process, exhibited high activities during the reduction of 4-nitrophenol and various other nitroaromatic compounds. Moreover, the catalytic activities of the HNTs@Fe3O4@AuPd nanocatalysts were tunable via adjusting the atomic ratio of AuPd during the synthesis. As compared with the monometallic nanocatalysts (HNTs@Fe3O4@Au and HNTs@Fe3O4@Pd, the bimetallic alloyed HNTs@Fe3O4@AuPd nanocatalysts exhibited excellent catalytic activities toward the reduction of 4-nitrophenol (4-NP to 4-aminophenol. Furthermore, the as-obtained HNTs@Fe3O4@AuPd can be recycled several times, while retaining its functionality due to the stability and magnetic separation property.

  16. One-step synthesis of PtPdAu ternary alloy nanoparticles on graphene with superior methanol electrooxidation activity

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Yuzhen; Gu Yonge; Lin Shaoxiong; Wei Jinping; Wang Zaihua [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Wang Chunming, E-mail: wangcm@lzu.edu.cn [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Du Yongling; Ye Weichun [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China)

    2011-10-01

    Highlights: > PtPdAu nanoparticles were synthesized on graphene sheets via chemical reduction method. > The prepared PtPdAu nanoparticles were ternary alloy with fcc structure. > The catalyst exhibited superior catalytic activity and stability for MOR in alkaline. - Abstract: Well-dispersed PtPdAu ternary alloy nanoparticles were synthesized on graphene sheets via a simple one-step chemical reduction method in ethylene glycol (EG) and water system, in which EG served as both reductive and dispersing agent. The electrocatalytic activity of PtPdAu/G was tested by methanol oxidation reaction (MOR). The catalyst was further characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), which indicated that the as-synthesized PtPdAu nanoparticles with alloy structures were successfully dispersed on the graphene sheets. Electrocatalytic properties of the catalyst for MOR in alkaline have been investigated by cyclic voltammetry (CV), chronoamperometry and Tafel curves. The electrocatalytic activity and stability of PtPdAu/G were superior to PtPd/G, PtAu/G and Pt/G. In addition, the anodic peak current on PtPdAu/G catalyst was proportional to the concentration of methanol in the range of 0.05-1.00 M. This study implies that the prepared catalyst have great potential applications in fuel cells.

  17. Geometric, stability, and electronic properties of gold-doped Pd clusters (Pd{sub n}Au, n = 3~20)

    Energy Technology Data Exchange (ETDEWEB)

    Huan, Hao; Chen, Yan; Wang, Tao; Ye, Xiang, E-mail: yexiang@shnu.edu.cn [Shanghai Normal University, Department of Physics (China); Gu, Xiao, E-mail: gx@cqu.edu.cn [Chongqing University, Department of Applied Physics (China)

    2016-11-15

    The structure, stability, and electronic properties of Pd{sub n}Au (n = 3~20) clusters are studied by density functional theory. The results show that the clusters studied here prefer three-dimensional structures even with very small atom number. It is found that the binding energies of Pd{sub n}Au clusters are higher than the corresponding pure Pd{sub n} clusters with the same atom number. Most Pd{sub n}Au clusters studied here are magnetic with magnetic moments ranging from 1.0 to 7.0 μ{sub B.} The dissociation energies of Pd atoms are lower than the doped gold atom, that is the doped Au atom will increase the mother clusters stability and activity.

  18. Controlling the size and morphology of Au@Pd core-shell nanocrystals by manipulating the kinetics of seeded growth.

    Science.gov (United States)

    Li, Jing; Zheng, Yiqun; Zeng, Jie; Xia, Younan

    2012-06-25

    This article reports a systematic study of the seed-mediated growth of Au@Pd core-shell nanocrystals with a variety of controlled sizes and morphologies. The key to the success of this synthesis is to manipulate the reaction kinetics by tuning a set of reaction parameters, including the type and concentration of capping agent, the amount of ascorbic acid used as the reducing agent, and the injection rate used for the precursor solution. Starting from Au nanospheres of 11 nm in diameter as the seeds, Au@Pd core-shell nanocrystals with a number of morphologies, including octahedra, concave octahedra, rectangular bars, cubes, concave cubes, and dendrites, could all be obtained by simply altering the reaction rate. For the first time, it was possible to generate Au@Pd nanocrystals with concave structures on the surfaces while their sizes were kept below 20 nm. In addition, the as-prepared Au@Pd nanocubes can be used as seeds to generate Au@Pd@Au and Au@Pd@Au@Pd nanocrystals with multishelled structures. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Optimised photocatalytic hydrogen production using core–shell AuPd promoters with controlled shell thickness

    DEFF Research Database (Denmark)

    Jones, Wilm; Su, Ren; Wells, Peter

    2014-01-01

    of these materials towards the reforming of alcohols for hydrogen production. The core–shell structured Au–Pd bimetallic nanoparticle supported on TiO2 has being of interest as it exhibited extremely high quantum efficiencies for hydrogen production. However, the effect of shell composition and thickness...... of the nanoparticles by a combination of X-ray absorption fine structure and X-ray photoelectron spectroscopy. Photocatalytic ethanol reforming showed that the core–shell structured Au–Pd promoters supported on TiO2 exhibit enhanced activity compared to that of monometallic Au and Pd as promoters, whilst the core......–shell Au–Pd promoters containing one ML equivalent Pd provide the optimum reactivity....

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

    International Nuclear Information System (INIS)

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

    2005-01-01

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

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

    Science.gov (United States)

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

  2. Water-dispersable hybrid Au-Pd nanoparticles as catalysts in ethanol oxidation, aqueous phase Suzuki-Miyaura and Heck reactions

    KAUST Repository

    Song, Hyon Min; Moosa, Basem; Khashab, Niveen M.

    2012-01-01

    The catalytic activities of water-dispersable Au@Pd core-shell nanoparticles (NPs) and Au-Pd alloy NPs were examined. There is growing interest in Au-Pd hybridized NPs in a supported matrix or non-supported forms as catalysts in various reactions

  3. Ethanol electro-oxidation in alkaline medium using Pd/MWCNT and PdAuSn/MWCNT electrocatalysts prepared by electron beam irradiation

    International Nuclear Information System (INIS)

    Geraldes, Adriana Napoleao; Silva, Dionisio Furtunato da; Andrade e Silva, Leonardo Gondin de; Spinace, Estevam Vitorio; Oliveira Neto, Almir; Santos, Mauro Coelho dos

    2015-01-01

    Environmental problems and the world growing demand for energy has mobilized the scientific community in finding of clean and renewable energy sources. In this context, fuel cells appear as appropriate technology for generating electricity through alcohols electro-oxidation. Multi Wall Carbon Nanotubes (MWCNT)-supported Pd and trimetallic PdAuSn (Pd:Au:Sn 50:10:40 atomic ratio) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by VC, Chronoamperometry, EDX, TEM and XRD. The catalytic activities of electrocatalysts toward ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC) in a range temperature 60 to 90 deg C. The best performances were obtained at 85 deg C: 33 mW.cm -2 and 31 mW.cm -2 for Pd/ MWCNT and PdAuSn/MWCNT electrocatalysts, respectively. X-ray diffractograms of electrocatalysts showed the presence of Pd-rich (fcc) and Au-rich (fcc) phases. Cyclic voltammetry and chronoamperometry experiments showed that PdAuSn/MWCNT electrocatalyst demonstrated similar activity toward ethanol electro-oxidation at room temperature, compared to electrocatalyst Pd/MWCNT. (author)

  4. Ethanol electro-oxidation in alkaline medium using Pd/MWCNT and PdAuSn/MWCNT electrocatalysts prepared by electron beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Geraldes, Adriana Napoleao; Silva, Dionisio Furtunato da; Andrade e Silva, Leonardo Gondin de; Spinace, Estevam Vitorio; Oliveira Neto, Almir, E-mail: drinager@ig.com.br, E-mail: dfsilva@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Santos, Mauro Coelho dos [Universidade Federal do ABC (LEMN/CCNH/UFABC), Santo Andre, SP (Brazil)

    2015-07-01

    Environmental problems and the world growing demand for energy has mobilized the scientific community in finding of clean and renewable energy sources. In this context, fuel cells appear as appropriate technology for generating electricity through alcohols electro-oxidation. Multi Wall Carbon Nanotubes (MWCNT)-supported Pd and trimetallic PdAuSn (Pd:Au:Sn 50:10:40 atomic ratio) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by VC, Chronoamperometry, EDX, TEM and XRD. The catalytic activities of electrocatalysts toward ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC) in a range temperature 60 to 90 deg C. The best performances were obtained at 85 deg C: 33 mW.cm{sup -2} and 31 mW.cm{sup -2} for Pd/ MWCNT and PdAuSn/MWCNT electrocatalysts, respectively. X-ray diffractograms of electrocatalysts showed the presence of Pd-rich (fcc) and Au-rich (fcc) phases. Cyclic voltammetry and chronoamperometry experiments showed that PdAuSn/MWCNT electrocatalyst demonstrated similar activity toward ethanol electro-oxidation at room temperature, compared to electrocatalyst Pd/MWCNT. (author)

  5. Recovery of high-purity metallic Pd from Pd(II)-sorbed biosorbents by incineration.

    Science.gov (United States)

    Won, Sung Wook; Lim, Areum; Yun, Yeoung-Sang

    2013-06-01

    This work reports a direct way to recover metallic palladium with high purity from Pd(II)-sorbed polyethylenimine-modified Corynebacterium glutamicum biosorbent using a combined method of biosorption and incineration. This study is focused on the incineration part which affects the purity of recovered Pd. The incineration temperature and the amount of Pd loaded on the biosorbent were considered as major factors in the incineration process, and their effects were examined. The results showed that both factors significantly affected the enhancement of the recovery efficiency and purity of the recovered Pd. SEM-EDX and XRD analyses were used to confirm that Pd phase existed in the ash. As a result, the recovered Pd was changed from PdO to zero-valent Pd as the incineration temperature was increased from 600 to 900°C. Almost 100% pure metallic Pd was recovered with recovery efficiency above 99.0% under the conditions of 900°C and 136.9 mg/g. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Au-Pt-Pd-U mineralization in the Coronation Hill-El Sherana region, NT

    International Nuclear Information System (INIS)

    Wyborn, L.

    1992-01-01

    In 1990 BMR's Minerals and Land Use program conducted an geochemical and geophysical survey to provide the best possible basis for estimating the resource potential of the Kakadu Conservation Zone. Combining the old and new data, an integrated model for the deposit types has been developed. Although differing in metal content, all mines and prospects of the Coronation Hill region share similar timing and structural controls, suggesting that they are related to one geochemical system. The presence or absence of U in the Au-Pt-Pd mineralisation appears related to geological differences, primarily in host-rock composition. U-bearing deposits are hosted mainly in carbonaceous shales, although some U is associated with chloritic zones. Deposits lacking U, best developed at Coronation Hill, occur in a broad range of host rocks, including quartz-feldspar porphyry, green tuffaceous shale, diorite, dolomite, and sedimentary breccias. Although seemingly diverse rock types, the common components of these U-poor host units are feldspar and/or carbonate. 1 tab., 3 figs

  7. The solubility of Pd and Au in hydrous intermediate silicate melts: The effect of oxygen fugacity and the addition of Cl and S

    Science.gov (United States)

    Sullivan, Neal A.; Zajacz, Zoltan; Brenan, James M.

    2018-06-01

    The solubilities of Pd and Au in a hydrous trachyandesitic melt were experimentally determined at 1000 °C and 200 MPa at oxygen fugacity (ƒO2) from 0.45 log units below to 6.55 log units above the Ni-NiO buffer (NNO). The effect of adding metal-binding ligands (i.e. Cl and S) to the silicate melt was also studied. The solubility of Au increases from 0.15 ± 0.1 to 3.85 ± 1.48 ppm in Cl- and S-free melts with ƒO2 increasing from NNO-0.45 to NNO+6.55 with a slope that suggests that it is present in 1+ oxidation state over the entire studied ƒO2 range. On the other hand, Pd solubility, shows a more moderate increase with ƒO2, especially in the lower half of the studied range, increasing from 2.66 ± 0.25 ppm at NNO-0.45 to only 3.62 ± 0.38 ppm at NNO+1.72 in Cl- and S-free melts. Overall, the variation in Pd solubility as a function of ƒO2 indicates Pd being dissolved in the silicate melt in both zero and 1+ oxidation state, with the former being dominant below NNO+4.5. At NNO-0.45 to +3.48, the addition of 3170-4060 ppm Cl to the silicate melt increased the solubility of Au by an average factor of 1.5, in comparison to Cl-free melts. However, at NNO+6.55, Au solubility increased by a factor of 2.5. The addition of Cl had a negligible effect on the solubility of Pd except for a large increase (factor of 2.4) at NNO+6.55. At reducing conditions (NNO-0.45), the addition of 170 ppm S to the silicate melt increased the solubility of Au by a factor of ∼4 but did not change the solubility of Pd in comparison to S-free melts. The observation that Pd is dominantly present as Pd0 at NNO one may expect similar behavior in fluids degassing from magmas at depth, the lack of oxidized Pd species could be an important factor behind the scarcity of economically viable Pd-rich magmatic-hydrothermal deposits observed in nature.

  8. Photoinduced Glycerol Oxidation over Plasmonic Au and AuM (M = Pt, Pd and Bi) Nanoparticle-Decorated TiO2 Photocatalysts

    Science.gov (United States)

    Jedsukontorn, Trin; Saito, Nagahiro; Hunsom, Mali

    2018-01-01

    In this study, sol-immobilization was used to prepare gold nanoparticle (Au NP)-decorated titanium dioxide (TiO2) photocatalysts at different Au weight % (wt. %) loading (Aux/TiO2, where x is the Au wt. %) and Au–M NP-decorated TiO2 photocatalysts (Au3M3/TiO2), where M is bismuth (Bi), platinum (Pt) or palladium (Pd) at 3 wt. %. The Aux/TiO2 photocatalysts exhibited a stronger visible light absorption than the parent TiO2 due to the localized surface plasmon resonance effect. Increasing the Au content from 1 wt. % to 7 wt. % led to increased visible light absorption due to the increasing presence of defective structures that were capable of enhancing the photocatalytic activity of the as-prepared catalyst. The addition of Pt and Pd coupled with the Au3/TiO2 to form Au3M3/TiO2 improved the photocatalytic activity of the Au3/TiO2 photocatalyst by maximizing their light-absorption property. The Au3/TiO2, Au3Pt3/TiO2 and Au3Pd3/TiO2 photocatalysts promoted the formation of glyceraldehyde from glycerol as the principle product, while Au3Bi3/TiO2 facilitated glycolaldehyde formation as the major product. Among all the prepared photocatalysts, Au3Pd3/TiO2 exhibited the highest photocatalytic activity with a 98.75% glycerol conversion at 24 h of reaction time. PMID:29690645

  9. Comparative Study on The Photocatalytic Hydrogen Production from Methanol over Cu-, Pd-, Co- and Au-Loaded TiO2

    Directory of Open Access Journals (Sweden)

    Udani P.P.C.

    2015-09-01

    Full Text Available Photocatalytic hydrogen production from a methanol-water solution was investigated in a semi-continuous reactor over different metal-loaded TiO2 catalysts under UltraViolet (UV light irradiation. The catalysts were mainly prepared by the incipient wetness impregnation method by varying the metal weight ratio in the range of 1-10 wt%. The effects of metal loading and H2 pre-treatment on the photocatalytic activity were investigated. In addition, the activity of the catalysts was also compared with a reference Au-TiO2 catalyst from the World Gold Council (WGC. The photocatalysts were characterized by using X-Ray Diffraction (XRD and N2 physisorption before and after the activity measurements. The photocatalytic activity decreased in the order of Pd > Au > Cu > Co in the comparative study of Cu-TiO2, Co-TiO2, Au-TiO2 and Pd-TiO2. Optimum hydrogen evolution was achieved with 5 wt% Pd-TiO2 and 5 wt% Cu-TiO2.

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

    OpenAIRE

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

    2014-01-01

    Anisotropic Au nanoparticles show unique localized surface plasmon resonance (LSPR) properties, which make it 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 observation and spectral monitoring, we found that the layered...

  11. Centrifugal Deposited Au-Pd Core-Shell Nanoparticle Film for Room-Temperature Optical Detection of Hydrogen Gas.

    Science.gov (United States)

    Song, Han; Luo, Zhijie; Liu, Mingyao; Zhang, Gang; Peng, Wang; Wang, Boyi; Zhu, Yong

    2018-05-06

    In the present work, centrifugal deposited Au-Pd core-shell nanoparticle (NP) film was proposed for the room-temperature optical detection of hydrogen gas. The size dimension of 44, 48, 54, and 62 nm Au-Pd core-shell nanocubes with 40 nm Au core were synthesized following a solution-based seed-mediated growth method. Compared to a pure Pd NP, this core-shell structure with an inert Au core could decrease the H diffusion length in the Pd shell. Through a modified centrifugal deposition process, continues film samples with different core-shell NPs were deposited on 10 mm diameter quartz substrates. Under various hydrogen concentration conditions, the optical response properties of these samples were characterized by an intensity-based optical fiber bundle sensor. Experimental results show that the continues film that was composed of 62 nm Au-Pd core-shell NPs has achieved a stable and repeatable reflectance response with low zero drift in the range of 4 to 0.1% hydrogen after a stress relaxation mechanism at first few loading/unloading cycles. Because of the short H diffusion length due to the thinner Pd shell, the film sample composed of 44 nm Au-Pd NPs has achieved a dramatically decreased response/recovery time to 4 s/30 s. The experiments present the promising prospect of this simple method to fabricate optical hydrogen sensors with controllable high sensitivity and response rate at low cost.

  12. Optimal level of Au nanoparticles on Pd nanostructures providing remarkable electro-catalysis in direct ethanol fuel cell

    Science.gov (United States)

    Dutta, Abhijit; Mondal, Achintya; Broekmann, Peter; Datta, Jayati

    2017-09-01

    The designing and fabrication of economically viable electro-catalysts for ethanol oxidation reaction (EOR) in direct ethanol fuel cell (DEFC) has been one of the challenging issues over the decades. The present work deals with controlled synthesis of Pd coupled Au nano structure, as the non Pt group of catalysts for DEFC. The catalytic proficiency of bimetallic NPs (2-10 nm) are found to be strongly dependent on the Pd:Au ratio. The over voltage of EOR is considerably reduced by ∼260 mV with 33% of Au content in PdAu composition compared to Pd alone, demonstrating the beneficial role of Au and/or its surface oxides providing oxygen species at much lower potentials compared to Pd. The catalysts are further subjected to electrochemical analysis through voltammetry along with the temperature study on activation parameters. The quantitative determination of EOR products during the electrolysis is carried out by ion chromatographic analysis; vis-a-vis the coulombic efficiency of the product yield were derived from each of the compositions. Furthermore, a strong correlation among catalytic performances and bimetallic composition is established by screening the catalysts in an in-house fabricated direct ethanol anion exchange membrane fuel cell, DE(AEM)FC. The performance testing demonstrates outstanding increase of peak power density (∼40 mWcm-2, 93%) for the best accomplishment Au (33%) covered Pd (67%) catalyst in comparison with the monometallic Pd.

  13. Architecture of Pd-Au bimetallic nanoparticles in sodium bis(2-ethylhexyl)sulfosuccinate reverse micelles as investigated by X-ray absorption spectroscopy.

    Science.gov (United States)

    Chen, Ching-Hsiang; Sarma, Loka Subramanyam; Chen, Jium-Ming; Shih, Shou-Chu; Wang, Guo-Rung; Liu, Din-Goa; Tang, Mau-Tsu; Lee, Jyh-Fu; Hwang, Bing-Joe

    2007-09-01

    In this study, we demonstrate the unique application of X-ray absorption spectroscopy (XAS) as a fundamental characterization tool to help in designing and controlling the architecture of Pd-Au bimetallic nanoparticles within a water-in-oil microemulsion system of water/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/n-heptane. Structural insights obtained from the in situ XAS measurements recorded at each step during the formation process revealed that Pd-Au bimetallic clusters with various Pd-Au atomic stackings are formed by properly performing hydrazine reduction and redox transmetalation reactions sequentially within water-in-oil microemulsions. A structural model is provided to explain reasonably each reaction step and to give detailed insight into the nucleation and growth mechanism of Pd-Au bimetallic clusters. The combination of in situ XAS analysis at both the Pd K-edge and the Au L(III)-edge and UV-vis absorption spectral features confirms that the formation of Pd-Au bimetallic clusters follows a (Pd(nuclei)-Au(stack))-Pd(surf) stacking. This result further implies that the thickness of Au(stack) and Pd(surf) layers may be modulated by varying the dosage of the Au precursor and hydrazine, respectively. In addition, a bimetallic (Pd-Au)(alloy) nanocluster with a (Pd(nuclei)-Au(stack))-(Pd-Au(alloy))(surf) stacking was also designed and synthesized in order to check the feasibility of Pd(surf) layer modification. The result reveals that the Pd(surf) layer of the stacked (Pd(nuclei)-Au)(stack) bimetallic clusters can be successfully modified to form a (Au-Pd alloy)(surf) layer by a co-reduction of Pd and Au ions by hydrazine. Further, we demonstrate the alloying extent or atomic distribution of Pd and Au in Pd-Au bimetallic nanoparticles from the derived XAS structural parameters. The complete XAS-based methodology, demonstrated here on the Pd-Au bimetallic system, can easily be extended to design and control the alloying extent or atomic distribution, atomic

  14. X-ray fluorescence determination of Au, Pd and Pt from chloride solutions after preconcentration on cellulose filters

    International Nuclear Information System (INIS)

    Gordeeva, V.P.; Glazkova, S.V.; Tsysin, G.I.; Ivanov, V.M.; Zolotov, Yu. A.

    2003-01-01

    The aim of this work was synthesis of new sorption cellulose filters for dynamic preconcentration of Au, Pd and Pt from chloride solutions and subsequent XRF determination of these elements on the filters. New filters were prepared by impregnation of a filter paper with solution of tri-n-octylamine and paraffin in hexane (TOA-filters). The effect of paraffin and TOA concentration in hexane on a content of nitrogen in a filter was studied. It was found that Au(III), Pd(II) and Pt(IV) were quantitatively recovered on the TOA-filters (filtering surface diameter of 23 mm, thickness of 0.15 mm) from 0.5 - 1 M HCl at a flow rates of 2-5 ml min-1 from 10-100 ml of solution. The mathematical model of sorption dynamics was offered for the estimation of potential possibilities of new impregnated sorbents and for the evaluation of optimum dynamic conditions allowing to achieve of maximum concentration efficiency (CE max ). The elements were determined directly on the filters by XRF spectrometer. Palladium was also determined on the TOA-filters after formation of coloured compounds of metal with 4-(2-pyridylazo)resorcinol (PAR) by diffuse reflectance spectroscopy with the calculation of calorimetric characteristics and using test-scale. (authors)

  15. Successful synthesis and thermal stability of immiscible metal Au-Rh, Au-Ir andAu-Ir-Rh nanoalloys

    Science.gov (United States)

    Shubin, Yury; Plyusnin, Pavel; Sharafutdinov, Marat; Makotchenko, Evgenia; Korenev, Sergey

    2017-05-01

    We successfully prepared face-centred cubic nanoalloys in systems of Au-Ir, Au-Rh and Au-Ir-Rh, with large bulk miscibility gaps, in one-run reactions under thermal decomposition of specially synthesised single-source precursors, namely, [AuEn2][Ir(NO2)6], [AuEn2][Ir(NO2)6] х [Rh(NO2)6]1-х and [AuEn2][Rh(NO2)6]. The precursors employed contain all desired metals ‘mixed’ at the atomic level, thus providing significant advantages for obtaining alloys. The observations using high-resolution transmission electron microscopy show that the nanoalloy structures are composed of well-dispersed aggregates of crystalline domains with a mean size of 5 ± 3 nm. Еnergy dispersive x-ray spectroscopy and x-ray powder diffraction (XRD) measurements confirm the formation of AuIr, AuRh, AuIr0.75Rh0.25, AuIr0.50Rh0.50 and AuIr0.25Rh0.75 metastable solid solutions. In situ high-temperature synchrotron XRD (HTXRD) was used to study the formation mechanism of nanoalloys. The observed transformations are described by the ‘conversion chemistry’ mechanism characterised by the primary development of particles comprising atoms of only one type, followed by a chemical reaction resulting in the final formation of a nanoalloy. The obtained metastable nanoalloys exhibit essential thermal stability. Exposure to 180 °C for 30 h does not cause any dealloying process.

  16. Shape-controlled synthesis of Au@Pd core-shell nanoparticles and their corresponding electrochemical properties

    KAUST Repository

    Song, Hyon Min; Anjum, Dalaver H.; Khashab, Niveen M.

    2012-01-01

    The shape-controlled synthesis of Au@Pd core-shell nanoparticles (NPs) was successfully achieved through the emulsion phase generated during the phase transfer from organic to aqueous medium. Contrary to conventional epitaxial growth for obtaining

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

    Science.gov (United States)

    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. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Synthesis and characterization of Pd@M(x)Cu(1-x) (M = Au, Pd, and Pt) nanocages with porous walls and a yolk-shell structure through galvanic replacement reactions.

    Science.gov (United States)

    Xie, Shuifen; Jin, Mingshang; Tao, Jing; Wang, Yucai; Xie, Zhaoxiong; Zhu, Yimei; Xia, Younan

    2012-11-19

    This paper describes the synthesis of Pd@M(x)Cu(1-x) (M = Au, Pd, and Pt) nanocages with a yolk-shell structure through galvanic replacement reactions that involve Pd@Cu core-shell nanocubes as sacrificial templates and ethylene glycol as the solvent. Compared with the most commonly used templates based on Ag, Cu offers a much lower reduction potential (0.34 versus 0.80 V), making the galvanic reaction more easily to conduct, even at room temperature. Our structural and compositional characterizations indicated that the products were hollow inside, and each one of them contained porous M-Cu alloy walls and a Pd cube in the interior. For the Pd@Au(x)Cu(1-x) yolk-shell nanocages, they displayed broad extinction peaks extending from the visible to the near-IR region. Our mechanistic study revealed that the dissolution of the Cu shell preferred to start from the slightly truncated corners and then progressed toward the interior, because the Cu {100} side faces were protected by a surface capping layer of hexadecylamine. This galvanic approach can also be extended to generating other hollow metal nanostructures by using different combinations of Cu nanostructures and salt precursors. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Haijun, E-mail: zhanghaijun@wust.edu.cn [College of Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan, Hubei Province 430081 (China); State Key Laboratory Breeding Base of Refractories and Ceramics, Wuhan University of Science and Technology, Wuhan 430081 (China); Lu, Lilin [College of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081 (China); Cao, Yingnan; Du, Shuang [College of Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan, Hubei Province 430081 (China); State Key Laboratory Breeding Base of Refractories and Ceramics, Wuhan University of Science and Technology, Wuhan 430081 (China); Cheng, Zhong [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Zhang, Shaowei [State Key Laboratory Breeding Base of Refractories and Ceramics, Wuhan University of Science and Technology, Wuhan 430081 (China)

    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.

  20. Fabrication of catalytically active Au/Pt/Pd trimetallic nanoparticles by rapid injection of NaBH4

    International Nuclear Information System (INIS)

    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 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

  1. Brazing of Cu with Pd-based metallic glass filler

    Energy Technology Data Exchange (ETDEWEB)

    Terajima, Takeshi [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan)], E-mail: terajima@jwri.osaka-u.ac.jp; Nakata, Kazuhiro [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Matsumoto, Yuji [Materials and Structures Laboratory, Tokyo Institute of Technology (Japan); Zhang, Wei; Kimura, Hisamichi; Inoue, Akihisa [Institute for Materials Research, Tohoku University (Japan)

    2008-02-25

    Metallic glass has several unique properties, including high mechanical strength, small solidification shrinkage, small elastic modulus and supercooling state, all of which are well suited as a residual stress buffer for metal and ceramic joining. In the present preliminary study, we demonstrated brazing of Cu rods with Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} metallic glass filler. The brazing was carried out at 873 K for 1 min in a vacuum atmosphere (1 x 10{sup -3} Pa), and then the specimens were quenched at the rate of 30 K/s by blowing He. The metallic glass brazing of Cu using Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler was successful, with the exception that several voids remained in the filler. According to micro-focused X-ray diffraction, no diffraction patterns were observed at both the center of the Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler and the Cu/Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} interface. The result showed that the Cu specimens were joined with Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler in the glassy state. The tensile fracture strength of the brazed specimens ranged from 20 to 250 MPa. The crack extension from the voids in the Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler may have caused the results to be uneven and very low compared to the strength of Pd-based bulk metallic glass.

  2. Synthesis and characterization of Pd-on-Pt and Au-on-Pt bimetallic nanosheaths on multiwalled carbon nanotubes

    International Nuclear Information System (INIS)

    Wang Shuangyin; Jiang, San Ping; Wang Xin

    2011-01-01

    The authors have successfully synthesized Pd-on-Pt (thickness: 12 nm) and Au-on-Pt bimetallic nanosheaths on multiwalled carbon nanotubes (MWCNTs) via a seed-mediated growth approach. Pt nanoparticles as seeds were pre-deposited on MWCNTs with uniform distribution followed by the successive seed-mediated growth of metal atoms reduced by a weak reducing agent, ascorbic acid. The essential role of pre-deposited nanoseed particles on MWCNTs was demonstrated. The as-prepared materials were characterization by transition electron microscopy, energy-dispersive X-ray spectroscopy, and element mapping tools. The current strategy extends the classical seed-mediated growth method to prepare bimetallic nanosheath on MWCNT support.

  3. Age-hardening and related phase transformation in an experimental Ag-Cu-Pd-Au alloy

    International Nuclear Information System (INIS)

    Seol, Hyo-Joung; Lee, Doung-Hun; Lee, Hee-Kyung; Takada, Yukyo; Okuno, Osamu; Kwon, Yong Hoon; Kim, Hyung-Il

    2006-01-01

    The age-hardening behaviour, phase transformation and related microstructural changes of an experimental Ag-Cu-Pd-Au alloy were examined by means of hardness test, X-ray diffraction (XRD), scanning electron microscopic (SEM) observations and electron probe microanalysis (EPMA). The specimen alloy showed apparent age-hardenability at the aging temperatures of 350 deg. C and 400 deg. C. By aging the solution-treated specimen at 400 deg. C, two phases of the Ag-rich α 1 phase and the Pd-containing Cu-rich α 2 phase were transformed into four phases of the Ag-rich α 1 ' phase, the Cu-rich α 2 ' phase, the CsCl-type CuPd phase and the AuCu(I) ordered phase. Microstructure of the solution-treated specimen consisted of the Ag-rich α 1 matrix, Cu-rich α 2 particle-like structures of various sizes and the lamellar structure of the α 1 and α 2 phases. When the peak hardness was obtained, the very fine lamellar structure consisting of the Ag-rich α 1 ' and Cu-rich α 2 ' phases was newly formed in the matrix. By further aging, the very fine lamellar structure grew and coarsened apparently, and the matrix was covered with the coarsened lamellar structure. The hardness increase was considered to be caused mainly by the diffusion and precipitation of Cu from the Ag-rich α 1 matrix, and the hardness decrease in the latter stage of age-hardening process was caused by the coarsening of the very fine lamellar structure. The CsCl-type CuPd phase and the AuCu(I) ordered phase did not contribute to the hardness increase

  4. Age-hardening and related phase transformation in an experimental Ag-Cu-Pd-Au alloy

    Energy Technology Data Exchange (ETDEWEB)

    Seol, Hyo-Joung [Department of Dental Materials, College of Dentistry, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of); Lee, Doung-Hun [Department of Dental Materials, College of Dentistry, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of); Lee, Hee-Kyung [Department of Dental Technology, Daegu Health College, San 7 Taejeon-dong, Buk-gu, Daegu 702-722 (Korea, Republic of); Takada, Yukyo [Division of Dental Biomaterials, Graduate School of Dentistry, Tohoku University, 4-1 Seiryo-machi, Aoba-ku, Sendai 980-8575 (Japan); Okuno, Osamu [Division of Dental Biomaterials, Graduate School of Dentistry, Tohoku University, 4-1 Seiryo-machi, Aoba-ku, Sendai 980-8575 (Japan); Kwon, Yong Hoon [Department of Dental Materials, College of Dentistry, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of); Kim, Hyung-Il [Department of Dental Materials, College of Dentistry, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of)]. E-mail: hilkim@pusan.ac.kr

    2006-01-05

    The age-hardening behaviour, phase transformation and related microstructural changes of an experimental Ag-Cu-Pd-Au alloy were examined by means of hardness test, X-ray diffraction (XRD), scanning electron microscopic (SEM) observations and electron probe microanalysis (EPMA). The specimen alloy showed apparent age-hardenability at the aging temperatures of 350 deg. C and 400 deg. C. By aging the solution-treated specimen at 400 deg. C, two phases of the Ag-rich {alpha}{sub 1} phase and the Pd-containing Cu-rich {alpha}{sub 2} phase were transformed into four phases of the Ag-rich {alpha}{sub 1}{sup '} phase, the Cu-rich {alpha}{sub 2}{sup '} phase, the CsCl-type CuPd phase and the AuCu(I) ordered phase. Microstructure of the solution-treated specimen consisted of the Ag-rich {alpha}{sub 1} matrix, Cu-rich {alpha}{sub 2} particle-like structures of various sizes and the lamellar structure of the {alpha}{sub 1} and {alpha}{sub 2} phases. When the peak hardness was obtained, the very fine lamellar structure consisting of the Ag-rich {alpha}{sub 1}{sup '} and Cu-rich {alpha}{sub 2}{sup '} phases was newly formed in the matrix. By further aging, the very fine lamellar structure grew and coarsened apparently, and the matrix was covered with the coarsened lamellar structure. The hardness increase was considered to be caused mainly by the diffusion and precipitation of Cu from the Ag-rich {alpha}{sub 1} matrix, and the hardness decrease in the latter stage of age-hardening process was caused by the coarsening of the very fine lamellar structure. The CsCl-type CuPd phase and the AuCu(I) ordered phase did not contribute to the hardness increase.

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

    Science.gov (United States)

    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.

  6. Fluid inclusion and oxygen-isotope evidence for low-temperature Au-Pt-Pd (± U) mineralization at Corronation Hill, NT

    International Nuclear Information System (INIS)

    Mernagh, T.

    1992-01-01

    The fluid inclusion and isotope data have been used to constrain the ore genesis models for the Au-Pt-Pd-U mineralization at Coronation Hill. The fluid inclusions demonstrate that the ore fluid was strongly saline with an unusually high CaCl 2 content, and that the mineralisation was probably formed from a boiling fluid at around 140 deg C. Furthermore, the fluids were highly oxidised and the replacement of earlier chlorite by hematite is common throughout the deposit. It is concluded that both U-rich and U-poor Au-Pt-Pd mineralisation were formed by descending, low-temperature, highly oxidised, very saline, meteoric fluids. The segregation of U was controlled by fluid-rock interaction in the feldspathic or carbonate rocks. Interaction with carbonaceous or chloritic rocks resulted in a reduction in fO 2 , and consequent precipitation of U, Au, Pt and Pd. The other two types of metal associations can be explained by further reaction of the mineralizing fluids. 3 figs

  7. Au-Biocompatible metallic nanostructures in metalloprotein electrochemistry and electrocatalysis

    DEFF Research Database (Denmark)

    Jensen, Palle Skovhus; Engelbrekt, Christian; Sørensen, Karsten Holm

    2012-01-01

    Molecular scale metallic nanoparticles coated by molecular monolayers and immobilized on single-crystal Au-electrode surfaces are efficient catalysts in metalloprotein voltammetry. Nanoparticles prepared by a new ‘‘green’’ method also exhibit strong electrocatalysis in both protein electrochemist...

  8. Pd@Au core-shell nanocrystals with concave cubic shapes: kinetically controlled synthesis and electrocatalytic properties.

    Science.gov (United States)

    Zhang, Ling; Niu, Wenxin; Zhao, Jianming; Zhu, Shuyun; Yuan, Yali; Hua, Lianzhe; Xu, Guobao

    2013-01-01

    A new type of concave cubic Pd@Au core-shell nanocrystals is synthesized through a kinetically controlled growth process. Pd nanocubes of 56 nm are used as the inner core, and CTAC and Br(-) are used as the capping agent and selective adsorbent, respectively. A suitable ratio of HAuCl4 and cubic Pd seeds and the presence of Br(-) anions are critical to the growth of the concave cubic Pd@Au core-shell nanocrystals. The fast deposition rate on the corners of the cubic Pd seeds promotes the overgrowth of the Au outer shell along the direction, leading to the formation of concave cubic nanostructures. The reduction process is monitored by the surface plasmon resonance spectra of the nanocrystals, and the extinction band became broader and red shifted as the nanocrystals became larger. The electrocatalytic properties of the concave cubic Pd@Au core-shell nanocrystals were investigated with the cathodic electrochemiluminescence reaction of luminol and H2O2. A possible electrocatalytic mechanism was proposed and analyzed.

  9. Microbially supported synthesis of catalytically active bimetallic Pd-Au nanoparticles

    DEFF Research Database (Denmark)

    Hosseinkhani, Baharak; Søbjerg, Lina Sveidal; Rotaru, Amelia-Elena

    2012-01-01

    Transformation (FFT) analyses confirmed that the nanoparticles indeed were bimetallic. The bimetallic nanoparticles did not have a core-shell structure, but were superior to monometallic particles at reducing p-nitrophenol to p-aminophenol. Hence, formation of microbially supported nanoparticles may be a cheap......(II) to the bio-supported particles resulted in increased particle size. UV-Vis spectrophotometry and HR-TEM analyses indicated that the previously monometallic nanoparticles had become fully or partially covered by Au(0) or Pd(0), respectively. Furthermore, Energy Dispersive Spectrometry (EDS) and Fast Fourier...

  10. Phase transformation and microstructural changes during ageing process of an Ag-Pd-Cu-Au alloy

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Chin-Ho; Park, Mi-Gyoung; Kwon, Yong Hoon; Seol, Hyo-Joung [Department of Dental Materials, School of Dentistry and Medical Research Institute, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of); Kim, Hyung-Il [Department of Dental Materials, School of Dentistry and Medical Research Institute, Pusan National University, 1-10 Ami-dong, Seo-gu, Pusan 602-739 (Korea, Republic of)], E-mail: hilkim@pusan.ac.kr

    2008-07-28

    Age-hardening behaviour and the related phase transformation and microstructural changes during isothermal ageing process were studied to elucidate the age-hardening mechanism of an Ag-based dental casting alloy composed of Ag-Pd-Cu-Au-Zn, Ir and In by means of hardness test, X-ray diffraction (XRD), scanning electron microscopic (SEM) observations and energy dispersive spectroscopic microanalysis (EDS). In the hardness test at 350 and 400 deg. C, the hardness of the solution-treated specimen began to increase and reached a maximum value with increasing ageing time, and subsequently the hardness decreased gradually. By considering XRD results and SEM observations together, the solution-treated specimen consisted of three phases, the Ag-rich {alpha}{sub 1} phase as a matrix, the Cu-Pd {alpha}{sub 2} phase and the CuPd {beta} phase with a CsCl-type as particle-like structures. By ageing the solution-treated specimen, the Ag-rich {alpha}{sub 1} and Cu-Pd {alpha}{sub 2} phases were transformed into the Ag-rich {alpha}{sup '}{sub 1} and Cu{sub 3}Pd {alpha}{sup '}{sub 2} phases, respectively. The CuPd {beta} phase with a CsCl-type was not changed apparently during the ageing process. From the results of the hardness test, XRD study, SEM observations and EDS analysis, it could be derived that the hardness increased by the diffusion and precipitation of the Cu-rich phase from the Ag-rich matrix during the early stage of phase transformation of {alpha}{sub 1} into {alpha}{sup '}{sub 1} and that the progress of coarsening of the Cu-rich precipitates with an entanglement structure caused the hardness decrease during the later stage of phase transformation of {alpha}{sub 1} into {alpha}{sup '}{sub 1}. The particle-like structures composed of the Cu-Pd {alpha}{sub 2} and the CuPd {beta} phase with a CsCl-type contributed little to the hardness increase which occurred in the early stage of aging process.

  11. Hardening mechanism of an Ag-Pd-Cu-Au dental casting alloy

    International Nuclear Information System (INIS)

    Seol, Hyo-Joung; Kim, Gi-Chul; Son, Kuk-Hyeon; Kwon, Yong Hoon; Kim, Hyung-Il

    2005-01-01

    Age-hardening behaviour and the related microstructural changes were studied to elucidate the hardening mechanism of an Ag-Pd-Cu-Au dental casting alloy by means of hardness test, X-ray diffraction (XRD), scanning electron microscopic (SEM) observations and electron probe microanalysis (EPMA). By considering hardness test and XRD results together, it was revealed that the hardness increased during the early stage of phase transformation of α into α 1 . In the SEM photographs, two phases of matrix and particle-like structures were observed, and the precipitation of element from the matrix progressed during isothermal aging. By SEM observations and EPMA analysis, it could be supposed that the increase in hardness was caused by the diffusion and aggregation of Cu atoms from the Ag-rich α matrix containing Au and Cu in the early stage of age-hardening process, and that the decrease in hardness was caused by the progress of coarsening of Cu-rich lamellar precipitates in the later stage of the age-hardening process. The changes in the Ag-rich matrix caused both the increase and decrease in hardness, and the CuPd phase containing small amounts of Zn and Sn did not contribute to the hardness changes

  12. Heterojunction metal-oxide-metal Au-Fe{sub 3}O{sub 4}-Au single nanowire device for spintronics

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, K. M., E-mail: mrkongara@boisestate.edu; Punnoose, Alex; Hanna, Charles [Department of Physics, Boise State University, Boise, Idaho 83725 (United States); Padture, Nitin P. [School of Engineering, Brown University, Providence, Rhode Island 02912 (United States)

    2015-05-07

    In this report, we present the synthesis of heterojunction magnetite nanowires in alumina template and describe magnetic and electrical properties from a single nanowire device for spintronics applications. Heterojunction Au-Fe-Au nanowire arrays were electrodeposited in porous aluminum oxide templates, and an extensive and controlled heat treatment process converted Fe segment to nanocrystalline cubic magnetite phase with well-defined Au-Fe{sub 3}O{sub 4} interfaces as confirmed by the transmission electron microscopy. Magnetic measurements revealed Verwey transition shoulder around 120 K and a room temperature coercive field of 90 Oe. Current–voltage (I-V) characteristics of a single Au-Fe{sub 3}O{sub 4}-Au nanowire have exhibited Ohmic behavior. Anomalous positive magnetoresistance of about 0.5% is observed on a single nanowire, which is attributed to the high spin polarization in nanowire device with pure Fe{sub 3}O{sub 4} phase and nanocontact barrier. This work demonstrates the ability to preserve the pristine Fe{sub 3}O{sub 4} and well defined electrode contact metal (Au)–magnetite interface, which helps in attaining high spin polarized current.

  13. Characterization of electroless Au, Pt and Pd contacts on CdTe and ZnTe by RBS and SIMS techniques

    Energy Technology Data Exchange (ETDEWEB)

    Roumie, M. E-mail: mroumie@cnrs.edu.lb; Hageali, M.; Zahraman, K.; Nsouli, B.; Younes, G

    2004-06-01

    Rutherford backscattering spectrometry (RBS) was applied to characterize Au, Pt and Pd contacts on II-VI semiconductor materials, CdTe and ZnTe, used as nuclear detectors. Electroless thin film depositions were prepared by changing the concentration of the reaction solution. Contrary to the deposition reaction time, it was observed that the amount of solution dilution degree had a considerable effect on increasing the thickness of the metal layer. Furthermore, PICTS electrical measurements confirmed the depth profile analysis performed by RBS and SIMS.

  14. Sodium citrate assisted facile synthesis of AuPd alloy networks for ethanol electrooxidation with high activity and durability

    Science.gov (United States)

    Zhai, Yanling; Zhu, Zhijun; Lu, Xiaolin; Zhou, H. Susan

    2016-10-01

    The direct ethanol fuel cell is an emerging energy conversion device for which palladium is considered as the one of the most effective components for anode catalyst, however, its widespread application has been still limited by the activity and durability of the anode catalyst. In this work, AuPd alloy networks (NWs) are synthesized using H2PdCl4 and HAuCl4 as precursors reduced by NaBH4 in the presence of sodium citrate (SC). The results reveal that SC plays significant role in network structure, resulting in the enhanced electrocatalytic activity of the catalyst. This self-supported AuPd NWs catalyst exhibits much higher electrochemical catalytic activity than commercial Pd/C catalyst toward ethanol electrooxidation in alkaline solution. Significantly, AuPd NWs catalyst shows extremely high durability at the beginning of the chronoamperometry test, and as high as 49% of the mass current density (1.41 A/mgPd) remains after 4000 s current-time test at -0.3 V (vs. Ag/AgCl) in N2-saturated KOH-ethanol solution. This strategy provides a facile method for the preparation of alloy networks with high electrochemical activity, and can be potentially expanded to a variety of electrochemical applications.

  15. Water-dispersable hybrid Au-Pd nanoparticles as catalysts in ethanol oxidation, aqueous phase Suzuki-Miyaura and Heck reactions

    KAUST Repository

    Song, Hyon Min

    2012-01-01

    The catalytic activities of water-dispersable Au@Pd core-shell nanoparticles (NPs) and Au-Pd alloy NPs were examined. There is growing interest in Au-Pd hybridized NPs in a supported matrix or non-supported forms as catalysts in various reactions that are not limited to conventional Pd-related reactions. Four different Au@Pd core-shell NPs in this study were prepared at room temperature with help from the emulsion phase surrounding the Au core NPs. Au-Pd alloy NPs were prepared over 90 °C, and underwent phase transfer to aqueous medium for their catalytic use. Au@Pd core-shell NPs show catalytic activity in ethanol oxidation reactions as electrocatalysts, and both core-shell and alloy NPs are good to excellent catalysts in various Suzuki-Miyaura and Heck reactions as heterogeneous catalysts. Specifically, Au@Pd core-shell NPs with sharp branched arms show the highest yield in the reactions tested in this study. A relatively small amount (0.25 mol%) was used throughout the catalytic reactions. © 2012 The Royal Society of Chemistry.

  16. PdM (M = Pt, Au) bimetallic alloy nanowires with enhanced electrocatalytic activity for electro-oxidation of small molecules.

    Science.gov (United States)

    Zhu, Chengzhou; Guo, Shaojun; Dong, Shaojun

    2012-05-02

    A facile and general method has been developed to synthesize well-defined PdPt and PdAu alloy nanowires, which exhibit significantly enhanced activity towards small molecules, such as ethanol, methanol, and glucose electro-oxidation in an alkaline medium. Considering the important role of one-dimensional alloy nanowires in electrocatalytic systems, the present Pd-based alloy nanostructures could offer a promising new class of advanced electrocatalysts for direct alcohol fuel cells and electrochemical sensors. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2012-07-23

    In this work, we utilize the galvanic displacement synthesis and make it a general and efficient method for the preparation of Au-M (M = Au, Pd, and Pt) core-shell nanostructures with porous shells, which consist of multilayer nanoparticles. The method is generally applicable to the preparation of Au-Au, Au-Pd, and Au-Pt core-shell nanostructures with typical porous shells. Moreover, the Au-Au isomeric core-shell nanostructure is reported for the first time. The lower oxidation states of Au(I), Pd(II), and Pt(II) are supposed to contribute to the formation of porous core-shell nanostructures instead of yolk-shell nanostructures. The electrocatalytic ethanol oxidation and oxygen reduction reaction (ORR) performance of porous Au-Pd core-shell nanostructures are assessed as a typical example for the investigation of the advantages of the obtained core-shell nanostructures. As expected, the Au-Pd core-shell nanostructure indeed exhibits a significantly reduced overpotential (the peak potential is shifted in the positive direction by 44 mV and 32 mV), a much improved CO tolerance (I(f)/I(b) is 3.6 and 1.63 times higher), and an enhanced catalytic stability in comparison with Pd nanoparticles and Pt/C catalysts. Thus, porous Au-M (M = Au, Pd, and Pt) core-shell nanostructures may provide many opportunities in the fields of organic catalysis, direct alcohol fuel cells, surface-enhanced Raman scattering, and so forth. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Separation of 103Pd from metal Rhodium by dry distillation

    International Nuclear Information System (INIS)

    Szuecs, Z.; Takacs, S.

    2009-01-01

    Complete text of publication follows. Introduction. The use of Auger emitters as potential radiopharmaceuticals is increasingly investigated. One such radionuclide of interest is 103m Rh. This can be produced from 103 Ru or from 103 Pd in an in vivo generator. It has been proven on theoretical considerations that use of 103 Pd/ 103m Rh in vivo generator will be successful in delivering 103 mRh to a target site when complexed to a tumor selective carrier. 103 Pd is widely used in internal radiotherapy with one of the production routes via the irradiation of Rh by protons in a cyclotron. The charged particle production of 103 Pd is the only way for no-carrier -added production of this radionuclide, which is required for use in nuclear medicine. However, the widely used separation technique to get 103 Pd from the target material (as well as recovery of the Rh) by wet chemistry is a very complicated, labour intensive and expensive procedure, resulting in low yields of 103 Pd and high amounts of radioactive waste. An alternative more efficient separation and production technology can be developed based on differential evaporation. The principle is the following: The produced 103 Pd 'contaminating' new element within the crystal structure of the Rh target can be forced to diffuse out from the deformed crystal lattice by heating up the target. In this process the 103 Pd accumulates on the surface of the target from where it can be evaporated. A prerequisite for this process is that the target metal (Rh) has a different partial pressure than the evaporated metal (Pd). The thick target yield is 6MBq/μ Ah and the activities of potential contaminating radioisotopes produced by side reaction are negligible, if the energy of the irradiating beam will be chosen precisely. The natural abundance of 116 Cd is 7,5%, it means that the price of the enriched material is reasonable. A potential cyclotron facility with α-beam was found at JINR, Dubna, Russia where the radiochemical

  19. Ultrasensitive and simultaneous detection of hydroquinone, catechol and resorcinol based on the electrochemical co-reduction prepared Au-Pd nanoflower/reduced graphene oxide nanocomposite

    International Nuclear Information System (INIS)

    Chen, Yuan; Liu, Xiaoying; Zhang, Si; Yang, Liuqing; Liu, Meiling; Zhang, Youyu; Yao, Shouzhuo

    2017-01-01

    A simple and efficient eletrochemical sensing platform for simultaneous detection of hydroquinone (HQ), catechol (CC) and resorcinol (RC) based on the Au-Pd bimetallic and graphene is described in this paper. The Au-Pd reduced graphene oxide (Au-Pd NF/rGO) was prepared by the electrochemical co-reduction deposition via cyclic voltammetry method (CV). The Au-Pd NF/rGO nanocomposite was examined by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and electrochemical methods CV and differential pulse voltammety (DPV) study showed that the three dihydroxybenzene isomers can be catalytically oxidized and discriminated simultaneously on the Au-Pd NF/rGO/GCE. The presence of Pd makes the performance of the sensor superior to that of in the absence of it. Owing to the integrated superior conductivity and excellent catalytic property of Au-Pd NF/rGO, the sensitive and simultaneous detection of HQ, CC and RC was realized in the individual or triple-components solution based on the as proposed Au-Pd NF/rGO/GCE, which shows wide linear range and low detection limit. The detection of them in tap water, river water and lake water were also successfully performed and good recovery was obtained.

  20. Amphiphilic hollow porous shell encapsulated Au@Pd bimetal nanoparticles for aerobic oxidation of alcohols in water

    KAUST Repository

    Zou, Houbing

    2015-01-01

    © The Royal Society of Chemistry 2015. This work describes the design, synthesis and analysis of an amphiphilic hollow mesoporous shell encapsulating catalytically active Au@Pd bimetal nanoparticles. The particles exhibited excellent catalytic activity and stability in the aerobic oxidation of primary and secondary alcohols to their corresponding aldehydes or ketones in water when using air as an oxidizing agent under atmospheric pressure.

  1. Shape-controlled synthesis of Au@Pd core-shell nanoparticles and their corresponding electrochemical properties

    KAUST Repository

    Song, Hyon Min

    2012-01-01

    The shape-controlled synthesis of Au@Pd core-shell nanoparticles (NPs) was successfully achieved through the emulsion phase generated during the phase transfer from organic to aqueous medium. Contrary to conventional epitaxial growth for obtaining core-shell structures, this method does not require high temperatures and does not have shape restrictions. © 2012 The Royal Society of Chemistry.

  2. Retrieval of Au, Ag, Cu precious metals coupled with electric energy production via an unconventional coupled redox fuel cell reactor.

    Science.gov (United States)

    Zhang, Hui-Min; Fan, Zheng; Xu, Wei; Feng, Xiao; Wu, Zu-Cheng

    2017-09-15

    The recovery of heavy metals from aqueous solutions or e-wastes is of upmost importance. Retrieval of Au, Ag, and Cu with electricity generation through building an ethanol-metal coupled redox fuel cells (CRFCs) is demonstrated. The cell was uniquely assembled on PdNi/C anode the electro-oxidation of ethanol takes place to give electrons and then go through the external circuit reducing metal ions to metallic on the cathode, metals are recovered. Taking an example of removal of 100mgL -1 gold in 0.5M HAc-NaAc buffer solution as the catholyte, 2.0M ethanol in 1.0M alkaline solution as the anolyte, an open circuit voltage of 1.4V, more than 96% of gold removal efficiency in 20h, and equivalent energy production of 2.0kWhkg -1 of gold can be readily achieved in this system. When gold and copper ions coexist, it was confirmed that metallic Cu is formed on the cathodic electrode later than metallic Au formation by XPS analysis. Thus, this system can achieve step by step electrodeposition of gold and copper while the two metal ions coexisting. This work develops a new approach to retrieve valuable metals from aqueous solution or e-wastes. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. DFT study of the structures and energetics of 98-atom AuPd clusters.

    Science.gov (United States)

    Bruma, Alina; Ismail, Ramli; Paz-Borbón, L Oliver; Arslan, Haydar; Barcaro, Giovanni; Fortunelli, Alessandro; Li, Z Y; Johnston, Roy L

    2013-01-21

    The energetics, structures and segregation of 98-atom AuPd nanoclusters are investigated using a genetic algorithm global optimization technique with the Gupta empirical potential (comparing three different potential parameterisations) followed by local minimizations using Density Functional Theory (DFT) calculations. A shell optimization program algorithm is employed in order to study the energetics of the highly symmetric Leary Tetrahedron (LT) structure and optimization of the chemical ordering of a number of structural motifs is carried out using the Basin Hopping Monte Carlo approach. Although one of the empirical potentials is found to favour the LT structure, it is shown that Marks Decahedral and mixed FCC-HCP motifs are lowest in energy at the DFT level.

  4. Microstructures and coherent phase diagram for the pseudobinary system (AuCu)1-xPd x with x ≤ 0.10

    International Nuclear Information System (INIS)

    Luciano, Rhodora H.; Shiraishi, Takanobu; Udoh, Koh-ichi; Tanaka, Yasuhiro; Hisatsune, Kunihiro

    2005-01-01

    A coherent phase diagram for the pseudobinary system (AuCu) 1-x Pd x with x ≤ 0.10 was constructed based on phase identification and microstructural analysis by transmission electron microscopy. It was confirmed that the addition of palladium exceeding 1.0 at.% to the equiatomic AuCu eliminated the AuCu II long-period superstructure from the phase equilibria and stabilized the AuCu I superstructure. The AuCu-0.5 at.% Pd and AuCu-1.0 at.% Pd alloys isothermally aged for long time at temperatures ranging from 380 to 420 deg. C exhibited seven distinguishable regions; a single-phase region of disordered solid solution (α); a single-phase region of AuCu I ordered phase; a single-phase region of AuCu II ordered phase; a region of the coexisting AuCu I and AuCu II ordered phases; a region of the coexisting AuCu I ordered and α phases; a region of the coexisting AuCu II ordered and α phases; and a region of the coexisting AuCu I and AuCu II ordered and α phases

  5. Fabrication of Ternary AgPdAu Alloy Nanoparticles on c-Plane Sapphire by the Systematical Control of Film Thickness and Deposition Sequence

    Science.gov (United States)

    Kunwar, Sundar; Pandey, Puran; Sui, Mao; Bastola, Sushil; Lee, Jihoon

    2018-06-01

    In this work, a systematic study on the fabrication of ternary AgPdAu alloy nanoparticles (NPs) on c-plane sapphire (0001) is presented and the corresponding structural and optical characteristics are demonstrated. The metallic trilayers of various thicknesses and deposition orders are annealed in a controlled manner (400 °C to 900 °C) to induce the solid-state dewetting that yields the various structural configurations of AgPdAu alloy NPs. The dewetting of relatively thicker trilayers (15 nm) is gradually progressed with void nucleation, growth, and coalescence, isolated NP formation, and shape transformation, along with the temperature control. For 6 nm thickness, owing to the sufficient dewetting of trilayers along with enhanced diffusion, dense and small spherical alloy NPs are fabricated. Depending on the specific growth condition, the surface diffusion and interdiffusion of metal atoms, surface and interface energy minimization, Rayleigh instability, and equilibrium configuration are correlated to describe the fabrication of ternary alloy NPs. Ternary alloy NPs exhibit morphology-dependent ultraviolet-visible-near infrared (UV-VIS-NIR) reflectance properties such as the inverse relationship of average reflectance with the surface coverage, absorption enhancement in specific regions, and reflectance maxima in UV and NIR regions. In addition, Raman spectra depict the six active phonon modes of sapphires and their intensity and position modulation by the alloy NPs.

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

    Science.gov (United States)

    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.

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

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Sholl, David S.

    2012-01-01

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

  8. Enzyme-Free Electrochemical Glucose Sensors Prepared by Dealloying Pd-Ni-P Metallic Glasses

    Directory of Open Access Journals (Sweden)

    Yuqiao Zeng

    2014-01-01

    Full Text Available We report the formation of enzyme-free electrochemical glucose sensors by electrochemical dealloying palladium-containing Pd-Ni-P metallic glasses. When metallic glasses with different Pd contents are used as the dealloying precursor alloys, palladium-based nanoporous metals with different ligament and pore sizes can be obtained. The chemical compositions of the nanoporous metals also vary according to the different precursor compositions. All the as-obtained nanoporous metals exhibit electrochemical catalytic activity towards the oxidation of d-glucose, indicating that the nanoporous metals prepared by dealloying the Pd-Ni-P metallic glasses are promising materials for enzyme-free electrochemical glucose sensor.

  9. Tailoring the synthesis of supported Pd catalysts towards desired structure and size of metal particles.

    Science.gov (United States)

    Suresh, Gatla; Radnik, Jörg; Kalevaru, Venkata Narayana; Pohl, Marga-Martina; Schneider, Matthias; Lücke, Bernhard; Martin, Andreas; Madaan, Neetika; Brückner, Angelika

    2010-05-14

    In a systematic study, the influence of different preparation parameters on phase composition and size of metal crystallites and particles in Pd-Cu/TiO(2) and Pd-Sb/TiO(2) catalyst materials has been explored. Temperature and atmosphere of thermal pretreatment (pure He or 10% H(2)/He), nature of metal precursors (chlorides, nitrates or acetates) as well as of ammonium additives (ammonium sulfate, nitrate, carbonate) and urea were varied with the aim of tailoring the synthesis procedure for the preferential formation of metal particles with similar size and structure as observed recently in active catalysts after long-term equilibration under catalytic reaction conditions in acetoxylation of toluene to benzylacetate. Among the metal precursors and additives, the chloride metal precursors and (NH(4))(2)SO(4) were most suitable. Upon thermal pretreatment of Pd-Sb or Pd-Cu precursors, chloroamine complexes of Pd and Cu are formed, which decompose above 220 degrees C to metallic phases independent of the atmosphere. In He, metallic Pd particles were formed with both the co-components. In H(2)/He flow, Pd-Cu precursors were converted to core-shell particles with a Cu shell and a Pd core, while Sb(1)Pd(1) and Sb(7)Pd(20) alloy phases were formed in the presence of Sb. Metal crystallites of about 40 nm agglomerate to particles of up to 150 nm in He and to even larger size in H(2)/He.

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

    Science.gov (United States)

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

    Anisotropic Au nanoparticles show unique localized surface plasmon resonance (LSPR) properties, which make it 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 observation and spectral monitoring, we found that the layered epitaxial growth mode (i.e., 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 for the formation of the nanostars. The LSPR properties of the Au nanoparticles have been well investigated with morphology control via 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 substrate to detect trace amount of molecules.

  11. Metal-phthalocyanine ordered layers on Au(110): Metal-dependent adsorption energy

    Energy Technology Data Exchange (ETDEWEB)

    Massimi, Lorenzo, E-mail: lorenzo.massimi@uniroma1.it; Angelucci, Marco; Gargiani, Pierluigi; Betti, Maria Grazia [Dipartimento di Fisica, Università di Roma La “Sapienza,” 00185 Roma (Italy); Montoro, Silvia [IFIS Litoral, CONICET-UNL, Laboratorio de Fisica de Superficies e Interfaces, Güemes 3450, Santa Fe (Argentina); Mariani, Carlo, E-mail: carlo.mariani@uniroma1.it [Dipartimento di Fisica, CNISM, Università di Roma La “Sapienza,” 00185 Roma (Italy)

    2014-06-28

    Iron-phthalocyanine and cobalt-phthalocyanine chains, assembled along the Au(110)-(1×2) reconstructed channels, present a strong interaction with the Au metallic states, via the central metal ion. X-ray photoemission spectroscopy from the metal-2p core-levels and valence band high-resolution ultraviolet photoelectron spectroscopy bring to light signatures of the interaction of the metal-phthalocyanine single-layer with gold. The charge transfer from Au to the molecule causes the emerging of a metal-2p core level component at lower binding energy with respect to that measured in the molecular thin films, while the core-levels associated to the organic macrocycle (C and N 1s) are less influenced by the adsorption, and the macrocycles stabilize the interaction, inducing a strong interface dipole. Temperature Programmed Desorption experiments and photoemission as a function of temperature allow to estimate the adsorption energy for the thin-films, mainly due to the molecule-molecule van der Waals interaction, while the FePc and CoPc single-layers remain adsorbed on the Au surface up to at least 820 K.

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

    Science.gov (United States)

    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.

  13. Ionic liquid assisted synthesis of nano Pd-Au particles and application for the detection of epinephrine, dopamine and uric acid

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, Tsung-Hsuan; Thiagarajan, Soundappan; Chen Shenming, E-mail: smchen78@ms15.hinet.net; Cheng Chingyi

    2012-01-31

    Nano Pd-Au particles have been electrochemically fabricated utilizing ionic liquid as green electrolyte (1-Butyl-3-methylimidazolium tetrafluoroborate). Nano Pd-Au particles modified glassy carbon electrode (GCE) and indium tin oxide coated glass electrodes were examined using atomic force microscopy, field emission scanning electron microscope and X-ray diffraction studies. Electrodeposited nano Pd-Au particles' average diameter was found as 33 nm. Nano Pd-Au particle modified GCE was electrochemically active and stable in various pH solutions. The proposed nano particle modified GCE reduces the over potential and shows the well defined oxidation peaks for the detection of epinephrine and simultaneous determination of dopamine and uric acid (in pH 7.0 phosphate buffer solution) using cyclic voltammetry and differential pulse voltammetry.

  14. Magnetic domains and frustration in metallic CePdAl

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-07-01

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

  15. Enhanced performance of a novel anodic PdAu/VGCNF catalyst for electro-oxidation in a glycerol fuel cell.

    Science.gov (United States)

    Yahya, N; Kamarudin, S K; Karim, N A; Masdar, M S; Loh, K S

    2017-11-25

    This study presents a novel anodic PdAu/VGCNF catalyst for electro-oxidation in a glycerol fuel cell. The reaction conditions are critical issues affecting the glycerol electro-oxidation performance. This study presents the effects of catalyst loading, temperature, and electrolyte concentration. The glycerol oxidation performance of the PdAu/VGCNF catalyst on the anode side is tested via cyclic voltammetry with a 3 mm 2 active area. The morphology and physical properties of the catalyst are examined using X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. Then, optimization is carried out using the response surface method with central composite experimental design. The current density is experimentally obtained as a response variable from a set of experimental laboratory tests. The catalyst loading, temperature, and NaOH concentration are taken as independent parameters, which were evaluated previously in the screening experiments. The highest current density of 158.34 mAcm -2 is obtained under the optimal conditions of 3.0 M NaOH concentration, 60 °C temperature and 12 wt.% catalyst loading. These results prove that PdAu-VGCNF is a potential anodic catalyst for glycerol fuel cells.

  16. Facile synthesis and electrochemiluminescence application of concave trisoctahedral Pd@Au core-shell nanocrystals bound by {331} high-index facets.

    Science.gov (United States)

    Zhang, Ling; Niu, Wenxin; Li, Zhiyuan; Xu, Guobao

    2011-10-07

    Concave trisoctahedral (TOH) Pd@Au core-shell nanocrystals bound by {331} facets have been synthesized for the first time. Pd nanocubes and cetyltrimethylammonium chloride were used as the structure-directing cores and capping agents, respectively. Their optical and electrocatalytic properties were investigated. This journal is © The Royal Society of Chemistry 2011

  17. DFT study on stability and H{sub 2} adsorption activity of bimetallic Au{sub 79−n}Pd{sub n} (n = 1–55) clusters

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xuejing [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Tian, Dongxu, E-mail: tiandx@dlut.edu.cn [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Meng, Changgong [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China)

    2013-03-29

    Highlights: ► Stability of Pd substitution type is face > mid-edge > corner > edge. ► H{sub 2} adsorption activity is in contrast with the stability of Pd substitution type. ► Non-activated dissociation of H{sub 2} occurs in Au{sub 36}Pd{sub 43−3} with high thermal stability. ► ε{sub d} agrees with that Pd at edge and corner are more active than face and mid-edge. - Abstract: The stability and H{sub 2} adsorption activity of bimetallic Au{sub 79−n}Pd{sub n} (n = 1–55) clusters were studied by density functional theory with GGA-PW91 functional. The stability order for four Pd substitution types is face > mid-edge > corner > edge, and the stability is improved with increasing Pd content. In contrast with the stability order, H{sub 2} adsorption activity is corner ≈ edge > mid-edge > face. The Au{sub 36}Pd{sub 43} (3) with Au:Pd ≈ 1:1 ratio and twenty-four Pd substitutions at (1 1 1) facets and nineteen Pd substitutions at subshell sites shows high stability and H{sub 2} non-activated dissociation activity. The partial density of d-states and d band center revealed that the electronic properties are closely associated with the geometric characteristic and adsorption activity. Correlating the d band center ε{sub d} and the adsorption energies, the ε{sub d} order agrees with the adsorption activity that the Pd substitution at edge and corner sites are more active than at face and mid-edge sites.

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

    Science.gov (United States)

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

    2017-06-01

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

  19. A density functional theory study on the conversion of ethylene to carbon monomer on PdAu(1 0 0) surface

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Minhua; Yang, Bing [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China)

    2015-11-30

    Graphical abstract: - Highlights: • The successive decomposition of ethylene on PdAu(1 0 0) was studied with DFT method. • The C−H, C−C bond scission and a hydrogen-shift process were investigated. • The alloying of Au with Pd affects the studied reactions on PdAu(1 0 0) greatly. - Abstract: Calculations based on the first-principles density functional theory (DFT) were performed to study the possible transformation pathways of ethylene on PdAu(1 0 0) surface to investigate the effect of Au atom alloying with Pd on the formation of CHx (x = 0–2), which may eventually form carbon monomer and lead to the deactivation of catalysts. The energetic properties of reactions including the scission of the C−H, C−C bond and a hydrogen-shift process were determined. The C−H bond scission is confirmed to be prone to happen on the studied surface, while it is difficult for the C−C bond scission to occur due to relatively high barriers, the values of which are as high as 2.72–4.62 eV. The activation barriers for all related reactions except for the dehydrogenation of vinyl, vinylidene and acetenyl demonstrate that it is harder for the conversion of ethylene to occur on PdAu(1 0 0) surface than on Pd(1 0 0) surface, especially for the C−C bond scission. All the results indicate that the alloying of Au atom with pure Pd catalyst can prevent the formation of carbon monomer, which may notably affect properties of catalysts.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xiang; Sun, Bingli [School of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou 450001 (China); National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China); Zhao, Na [National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China); National Engineering Research Center for Advanced Polymer Processing Technology, Zhengzhou University, Zhengzhou 450002 (China); Li, Qian, E-mail: qianli@zzu.edu.cn [School of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou 450001 (China); National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China); National Engineering Research Center for Advanced Polymer Processing Technology, Zhengzhou University, Zhengzhou 450002 (China); Hou, Jianhua; Feng, Weina [School of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou 450001 (China); National Center for International Joint Research of Micro-nano Molding Technology, Zhengzhou University, Zhengzhou 450001 (China); Key Laboratory for Micro Molding Technology of Henan Province, Zhengzhou University, Zhengzhou, 450001 (China)

    2014-12-01

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

  1. Innate stimulatory capacity of high molecular weight transition metals Au (gold) and Hg (mercury).

    Science.gov (United States)

    Rachmawati, Dessy; Alsalem, Inás W A; Bontkes, Hetty J; Verstege, Marleen I; Gibbs, Sue; von Blomberg, B M E; Scheper, Rik J; van Hoogstraten, Ingrid M W

    2015-03-01

    Nickel, cobalt and palladium ions can induce an innate immune response by triggering Toll-like receptor (TLR)-4 which is present on dendritic cells (DC). Here we studied mechanisms of action for DC immunotoxicity to gold and mercury. Next to gold (Na3Au (S2O3)2⋅2H2O) and mercury (HgCl2), nickel (NiCl2) was included as a positive control. MoDC activation was assessed by release of the pro-inflammatory mediator IL-8. Also PBMC were studied, and THP-1 cells were used as a substitution for DC for evaluation of cytokines and chemokines, as well as phenotypic, alterations in response to gold and mercury. Our results showed that both Na3Au (S2O3)2⋅2H2O and HgCl2 induce substantial release of IL-8, but not IL-6, CCL2 or IL-10, from MoDc, PBMC, or THP-1 cells. Also gold and, to a lesser extent mercury, caused modest dendritic cell maturation as detected by increased membrane expression of CD40 and CD80. Both metals thus show innate immune response capacities, although to a lower extent than reported earlier for NiCl2, CoCl2 and Na2 [PdCl4]. Importantly, the gold-induced response could be ascribed to TLR3 rather than TLR4 triggering, whereas the nature of the innate mercury response remains to be clarified. In conclusion both gold and mercury can induce innate immune responses, which for gold could be ascribed to TLR3 dependent signalling. These responses are likely to contribute to adaptive immune responses to these metals, as reflected by skin and mucosal allergies. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Effect of Silicon on Activity Coefficients of Siderophile Elements (P, Au, Pd, As, Ge, Sb, and In) in Liquid Fe, with Application to Core Formation

    Science.gov (United States)

    Righter, K.; Pando, K.; Danielson, L. R.; Humayun, M.; Righter, M.; Lapen, T.; Boujibar, A.

    2016-01-01

    Earth's core contains approximately 10 percent light elements that are likely a combination of S, C, Si, and O, with Si possibly being the most abundant. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE) in Fe liquids, and thus the partitioning behavior of those elements between core and mantle. The effect of Si can be small such as for Ni and Co, or large such as for Mo, Ge, Sb, As. The effect of Si on many siderophile elements is unknown yet could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of P, Au, Pd, and many other SE between metal and silicate melt. The results will be applied to Earth, for which we have excellent constraints on the mantle siderophile element concentrations.

  3. Synthesis of Pd and Rh metal nanoparticles in the interlayer space of organically modified montmorillonite

    International Nuclear Information System (INIS)

    Patel, Hasmukh A.; Bajaj, Hari C.; Jasra, Raksh Vir

    2008-01-01

    This study reports the synthesis of palladium and rhodium metal nanoparticles supported on montmorillonite (MMT) and partially organically modified MMT (POMM) using tetraamine palladium and hexaamine rhodium complex as precursor for palladium and rhodium respectively. The synthesized nanoparticles were characterized by powder X-ray diffraction PXRD and TEM. The PXRD study shows characteristic crystallographic planes for Pd and Rh metal and confirm the formation of metal nanoparticles in MMT and POMM. The TEM images reveal the effect of organic modification of MMT on decreasing particle size of Pd and Rh metal. The Pd and Rh metal nanoparticles are agglomerated in pristine MMT while nanoparticles are well dispersed in POMM. ICP-AES analysis was carried out to estimate quantitative amount of Pd and Rh metal in MMT and POMM

  4. Magnetic-property changes in epitaxial metal-film sandwiches

    International Nuclear Information System (INIS)

    Brodsky, M.B.

    1982-08-01

    Epitaxial metal-film sandwiches (EMFS) containing Pd or Cr, have been prepared between single-crystal Ag or Au. The modified Pd/Cr show major changes in physical properties. Pd has a stretched lattice parameter in Au-Pd-Au, which combines with a tetragonal distortion to cause exchange enhancements up to 28,000 and spin-fluctuation temperatures of 1 to 10 K. In Au-Cr-Au, Cr takes up the fcc structure, leading to superconductivity due to a high N(E/sub F/). These results are contrasted to data for Ag-Pd-Ag and Ag-Cr-Ag EMFS

  5. Total oxidation of VOCs on Pd and/or Au supported on TiO2/ZrO2 followed by ''operando'' Drift

    International Nuclear Information System (INIS)

    Hosseini, M.; Siffert, St.; Cousin, R.; Aboukais, A.; Hadj-Sadok, Z.; Bao-Lian, Su

    2009-01-01

    Catalytic performances of nano-structured meso-porous TiO 2 -ZrO 2 mixed oxides impregnated by Pd and/or Au were studied in toluene total oxidation in a fixed bed micro-reactor and with 'operando' DRIFT. Meso-porous TiO 2 -ZrO 2 mixed oxides with various Ti:Zr mole ratio of 80/20, 50/50 and 20/80, high surface areas were synthesised using a mixture of zirconium prop-oxide and titanium iso-prop-oxide as Zr and Ti sources and also CTMABr as surfactant. The new supports are impregnated by 0.5 or 1.5 wt% of palladium and 1 wt% of gold using impregnation and Deposition-Precipitation methods. The catalytic activity for the nano-structured meso-porous TiO 2 -ZrO 2 mixed oxides varies depending on the molar ratio of Ti:Zr and also for all series of the studied catalysts impregnated by Pd and/or Au, when the gold is loaded firstly the activity in toluene complete oxidation is higher than when Pd was deposited firstly (PdAu/TZ ≥ 1.5Pd/TZ ≥ AuPd/TZ ≥ Pd/TZ ≥ Au/TZ ≥ TZ). The highest activity of PdAu/TZ (80/20) can be related to the higher acid sites density of the support and also to the presence of a synergetic effect between palladium and gold. 'Operando' DRIFT allowed following the VOCs oxidation but also suggesting an interaction between the adsorbed molecule and the catalyst which decreases when the activity for oxidation reaction increases. (authors)

  6. Magnesium and cadmium in covalently-bonded Lonsdaleite networks: Synthesis, structure, and conding of AETMg{sub 2} and SrTCd{sub 2} (AE = Ca, Sr; T = Pd, Ag, Pt, Au)

    Energy Technology Data Exchange (ETDEWEB)

    Kersting, Marcel; Johnscher, Michael; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster, Corrensstrasse 30, 48149 Muenster (Germany); Matar, Samir F. [Universite Bordeaux, ICMCB, UPR 9048, 33600 Pessac (France)

    2013-04-15

    The alkaline earth metal compounds AETMg{sub 2} and AETCd{sub 2} (AE = Ca, Sr; T = Pd, Ag, Pt, Au) were synthesized by induction-melting (or in muffle furnaces) of the elements in sealed niobium ampoules. The new phases were characterized by powder X-ray diffraction. The structures of SrPdMg{sub 2} and SrPdCd{sub 2} were investigated by X-ray diffraction on single crystals: MgCuAl{sub 2} type, Cmcm, a = 436.42(4), b = 1130.1(1), c = 820.54(7) pm, wR{sub 2} = 0.0115, 511 F{sup 2} values for SrPdMg{sub 2} and a = 443.5(2), b = 1063.0(2), c = 810.2(2) pm, wR{sub 2} = 0.0296, 386 F{sup 2} values for SrPdCd{sub 2} with 16 variables for each refinement. The magnesium and cadmium atoms build up [TMg{sub 2}] and [TCd{sub 2}] polyanionic networks, which leave cavities for the calcium and strontium atoms. The bonding variations within the polyanions, which are mainly influenced by the length of the b axis are discussed. Ab initio calculations of electronic structure, charge densities, and chemical bonding, characterize SrPdMg{sub 2} with a larger cohesive energy than SrPdCd{sub 2}. This is illustrated by larger bonding Pd-Mg interactions, opposite to compensating Pd-Cd between bonding and antibonding states. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Electronic Absorption and MCD Spectra for Pd(AuPPh(3))(8)(2+), Pt(AuPPh(3))(8)(2+), and Related Platinum-Centered Gold Cluster Complexes.

    Science.gov (United States)

    Adrowski, Michael J.; Mason, W. Roy

    1997-03-26

    Electronic absorption and 7.0 T magnetic circular dichroism (MCD) spectra in the UV-vis region, 1.6 to approximately 4.0 &mgr;m(-)(1) (1 &mgr;m(-)(1) = 10(4) cm(-)(1)) are reported for [Pd(AuPPh(3))(8)](NO(3))(2) and [Pt(AuPPh(3))(8)](NO(3))(2) in acetonitrile solutions at room temperature. The MCD spectra are better resolved than the absorption spectra and consist of both A and B terms. The spectra are interpreted in terms of D(4)(d)() skeletal geometry and MO's that are approximated by 5s and 6s orbitals for Pd and Pt/Au atoms, respectively. The lowest energy excited configurations and states are attributed to intraframework (IF) Au(8)(2+) transitions. Evidence is also presented for Pt 5d --> Au 6s transitions in the MCD spectra for Pt(AuPPh(3))(8)(2+). Acetonitrile solution absorption and MCD spectra for the related Pt-centered cluster complexes [Pt(CO)(AuPPh(3))(8)](NO(3))(2), [Pt(AuP(p-tolyl)(3))(8)](NO(3))(2), [Pt(CuCl)(AuPPh(3))(8)](NO(3))(2), [Pt(AgNO(3))(AuPPh(3))(8)](NO(3))(2), [Pt(Hg)(2)(AuPPh(3))(8)](NO(3))(2), [Pt(HgCl)(2)(AuPPh(3))(8)](BF(4))(2), and [Pt(HgNO(3))(2)(AuPPh(3))(8)](BF(4))(2) are also reported and interpreted within the context of the model developed for the M(AuPPh(3))(8)(2+) complexes.

  8. Application of a parallel genetic algorithm to the global optimization of medium-sized Au-Pd sub-nanometre clusters

    Science.gov (United States)

    Hussein, Heider A.; Demiroglu, Ilker; Johnston, Roy L.

    2018-02-01

    To contribute to the discussion of the high activity and reactivity of Au-Pd system, we have adopted the BPGA-DFT approach to study the structural and energetic properties of medium-sized Au-Pd sub-nanometre clusters with 11-18 atoms. We have examined the structural behaviour and stability as a function of cluster size and composition. The study suggests 2D-3D crossover points for pure Au clusters at 14 and 16 atoms, whereas pure Pd clusters are all found to be 3D. For Au-Pd nanoalloys, the role of cluster size and the influence of doping were found to be extensive and non-monotonic in altering cluster structures. Various stability criteria (e.g. binding energies, second differences in energy, and mixing energies) are used to evaluate the energetics, structures, and tendency of segregation in sub-nanometre Au-Pd clusters. HOMO-LUMO gaps were calculated to give additional information on cluster stability and a systematic homotop search was used to evaluate the energies of the generated global minima of mono-substituted clusters and the preferred doping sites, as well as confirming the validity of the BPGA-DFT approach.

  9. [Au]/[Pd] Multicatalytic Processes: Direct One-Pot Access to Benzo[ c ]chromenes and Benzo[ b ]furans

    KAUST Repository

    Oonishi, Yoshihiro

    2014-08-28

    A new synthetic protocol that combines the advantages offered by eco-friendly solvent-free reactions and sequential transformations is reported. This strategy offers straightforward access to benzo[c]chromenes and benzo[b]furans from commercially available starting materials. This two-step, one-pot strategy consists of an Au-catalyzed hydrophenoxylation process followed by Pd-catalyzed C-H activation or Mizoroki-Heck reactions. The selectivity of the process towards C-H activation or Mizoroki-Heck reaction can be easily tuned. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Thermodynamic excess quantities of ternary Au-Co-Pd melts by computer-aided Knudsen cell mass spectrometry

    International Nuclear Information System (INIS)

    Tomiska, Josef

    2009-01-01

    Computer-aided Knudsen cell mass spectrometry is used for the thermodynamic investigations on ternary Au-Co-Pd melts over the entire range of composition. The 'digital intensity-ratio' (DIR)-method has been applied for the determination of the thermodynamic excess quantities, and the ternary thermodynamically adapted power (TAP) series concept is used for algebraic representation of the thermodynamic mixing behavior. The corresponding TAP parameters as well as the values of the molar excess Gibbs energies G E , of the molar heats of mixing H E , of the molar excess entropies S E , and of the thermodynamic activities at 1800 K are presented.

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

    International Nuclear Information System (INIS)

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

    1988-01-01

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

  12. Kinetically controlled synthesis of AuPt bi-metallic aerogels and their enhanced electrocatalytic performances

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Qiurong [School of Mechanical and Materials Engineering; Washington State University; Pullman; USA; Zhu, Chengzhou [School of Mechanical and Materials Engineering; Washington State University; Pullman; USA; Du, Dan [School of Mechanical and Materials Engineering; Washington State University; Pullman; USA; Key Laboratory of Pesticides and Chemical Biology; Bi, Cuixia [Institute of Crystal Materials; Shandong University; Jinan 250100; P. R. China; Xia, Haibing [Institute of Crystal Materials; Shandong University; Jinan 250100; P. R. China; Feng, Shuo [School of Mechanical and Materials Engineering; Washington State University; Pullman; USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory; Pacific Northwest National Laboratory; Richland; USA; Lin, Yuehe [School of Mechanical and Materials Engineering; Washington State University; Pullman; USA

    2017-01-01

    Kinetically controlled synthesis of AuPtxbi-metallic hydrogels/aerogels was efficiently achieved for the first timeviatuning the reaction temperature or adding a surfactant.

  13. Effects of Metal Composition and Ratio on Peptide-Templated Multimetallic PdPt Nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Merrill, Nicholas A.; Nitka, Tadeusz T.; McKee, Erik M.; Merino, Kyle C.; Drummy, Lawrence F.; Lee, Sungsik; Reinhart, Benjamin; Ren, Yang; Munro, Catherine J.; Pylypenko, Svitlana; Frenkel, Anatoly I.; Bedford, Nicholas M.; Knecht, Marc R.

    2017-02-22

    It can be difficult to simultaneously control the size, composition, and morphology of metal nanomaterials under benign aqueous conditions. For this, bio-inspired approaches have become increasing popular due to their ability to stabilize a wide array of metal catalysts under ambient conditions. In this regard, we used the R5 peptide as a 3D template for the formation of PdPt bimetallic nanomaterials. Monometallic Pd and Pt nanomaterials have been shown to be highly reactive towards a variety of catalytic processes, but by forming bimetallic species, increased catalytic activity may be realized. The optimal metal-to-metal ratio was determined by varying the Pd:Pt ratio to obtain the largest increase in catalytic activity. To better understand the morphology and the local atomic structure of the materials, the bimetallic PdPt nanomaterials were extensively studied using transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and pair distribution function analysis. The resulting PdPt materials were determined to form multicomponent nanostructures where the Pt component demonstrated varying degrees of oxidation based upon the Pd:Pt ratio. To test the catalytic reactivity of the materials, olefin hydrogenation was conducted which indicated a slight catalytic enhancement for the multicomponent materials. These results suggest a strong correlation between the metal ratio and the stabilizing biotemplate in controlling the final materials morphology, composition, and the interactions between the two metal species.

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

  15. Influence of the preparation conditions of Pd-ZrO.sub.2./sub. and AuPd-ZrO.sub.2./sub. nanoparticle-decorated functionalised MWCNTs: Electron spectroscopy study aided with the QUASES

    Czech Academy of Sciences Publication Activity Database

    Lesiak, B.; Zemek, Josef; Jiříček, Petr; Malolepszy, A.; Stobinski, L.

    2017-01-01

    Roč. 49, č. 11 (2017), s. 1124-1134 ISSN 0142-2421 R&D Projects: GA MŠk LM2015088 Institutional support: RVO:68378271 Keywords : AuPd-ZrO2/f-MWCNTs * high pressure microwave reactor * Pd-ZrO2/f-MWCNTs * XPS * QUASES Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.132, year: 2016

  16. X-ray and magnetic studies on intermetallic phases of the type CaCu5 using noble metals and strontium

    International Nuclear Information System (INIS)

    Heumann, T.; Birnschein, R.R.

    1976-01-01

    The intermetallic phases SrAu 5 , SrAg 5 and SrPd 5 and their binary part systems with the specific noble metals as well as the pseudobinary series SrAu 5 -SrPd 5 and SrAg 5 -SrPd 5 are dealt with within the framework of this lecture. The noble metals gold, silver and palladium form AB 5 phases with strontium which cristallize in CaCu 5 structure. The atomic susceptibilities of the part systems Ag-SrAg 5 and Au-SrAu 5 as a function of the Sr concentration, of the part system Pd-SrPd 5 as a function of the temperature and the Sr concentration, of Au-Pd as a function of the Pd concentration, of the series SrAu 5 -SrPd 5 as a function of the SrPd 5 concentration, of the series SrAg 5 -SrPd 5 as function of the SrPd 5 concentration, the electrical resistance of Ag-SrAg 5 and Au-SrAu 5 as function of the Sr concentration, the lattice constants of the series SrAu 5 -SrPd 5 as a function of the SrPd 5 concentration, as well as the number of effective magnetones in the system Au-Pd as a function of the Pd concentration, were measured and evaluated. (orig./LH) [de

  17. Novel condensation of Au-centered trigonal prisms in rare-earth-metal-rich tellurides: Er7Au2Te2 and Lu7Au2Te2.

    Science.gov (United States)

    Gupta, Shalabh; Corbett, John D

    2010-07-14

    A new monoclinic structure occurs for Er(7)Au(2)Te(2) according to X-ray diffraction analysis of single crystals grown at 1200 degrees C: C2/m, Z = 4, a = 17.8310(9) A, b = 3.9819(5) A, c = 16.9089(9) A, beta = 104.361(4) degrees. The isostructural Lu(7)Au(2)Te(2) also exists according to X-ray powder pattern means, a = 17.536(4) A, b = 3.9719(4) A, c = 16.695(2) A, beta = 104.33(1) degrees. The structure contains zigzag chains of condensed, Au-centered tricapped trigonal prisms (TCTP) of Er along c that also share basal faces along b to generate puckered sheets. Further bi-face-capping Er atoms between these generate the three dimensional network along a, with tellurium in cavities outlined by augmented trigonal prismatic Er polyhedra. Bonding analysis via LMTO-DFT methods reveal very significant Er-Au bonding interactions, as quantified by their energy-weighted Hamilton overlap populations (-ICOHP), approximately 49% of the total for all interactions. These and similar Er-Te contributions sharply contrast with the small Er-Er population, only approximately 14% of the total in spite of the high proportion of Er-Er contacts. The strong polar bonding of Er to the electronegative Au and Te leaves Er relatively oxidized, with many of its 5d states falling above the Fermi level and empty. The contradiction with customary representations of structures that highlight rare-earth metal clusters is manifest. The large Er-Au Hamilton overlap population is in accord with the strong bonding between early and late transition metals first noted by Brewer in 1973. The relationship of this structure to the more distorted orthorhombic (Imm2) structure type of neighboring Dy(7)Ir(2)Te(2) is considered.

  18. Synthesis of PdO/MCM-41 nanocomposites using trans-[PdCl2(PEt3)2] as the source of metal

    International Nuclear Information System (INIS)

    Hernandez-Pineda, Jessica; Rio, Jose Manuel del; Carreto, Enrique; Terres, Eduardo; Montoya, J. Asencion; Zuniga-Gonzalez, Maria de Jesus; Morgado, Jorge

    2009-01-01

    Three PdO/MCM-41 nanocomposites containing PdO species that are dispersed on an MCM-41 support have been prepared using trans-[PdCl 2 (PEt 3 ) 2 ] as the source of metal. Thermal gravimetric analysis of the decomposition of this complex in air reveals a remarkable mass loss of all nonmetallic elements centered at 300 deg. C. The materials were characterized with X-ray powder diffraction (XRPD), nitrogen sorption and TEM, which showed that the PdO nanoparticles were present inside the pores of MCM-41. XRPD analysis confirms formation of PdO (palladinite) nanocrystals, as the sole crystalline phase present in the nanocomposites.

  19. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification.

    Science.gov (United States)

    Castro-Dominguez, Bernardo; Mardilovich, Ivan P; Ma, Liang-Chih; Ma, Rui; Dixon, Anthony G; Kazantzis, Nikolaos K; Ma, Yi Hua

    2016-09-19

    Palladium-based catalytic membrane reactors (CMRs) effectively remove H₂ to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H₂, CO and CO₂. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H₂O, CO₂ and H₂. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H₂ and induce higher methane and CO conversions while yielding ultrapure H₂ and compressed CO₂ ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H₂ permeance and purity, high CH₄ conversion levels and reduced CO yields.

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

    International Nuclear Information System (INIS)

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

    2002-01-01

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

  1. Hydrogen storage in Pd nanocrystals covered with a metal-organic framework

    Science.gov (United States)

    Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M.; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

    2014-08-01

    Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

  2. Preparation and characterization of metallic supported thin Pd-Ag membranes for hydrogen separation

    OpenAIRE

    Fernandez, Ekain; Medrano, Jose Antonio; Melendez, Jon; Parco, Maria; Viviente, J.L.; van Sint Annaland, Martin; Gallucci, Fausto; Pacheco Tanaka, David A.

    2015-01-01

    This paper reports the preparation and characterization of thin-film (4-5 µm thick) Pd-Ag metallic supported membranes for high temperature applications. Various thin film membranes have been prepared by depositing a ceramic interdiffusion barrier layer prior to the simultaneous Pd-Ag electroless plating deposition. Two deposition techniques for ceramic layers (made of zirconia and alumina) have been evaluated: atmospheric plasma spraying and dip coating of a powder suspension. Initially, the...

  3. Voltage Controlled Hot Carrier Injection Enables Ohmic Contacts Using Au Island Metal Films on Ge.

    Science.gov (United States)

    Ganti, Srinivas; King, Peter J; Arac, Erhan; Dawson, Karl; Heikkilä, Mikko J; Quilter, John H; Murdoch, Billy; Cumpson, Peter; O'Neill, Anthony

    2017-08-23

    We introduce a new approach to creating low-resistance metal-semiconductor ohmic contacts, illustrated using high conductivity Au island metal films (IMFs) on Ge, with hot carrier injection initiated at low applied voltage. The same metallization process simultaneously allows ohmic contact to n-Ge and p-Ge, because hot carriers circumvent the Schottky barrier formed at metal/n-Ge interfaces. A 2.5× improvement in contact resistivity is reported over previous techniques to achieve ohmic contact to both n- and p- semiconductor. Ohmic contacts at 4.2 K confirm nonequilibrium current transport. Self-assembled Au IMFs are strongly orientated to Ge by annealing near the Au/Ge eutectic temperature. Au IMF nanostructures form, provided the Au layer is below a critical thickness. We anticipate that optimized IMF contacts may have applicability to many material systems. Optimizing this new paradigm for metal-semiconductor contacts offers the prospect of improved nanoelectronic systems and the study of voltage controlled hot holes and electrons.

  4. Sensitive electrochemical sensors for simultaneous determination of ascorbic acid, dopamine, and uric acid based on Au@Pd-reduced graphene oxide nanocomposites

    Science.gov (United States)

    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

  5. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification

    Directory of Open Access Journals (Sweden)

    Bernardo Castro-Dominguez

    2016-09-01

    Full Text Available Palladium-based catalytic membrane reactors (CMRs effectively remove H2 to induce higher conversions in methane steam reforming (MSR and water-gas-shift reactions (WGS. Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H2, CO and CO2. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H2O, CO2 and H2. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed CO2 ready for dehydration. Experimental results involving (i a conventional packed bed reactor packed (PBR for MSR, (ii a PBR with five layers of two catalysts in series and (iii a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and reduced CO yields.

  6. Protein mediated synthesis of fluorescent Au-nanoclusters for metal sensory coatings

    Energy Technology Data Exchange (ETDEWEB)

    Vogel, Manja; Raff, Johannes [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry

    2017-06-01

    Fluorescent Au-nanocluster were successfully synthesized and used for the selective detection of Cu{sup 2} {sup +}. The synthesized Au-BSA-nanoclusters remain functional also after immobilization and show high thermal stability. Additionally, the transfer of the protein mediated Au-nanocluster synthesis route to S-layer proteins was achieved. (The presented work is part of the project BIONEWS dealing with long-term stable cells for the set-up and regeneration of sensor and actor materials for strategic relevant metals, in particular rare earth elements).

  7. Facile synthesis of highly active PdAu nanowire networks as self-supported electrocatalyst for ethanol electrooxidation.

    Science.gov (United States)

    Hong, Wei; Wang, Jin; Wang, Erkang

    2014-06-25

    In recent years, direct ethanol fuel cells (DEFCs) are attracting increasing attention owing to their wide applications. However, a significant challenge in the development of DEFC technology is the urgent need for highly active anode catalysts for the ethanol oxidation reaction. In this work, a facile and reproducible method for the high-yield synthesis of PdAu nanowire networks is demonstrated. The whole synthetic process is very simple, just mixing Na2PdCl4, HAuCl4, and KBr in an aqueous solution and using polyvinylpyrrolidone as a protective reagent while sodium borohydride as a reductant. The whole synthetic process can be simply performed at room temperature and completed in 30 min, which can greatly simplify the synthetic process and lower the preparation cost. Electrochemical catalytic measurement results prove that the as-prepared catalysts exhibit dramatically enhanced electrocatalytic activity for ethanol electrooxidation in alkaline solution. The facile synthetic process and excellent catalytic performance of the as-prepared catalysts demonstrate that they can be used as a promising catalyst for DEFCs.

  8. Fast microwave-assisted solvothermal synthesis of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated MWCNTs: Pd-based bimetallic catalysts for ethanol oxidation in alkaline medium

    CSIR Research Space (South Africa)

    Ramulifho, T

    2012-01-01

    Full Text Available The preparation of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated multi-walled carbon nanotubes (SF-MWCNTs) using a very rapid microwave-assisted solvothermal strategy has been described. Electrocatalytic behaviour of the SF...

  9. Electronic structure of transition metal dichalcogenides PdTe2 and Cu0.05PdTe2 superconductors obtained by angle-resolved photoemission spectroscopy

    International Nuclear Information System (INIS)

    Liu Yan; Zhao Jian-Zhou; Yu Li; Hu Cheng; Liu De-Fa; Peng Ying-Ying; Xie Zhuo-Jin; He Jun-Feng; Chen Chao-Yu; Feng Ya; Yi He-Mian; Liu Xu; Zhao Lin; He Shao-Long; Liu Guo-Dong; Dong Xiao-Li; Zhang Jun; Lin Cheng-Tian; Chen Chuang-Tian; Xu Zu-Yan

    2015-01-01

    The layered transition metal chalcogenides have been a fertile land in solid state physics for many decades. Various MX 2 -type transition metal dichalcogenides, such as WTe 2 , IrTe 2 , and MoS 2 , have triggered great attention recently, either for the discovery of novel phenomena or some extreme or exotic physical properties, or for their potential applications. PdTe 2 is a superconductor in the class of transition metal dichalcogenides, and superconductivity is enhanced in its Cu-intercalated form, Cu 0.05 PdTe 2 . It is important to study the electronic structures of PdTe 2 and its intercalated form in order to explore for new phenomena and physical properties and understand the related superconductivity enhancement mechanism. Here we report systematic high resolution angle-resolved photoemission (ARPES) studies on PdTe 2 and Cu 0.05 PdTe 2 single crystals, combined with the band structure calculations. We present in detail for the first time the complex multi-band Fermi surface topology and densely-arranged band structure of these compounds. By carefully examining the electronic structures of the two systems, we find that Cu-intercalation in PdTe 2 results in electron-doping, which causes the band structure to shift downwards by nearly 16 meV in Cu 0.05 PdTe 2 . Our results lay a foundation for further exploration and investigation on PdTe 2 and related superconductors. (rapid communication)

  10. Formation of hydroxyapatite on Ti-coated Ti-Zr-Cu-Pd bulk metallic glass

    International Nuclear Information System (INIS)

    Qin, F.X.; Wang, X.M.; Wada, T.; Xie, G.Q.; Asami, K.; Inoue, A.

    2009-01-01

    In this research, Ti coating was conducted on Ti 40 Zr 10 Cu 36 Pd 14 bulk metallic glass (BMG) in order to increase the formation rate of hydroxyapatite layer. The formation behavior of bone-like hydroxyapatite on Ti-coated and uncoated Ti 40 Zr 10 Cu 36 Pd 14 bulk metallic glasses (BMGs) was studied. The surface morphology of Ti-coated and uncoated Ti 40 Zr 10 Cu 36 Pd 14 BMG was investigated by scanning electron microscopy and energy dispersive X-ray spectroscopy. The results revealed that the alkali pretreatment in 5 M NaOH solution at 60degC for 24 h had a beneficial effect on the formation of porous sodium titanate on Ti-coated Ti 40 Zr 10 Cu 36 Pd 14 BMG. A bone-like hydroxyapatite layer was able to form on the alkali-treated Ti-coated Ti 40 Zr 10 Cu 36 Pd 14 BMG after a short-time immersion in simulated body fluid (SBF). On the contrary, hydroxyapatite formation was not observed on the uncoated Ti 40 Zr 10 Cu 36 Pd 14 BMG after the same chemical treatments. (author)

  11. First-principles theory of short-range order in size-mismatched metal alloys: Cu-Au, Cu-Ag, and Ni-Au

    International Nuclear Information System (INIS)

    Wolverton, C.; Ozolins, V.; Zunger, A.

    1998-01-01

    We describe a first-principles technique for calculating the short-range order (SRO) in disordered alloys, even in the presence of large anharmonic atomic relaxations. The technique is applied to several alloys possessing large size mismatch: Cu-Au, Cu-Ag, Ni-Au, and Cu-Pd. We find the following: (i) The calculated SRO in Cu-Au alloys peaks at (or near) the left-angle 100 right-angle point for all compositions studied, in agreement with diffuse scattering measurements. (ii) A fourfold splitting of the X-point SRO exists in both Cu 0.75 Au 0.25 and Cu 0.70 Pd 0.30 , although qualitative differences in the calculated energetics for these two alloys demonstrate that the splitting in Cu 0.70 Pd 0.30 may be accounted for by T=0 K energetics while T≠0 K configurational entropy is necessary to account for the splitting in Cu 0.75 Au 0.25 . Cu 0.75 Au 0.25 shows a significant temperature dependence of the splitting, in agreement with recent in situ measurements, while the splitting in Cu 0.70 Pd 0.30 is predicted to have a much smaller temperature dependence. (iii) Although no measurements exist, the SRO of Cu-Ag alloys is predicted to be of clustering type with peaks at the left-angle 000 right-angle point. Streaking of the SRO peaks in the left-angle 100 right-angle and left-angle 1 (1) /(2) 0 right-angle directions for Ag- and Cu-rich compositions, respectively, is correlated with the elastically soft directions for these compositions. (iv) Even though Ni-Au phase separates at low temperatures, the calculated SRO pattern in Ni 0.4 Au 0.6 , like the measured data, shows a peak along the left-angle ζ00 right-angle direction, away from the typical clustering-type left-angle 000 right-angle point. (v) The explicit effect of atomic relaxation on SRO is investigated and it is found that atomic relaxation can produce significant qualitative changes in the SRO pattern, changing the pattern from ordering to clustering type, as in the case of Cu-Ag. copyright 1998 The American

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-12-16

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

  13. Carbon-supported PdM (M = Au and Sn) nanocatalysts for the electrooxidation of ethanol in high pH media

    Science.gov (United States)

    He, Qinggang; Chen, Wei; Mukerjee, Sanjeev; Chen, Shaowei; Laufek, František

    Carbon-supported Pd 4Au- and Pd 2.5Sn-alloyed nanoparticles were prepared by a chemical reduction method, and characterized by a wide array of experimental techniques including mass spectrometry, transmission electron microscopy, and X-ray diffraction spectroscopy. Ethanol electrooxidation on the as-synthesized catalysts and commercial Pt/C was then investigated and compared in alkaline media by cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy studies at room temperature. Voltammetric and chronoamperometric measurements showed higher current density and longer term stability in ethanol oxidation with the palladium alloy nanocatalysts than with the commercial one. Electrochemical impedance spectroscopy and Tafel plots were employed to examine the charge-transfer kinetics of ethanol electrooxidation. The results suggest that whereas the reaction kinetics might be somewhat more sluggish on the Pd-based alloy catalysts than on commercial Pt/C, the former appeared to have a higher tolerance to surface poisoning. Overall, the Pd-based alloy catalysts represent promising candidates for the electrocatalytic oxidation of ethanol, and Pd 4Au/C displays the best catalytic activity among the series for the ethanol oxidation in alkaline media.

  14. Carbon-supported PdM (M = Au and Sn) nanocatalysts for the electrooxidation of ethanol in high pH media

    Energy Technology Data Exchange (ETDEWEB)

    He, Qinggang; Mukerjee, Sanjeev [Department of Chemistry and Chemical Biology, Northeastern University, 360 Huntington Avenue, Boston, MA 02115 (United States); Chen, Wei; Chen, Shaowei [Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, CA 95064 (United States); Laufek, Frantisek [Czech Geological Survey (Czech Republic)

    2009-02-15

    Carbon-supported Pd{sub 4}Au- and Pd{sub 2.5}Sn-alloyed nanoparticles were prepared by a chemical reduction method, and characterized by a wide array of experimental techniques including mass spectrometry, transmission electron microscopy, and X-ray diffraction spectroscopy. Ethanol electrooxidation on the as-synthesized catalysts and commercial Pt/C was then investigated and compared in alkaline media by cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy studies at room temperature. Voltammetric and chronoamperometric measurements showed higher current density and longer term stability in ethanol oxidation with the palladium alloy nanocatalysts than with the commercial one. Electrochemical impedance spectroscopy and Tafel plots were employed to examine the charge-transfer kinetics of ethanol electrooxidation. The results suggest that whereas the reaction kinetics might be somewhat more sluggish on the Pd-based alloy catalysts than on commercial Pt/C, the former appeared to have a higher tolerance to surface poisoning. Overall, the Pd-based alloy catalysts represent promising candidates for the electrocatalytic oxidation of ethanol, and Pd{sub 4}Au/C displays the best catalytic activity among the series for the ethanol oxidation in alkaline media. (author)

  15. Formation of Ag2, Au2 and AgAu particles on MgO(1 0 0): DFT study on the role of support-induced charge transfer in metal-metal interactions

    International Nuclear Information System (INIS)

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

    2009-01-01

    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.

  16. In vitro corrosion of dental Au-based casting alloys in polyvinylpyrrolidone-iodine solution.

    Science.gov (United States)

    Takasusuki, Norio; Ida, Yusuke; Hirose, Yukito; Ochi, Morio; Endo, Kazuhiko

    2013-01-01

    The corrosion and tarnish behaviors of two Au-based casting alloys (ISO type 1 and type 4 Au alloys) and their constituent pure metals, Au, Ag, Cu, Pt, and Pd in a polyvinylpyrrolidone-iodine solution were examined. The two Au alloys actively corroded, and the main anodic reaction for both was dissolution of Au as AuI₂(-). The amount of Au released from the ISO type 1 Au alloy was significantly larger than that from the ISO type 4 Au alloy (Palloy exhibited higher susceptibility to tarnishing than the type 4 alloy. The corrosion forms of the two Au alloys were found to be completely different, i.e., the type 1 alloy exhibited the corrosion attack over the entire exposed surface with a little irregularity whereas the type 4 alloy exhibited typical intergranular corrosion, which was caused by local cells produced by segregation of Pd and Pt.

  17. Activation analysis for platinum in gold and metals of the platinum group through 199Au

    International Nuclear Information System (INIS)

    Foerster, H.

    1976-01-01

    Platinum was determined in gold and in metals of the platinum group through 199 Au by activation analysis. The matrix was separated at the end of irradiation before the daughter nuclide was formed. Gold was separated by extraction with MIBK from 1

  18. Heavy metals contamination and their risk assessment around the abandoned base metals and Au-Ag mines in Korea

    Science.gov (United States)

    Chon, Hyo-Taek

    2017-04-01

    Heavy metals contamination in the areas of abandoned Au-Ag and base metal mines in Korea was investigated in order to assess the level of metal pollution, and to draw general summaries about the fate of toxic heavy metals in different environments. Efforts have been made to compare the level of heavy metals, chemical forms, and plant uptake of heavy metals in each mine site. In the base-metals mine areas, significant levels of Cd, Cu, Pb and Zn were found in mine dump soils developed over mine waste materials and tailings. Leafy vegetables tend to accumulate heavy metals(in particular, Cd and Zn) higher than other crop plants, and high metal concentrations in rice crops may affect the local residents' health. In the Au-Ag mining areas, arsenic would be the most characteristic contaminant in the nearby environment. Arsenic and heavy metals were found to be mainly associated with sulfide gangue minerals, and the mobility of these metals would be enhanced by the effect of continuing weathering and oxidation. According to the sequential extraction of metals in soils, most heavy metals were identified as non-residual chemical forms, and those are very susceptible to the change of ambient conditions of a nearby environment. The concept of pollution index(PI) of soils gives important information on the extent and degree of multi-element contamination, and can be applied to the evaluation of mine soils before their agricultural use and remediation. The risk assessment process comprising exposure assessment, dose-response assessment, and risk characterization was discussed, and the results of non-cancer risk of As, Cd, and Zn, and those of cancer risk of As were suggested.

  19. Comparison of Au and Ag nanoshells' metal-enhanced fluorescence

    International Nuclear Information System (INIS)

    Liaw, Jiunn-Woei; Chen, Huang-Chih; Kuo, Mao-Kuen

    2014-01-01

    The average enhancement factors of Au and Ag nanoshells (NSs) were analyzed theoretically to compare their overall performances on metal-enhanced fluorescence. We used the Mie theory and dyadic Green's functions to calculate the excitation rate and apparent quantum yield of NS interacting with a plane wave and a dipole, respectively, and then to obtain the enhancement factor. Moreover, the average enhancement factor (AEF) of NS on the fluorescence of a nearby molecule was obtained by averaging all possible orientations and locations of the molecule with a constant distance from NS. Our results show that the maximum AEF of Au NS occurs at the wavelength of the dipole mode, which is broadband. In contrast, the maximum AEF of Ag NS is at the narrowband quadrupole mode. In addition, the Stokes shift effect on AEF was studied for Au and Ag NSs. - Highlights: • The average enhancement factors of Au and Ag nanoshells were analyzed theoretically. • The maximum AEF of Au NS occurs at the wavelength of the dipole mode. • The maximum AEF of Ag NS is at the narrowband quadrupole mode. • The Stokes shift effect on AEF is discussed for Au and Ag NSs

  20. A label-free electrochemical immunosensor based on the novel signal amplification system of AuPdCu ternary nanoparticles functionalized polymer nanospheres.

    Science.gov (United States)

    Yan, Qin; Yang, Yuying; Tan, Zhaoling; Liu, Qing; Liu, Hui; Wang, Ping; Chen, Lei; Zhang, Daopeng; Li, Yueyun; Dong, Yunhui

    2018-04-30

    A sensitive label-free electrochemical immunosensor was designed using a novel signal amplification system for quantitative detecting hepatitis B surface antigen (HBsAg). Nitrogen-doped graphene quantum dots (N-GQDs) supported surfactant-free AuPdCu ternary nanoparticles (AuPdCu/N-GQDs), which featured with good conductivity and excellent catalytic properties for the reduction of hydrogen peroxide (H 2 O 2 ), was synthesized by a simple and benign hydrothermal procedure. At the same time, the electroactive polymer nanospheres (PS) was synthesized by infinite coordination polymers of ferrocenedicarboxylic acid, which could play as carrier and electronic mediator to load AuPdCu/N-GQDs. The PS not only improved the ability to load antibodies because of the good biocompatibility, but also accelerated electron transport of the electrode interface attribute to plentiful ferrocene unit. Thus, the prepared AuPdCu/N-GQDs@PS has abilities of good biocompatibility, catalytic activity and electrical conductivity to be applied as transducing materials to amplify electrochemical signal in detection of HBsAg. Under optimal conditions, the fabricated immunosensor exhibited high sensitivity and stability in the detection of HBsAg. A linear relationship between current signals and the concentrations of HBsAg was obtained in the range from 10fg/mL to 50ng/mL and the detection limit of HBsAg was 3.3fg/mL (signal-to-noise ratio of 3). Moreover, the designed immunosensor with excellent selectivity, reproducibility and stability shows excellent performance in detection of human serum samples. Furthermore, this label-free electrochemical immunosensor has promising application in clinical diagnosis of HBsAg. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Porobova, Svetlana, E-mail: porobova.sveta@yandex.ru; Loskutov, Oleg, E-mail: lom58@mail.ru [Tomsk State University of Architecture and Building, Russia, Tomsk, 2 Solyanaya sq, Tomsk, 634003 (Russian Federation); Markova, Tat’jana, E-mail: patriot-rf@mail.ru [Siberian State Industrial University. 42 Kirov St., Novokuznetsk, 654007 (Russian Federation); Klopotov, Vladimir, E-mail: vdklopotov@mail.ru [Research Tomsk Polytechnic University, 30 Lenin Ave., Tomsk, 634050 (Russian Federation); Klopotov, Anatoliy, E-mail: klopotovaa@tsuab.ru [Tomsk State University of Architecture and Building, Russia, Tomsk, 2 Solyanaya sq, Tomsk, 634003 (Russian Federation); National Research Tomsk State University, 36, Lenin Ave., Tomsk, 634050 (Russian Federation); Vlasov, Viktor, E-mail: vik@tsuab.ru [Tomsk State University of Architecture and Building, Russia, Tomsk, 2 Solyanaya sq, Tomsk, 634003 (Russian Federation); Research Tomsk Polytechnic University, 30 Lenin Ave., Tomsk, 634050 (Russian Federation)

    2016-01-15

    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.

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

    DEFF Research Database (Denmark)

    Andersen, O. Krogh

    1970-01-01

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

  3. Enzyme-free electrochemical immunosensor configured with Au-Pd nanocrystals and N-doped graphene sheets for sensitive detection of AFP.

    Science.gov (United States)

    Zhao, Lifang; Li, Songjun; He, Jing; Tian, Guihong; Wei, Qin; Li, He

    2013-11-15

    A novel electrochemical immunosensor capable of enzyme-free detection of alpha fetoprotein (AFP) is reported. This immunosensor was fabricated in a sandwich-like format where catalytic Au-Pd nanocrystals and highly conductive N-doped graphene sheets were incorporated. The significant catalysis by Au-Pd nanocrystals toward hydrogen peroxide, along with the increased electron transfer by graphene sheets, caused signal generation and increased sensitivity, which enables the enzyme-free detection of AFP. With a low detection limit at 0.005 ng mL(-1), this novel immunosensor worked well over the broad linear range of 0.05-30 ng mL(-1). Unlike previously reported enzyme-based electrochemical immunosensors, which often involve the complicated steps for enzyme loading and necessary treatments to keep the activity of enzyme, this novel immunosensor is simple in nature and employed catalytic Au-Pd nanoparticles and highly conductive graphene, which thus enables reliable and sensitive detection for clinic usage. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Fatigue and corrosion of a Pd-based bulk metallic glass in various environments

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, L.Y. [East Los Angeles College, Monterey Park, CA 91754 (United States); Roberts, S.N. [Keck Laboratory of Materials Science, California Institute of Technology, Pasadena, CA 91125 (United States); Baca, N. [Department of Chemistry and Biochemistry, California State University Northridge, Northridge, CA 91330 (United States); Wiest, A. [Naval Surface Warfare Center, Norco, CA (United States); Garrett, S.J. [Department of Chemistry and Biochemistry, California State University Northridge, Northridge, CA 91330 (United States); Conner, R.D., E-mail: rdconner@csun.edu [Department of Manufacturing Systems Engineering and Management, California State University Northridge, 18111 Nordhoff St., Mail Code 8295, Northridge, CA 91330 (United States)

    2013-10-15

    Bulk metallic glasses (BMGs) possess attractive properties for biomedical applications, including high strength, hardness and corrosion resistance, and low elastic modulus. In this study, we conduct rotating beam fatigue tests on Pd{sub 43}Ni{sub 10}Cu{sub 27}P{sub 20} bulk metallic glass in air and Eagle's medium (EM) and measure the corrosive resistance of the alloy by submersion in acidic and basic electrolytes. Fatigue results are compared to those of commonly used biometals in EM. Rotating beam fatigue tests conducted in air and in Eagle's medium show no deterioration in fatigue properties in this potentially corrosive environment out to 10{sup 7} cycles. A specimen size effect is revealed when comparing fatigue results to those of a similar alloy of larger minimum dimensions. Corrosion tests show that the alloy is not affected by highly basic (NaOH) or saline (NaCl) solutions, nor in EM, and is affected by chlorinated acidic solutions (HCl) to a lesser extent than other commonly used biometals. Corrosion in HCl initiates with selective leaching of late transition metals, followed by dissolution of Pd. - Highlights: • Fatigue limit of 600 MPa with no deterioration when exposed to Eagle's medium. • Fatigue shows sample size effect. • Pd-based BMG is unaffected by saline or strong basic solutions. • Pd-based BMG is substantially more resistant to chlorinated acids than CoCrMo, 316 L Stainless, or Ti6Al4V alloys. • Corrosion shows selective leaching of late transition metals, followed by Pd and P.

  5. Extracellular Saccharide-Mediated Reduction of Au3+ to Gold Nanoparticles: New Insights for Heavy Metals Biomineralization on Microbial Surfaces.

    Science.gov (United States)

    Kang, Fuxing; Qu, Xiaolei; Alvarez, Pedro J J; Zhu, Dongqiang

    2017-03-07

    Biomineralization is a critical process controlling the biogeochemical cycling, fate, and potential environmental impacts of heavy metals. Despite the indispensability of extracellular polymeric substances (EPS) to microbial life and their ubiquity in soil and aquatic environments, the role played by EPS in the transformation and biomineralization of heavy metals is not well understood. Here, we used gold ion (Au 3+ ) as a model heavy metal ion to quantitatively assess the role of EPS in biomineralization and discern the responsible functional groups. Integrated spectroscopic analyses showed that Au 3+ was readily reduced to zerovalent gold nanoparticles (AuNPs, 2-15 nm in size) in aqueous suspension of Escherichia coli or dissolved EPS extracted from microbes. The majority of AuNPs (95.2%) was formed outside Escherichia coli cells, and the removal of EPS attached to cells pronouncedly suppressed Au 3+ reduction, reflecting the predominance of the extracellular matrix in Au 3+ reduction. XPS, UV-vis, and FTIR analyses corroborated that Au 3+ reduction was mediated by the hemiacetal groups (aldehyde equivalents) of reducing saccharides of EPS. Consistently, the kinetics of AuNP formation obeyed pseudo-second-order reaction kinetics with respect to the concentrations of Au 3+ and the hemiacetal groups in EPS, with minimal dependency on the source of microbial EPS. Our findings indicate a previously overlooked, universally significant contribution of EPS to the reduction, mineralization, and potential detoxification of metal species with high oxidation state.

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

    DEFF Research Database (Denmark)

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

    2007-01-01

    The glass-transition behavior of Pd40Cu30Ni10P20 bulk metallic glass was investigated by differential scanning calorimetry (DSC) and X-ray powder diffraction (XRD). The effect of pressure on the crystallization behavior of Pd40Cu30Ni10P20 bulk glass was studied by in situ high-pressure and high...

  7. Determination of Au, Pt, Pd in gold ore mineral raw materials by stripping voltammetry

    Directory of Open Access Journals (Sweden)

    Kolpakova N.A.

    2016-01-01

    Full Text Available The paper considers the possibilities of use of the method of stripping voltammetry for finding platinum metals in mineral gold and ore raw material. A review of new options of electro-concentration of platinum metals on the surface of graphite electrode with the following sediment electro-oxidation and receipt of an analytical signal is presented: platinum finding was carried out by picks of selective electro-oxidation of iridium from intermetallic compound with platinum; gold finding was carried out by picks of gold electro-oxidation on the surface of graphite electrode modified by bismuth; palladium finding was performed by picks of palladium electro-oxidation on the surface of graphite electrode. 1M HCL solution was selected as a supporting electrolyte. Gold and hydrogen elimination on the process of palladium electro-oxidation was performed by means of UV irradiation of solution in the process of electro-concentration of palladium sediment. Gold, platinum and palladium determination was carried out in mineral gold and ore raw material of Verkhneamylskiy gold and ore district.

  8. Deactivation of Pd particles supported on Nb 2O 5/Cu 3Au(1 0 0): SFG and TPD studies from UHV to 100 mbar

    Science.gov (United States)

    Höbel, Frank; Bandara, Athula; Rupprechter, Günther; Freund, Hans-Joachim

    2006-02-01

    Structural changes that occur on Pd-Nb 2O 5/Cu 3Au(1 0 0) model catalysts upon thermal annealing were followed by sum frequency generation (SFG) and temperature-programmed desorption (TPD) using CO as probe molecule. SFG experiments were performed both under ultrahigh vacuum and mbar pressure. Heating the catalyst to temperatures above 300 K lead to an irreversible 50% decrease in the CO adsorption capacity and modified the remaining adsorption sites. Alterations of the phase between resonant and non-resonant SFG signals upon annealing indicate a change in the electronic structure of the surface, which excludes Pd sintering or migration of Nb 2O 5 over Pd particles to cause the observed effect and rather suggests the formation of "mixed Pd-NbO x" sites. The same changes in surface properties also occur during CO hydrogenation at 1 bar and high temperature, pointing to an involvement of "mixed Pd-NbO x" sites in catalytic reactions.

  9. Pressure effect on crystallization temperature in Zr70Pd30 metallic glass

    DEFF Research Database (Denmark)

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

    2004-01-01

    The pressure effect on amorphous-to-quasicrystalline-to-intermetallic phase transformations in a Zr70Pd30 metallic glass has been investigated by in situ x-ray diffraction measurements using synchrotron radiation. It is found that the glass crystallizes in two steps: (1) amorphous...... temperature for the formation of quasicrystals has been further discussed with the nucleation theory. ©2004 American Institute of Physics....

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

    International Nuclear Information System (INIS)

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

    2010-01-01

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

  11. Determination of the compositions of the DIGM zone in nanocrystalline Ag/Au and Ag/Pd thin films by secondary neutral mass spectrometry

    Directory of Open Access Journals (Sweden)

    Gábor Y. Molnár

    2016-03-01

    Full Text Available 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.

  12. CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO₂ Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al₂O₃.

    Science.gov (United States)

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

    2015-12-15

    The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO₂ and Pt/α-Al₂O₃ catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO₂, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H₂, while H₂ combustion was activated by repeated exposure to H₂ gas during the periodic gas test. Selective CO sensing of the micro-TGS against H₂ was attempted using a double catalyst structure with 0.3-30 wt% Pt/α-Al₂O₃ as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al₂O₃ catalyst, by cancelling out the combustion heat from the AuPtPd/SnO₂ catalyst. In addition, the AuPtPd/SnO₂ and 0.3 wt% Pt/α-Al₂O₃ double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H₂.

  13. Electron-positron pair production in ultrarelativistic atomic collisions: 6.4 TeV S16+ with Au, Pd and Al

    International Nuclear Information System (INIS)

    Datz, S.; Vane, C.R.; Dittner, P.F.; Krause, H.F.; Schuch, R.; Gao, H.; Hutton, R.

    1994-01-01

    Angular and momentum distributions have been measured for electron-positron pairs created in peripheral collisions of 6.4 TeV bare sulfur ions with thin targets of Al, Pd, and Au. Singly- and doubly-differential cross sections are presented for 1--17 MeV/c electrons and positrons detected independently and in coincidence as pairs. Various physical parameters are deduced from the coincident electron and positron data, including probability distributions for the pair transverse momentum, the pair total energy, and the positron fraction of the pair energy

  14. Magnetism in ordered metallic perovskite compound GdPd3BxC1-x

    International Nuclear Information System (INIS)

    Pandey, Abhishek; Mazumdar, Chandan; Ranganathan, R.; Dattagupta, S.

    2009-01-01

    We report results of dc-magnetization, ac-susceptibility and magnetoresistance measurements on crystalline metallic-perovskite compounds GdPd 3 B x C 1-x (x=0.25, 0.50, 0.75 and 1.00) and the parent cubic compound GdPd 3 . The interest in these materials stems from the observation of negative temperature coefficient of resistance and negative thermal expansion in some of the members of this series. In the present study, we show that by substitution of non-magnetic elements, boron and carbon, the nature of the magnetic interaction can be varied from dominating ferromagnetic to antiferromagnetic and finally to a canted magnetic structure without altering the crystal symmetry of the compounds. The variation of magnetic interaction by modifying the lattice parameter resembles Ruderman-Kittel-Kasuya-Yosida (RKKY) oscillations.

  15. Vibration-accelerated activation of flow units in a Pd-based bulk metallic glass

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ning, E-mail: hslining@mail.hust.edu.cn [School of Materials Science and Engineering, and State Key Laboratory of Material Processing and Die & Mould Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Liu, Ze [Department of Engineering Mechanics, School of Civil Engineering, Wuhan University, Wuhan 430072 (China); Wang, Xinyun [School of Materials Science and Engineering, and State Key Laboratory of Material Processing and Die & Mould Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Zhang, Meng [Institute of Advanced Wear & Corrosion Resistant and Functional Materials, Jinan University, Guangzhou 510632 (China)

    2017-04-24

    Controlled activation of flow units and in-situ characterization of mechanical properties in metallic glasses are facing challenges thus far. Here, vibrational loading is introduced through nanoscale dynamic mechanical analysis technique to probe vibration-accelerated atomic level flow that plays a crucial role in the mechanical behavior of metallic glasses. The intriguing finding is that high vibrational frequency induces deep indentation depth, prominent pop-in events on load–depth curves and low storage modulus, exhibiting a vibration-facilitated activation of flow units in Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} metallic glass. Theoretical analysis revealed that vibration-moderated activation time-scale accelerate the activation of flow units and responsible for the above scenario.

  16. Enhancing the biofuel upgrade performance for Pd nanoparticles via increasing the support hydrophilicity of metal-organic frameworks.

    Science.gov (United States)

    Sun, Qi; Chen, Meng; Aguila, Briana; Nguyen, Nicholas; Ma, Shengqian

    2017-09-08

    In this work, the influence of the hydrophilic/hydrophobic nature of metal-organic framework (MOF) materials on the catalytic performance of supported Pd nanoparticles for biofuel upgrade was studied. We show that the introduction of hydrophilic groups on a MOF can greatly enhance the performance of the resultant catalyst. Specifically, Pd nanoparticles supported on MIL-101-SO 3 Na with superhydrophilicity (Pd/MIL-101-SO 3 Na) far outperforms pristine MIL-101 and the benchmark catalyst Pd/C in the hydrodeoxygenation reaction of vanillin, a model component of pyrolysis oil derived from the lignin fraction. This is attributed to a favorable mode of adsorption of the highly water soluble reactants on the more hydrophilic support in the vicinity of the catalytically active Pd nanoparticles, thereby promoting their transformation.

  17. Metadislocation reactions and metadislocation networks in the complex metallic alloy ξ'-Al-Pd-Mn

    International Nuclear Information System (INIS)

    Heggen, Marc; Feuerbacher, Michael

    2005-01-01

    Metadislocations are novel structural defects firstly observed in the complex metallic alloy ξ'-Al-Pd-Mn. We present a transmission electron microscopy study on metadislocation reactions and networks. It is shown that metadislocations can dissociate into partials, which leads to a decrease of the elastic line energy. Connected groups of metadislocations can assume large and complex network structures with large total Burgers vectors. However, the local elastic strain at the individual metadislocation cores as well as the fault-plane energies remain small. By this mechanism, effective large Burgers vectors, contributing massively to plastic strain, can be distributed over a large portion of the material

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

    Science.gov (United States)

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

    2015-11-01

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

  19. Metal-organic extended 2D structures: Fe-PTCDA on Au(111)

    International Nuclear Information System (INIS)

    Alvarez, Lucia; Caillard, Renaud; MartIn-Gago, Jose A; Mendez, Javier; Pelaez, Samuel; Serena, Pedro A

    2010-01-01

    In this work we combine organic molecules of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) with iron atoms on an Au (111) substrate in ultra-high vacuum conditions at different temperatures. By means of scanning tunnelling microscopy (STM) we study the formation of stable 2D metal-organic structures. We show that at certain growth conditions (temperature, time and coverage) stable 'ladder-like' nanostructures are obtained. These are the result of connecting together two metal-organic chains through PTCDA molecules placed perpendicularly, as rungs of a ladder. These structures, stable up to 450 K, can be extended in a 2D layer covering the entire surface and presenting different rotation domains. STM images at both polarities show a contrast reversal between the two molecules at the unit cell. By means of density functional theory (DFT) calculations, we confirm the stability of these structures and that their molecular orbitals are placed separately at the different molecules.

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

    Science.gov (United States)

    Ray, Siba P.; Liu, Xinghua

    2000-01-01

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

  1. Au279(SR)84: The Smallest Gold Thiolate Nanocrystal That Is Metallic and the Birth of Plasmon.

    Science.gov (United States)

    Sakthivel, Naga Arjun; Stener, Mauro; Sementa, Luca; Fortunelli, Alessandro; Ramakrishna, Guda; Dass, Amala

    2018-03-15

    We report a detailed study on the optical properties of Au 279 (SR) 84 using steady-state and transient absorption measurements to probe its metallic nature, time-dependent density functional theory (TDDFT) studies to correlate the optical spectra, and density of states (DOS) to reveal the factors governing the origin of the collective surface plasmon resonance (SPR) oscillation. Au 279 is the smallest identified gold nanocrystal to exhibit SPR. Its optical absorption exhibits SPR at 510 nm. Power-dependent bleach recovery kinetics of Au 279 suggests that electron dynamics dominates its relaxation and it can support plasmon oscillations. Interestingly, TDDFT and DOS studies with different tail group residues (-CH 3 and -Ph) revealed the important role played by the tail groups of ligands in collective oscillation. Also, steady-state and time-resolved absorption for Au 36 , Au 44 , and Au 133 were studied to reveal the molecule-to-metal evolution of aromatic AuNMs. The optical gap and transient decay lifetimes decrease as the size increases.

  2. N-Heterocyclic carbenes on close-packed coinage metal surfaces: bis-carbene metal adatom bonding scheme of monolayer films on Au, Ag and Cu.

    Science.gov (United States)

    Jiang, Li; Zhang, Bodong; Médard, Guillaume; Seitsonen, Ari Paavo; Haag, Felix; Allegretti, Francesco; Reichert, Joachim; Kuster, Bernhard; Barth, Johannes V; Papageorgiou, Anthoula C

    2017-12-01

    By means of scanning tunnelling microscopy (STM), complementary density functional theory (DFT) and X-ray photoelectron spectroscopy (XPS) we investigate the binding and self-assembly of a saturated molecular layer of model N -heterocyclic carbene (NHC) on Cu(111), Ag(111) and Au(111) surfaces under ultra-high vacuum (UHV) conditions. XPS reveals that at room temperature, coverages up to a monolayer exist, with the molecules engaged in metal carbene bonds. On all three surfaces, we resolve similar arrangements, which can be interpreted only in terms of mononuclear M(NHC) 2 (M = Cu, Ag, Au) complexes, reminiscent of the paired bonding of thiols to surface gold adatoms. Theoretical investigations for the case of Au unravel the charge distribution of a Au(111) surface covered by Au(NHC) 2 and reveal that this is the energetically preferential adsorption configuration.

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

    Directory of Open Access Journals (Sweden)

    Huy Binh Do

    2017-08-01

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

  4. Effects of composition and microstructure of Pd-Cu-Si metallic glassy alloy thin films on hydrogen absorbing properties

    International Nuclear Information System (INIS)

    Kajita, Susumu; Kohara, Shinji; Onodera, Yohei; Fukunaga, Toshiharu; Matsubara, Eiichiro

    2011-01-01

    Thin films of Pd-Cu-Si metallic glassy alloys for a hydrogen sensor were fabricated by a sputtering method. In order to find out the effect of the composition and the microstructure of them on the hydrogen absorbing property (the H 2 response), the structural parameters based on the short-range order (SRO) were measured. Additionally, the change of the structural parameters with hydrogen absorption was measured, and the correlations of the change with the H 2 response and the hydrogen induced linear expansion coefficient (LEC) were examined. The H 2 response decreased with increases in Si content and the structural parameters. These results can be explained by the positive effects of Si content and the structural parameters on the formation of a trigonal prism which is a structural unit of Pd-based amorphous alloys, and by the negative effect of the trigonal prism on absorbing hydrogen. From the observation of the elongation of the Pd-Pd atomic distance with absorbing hydrogen, H atoms are supposed to occupy the space between Pd atoms. The amount of the change in the Pd-Pd atomic distance showed the positive correlations with the H 2 response and the LEC. (author)

  5. Efficient Aerobic Oxidation of 5-Hydroxymethylfurfural in Aqueous Media with Au-Pd Supported on Zinc Hydroxycarbonate

    DEFF Research Database (Denmark)

    Gui, Zhenyou; Cao, Wenrong; Shunmugavel, Saravanamurugan

    2016-01-01

    Bimetallic catalysts with Au–Pd supported on zinc hydroxycarbonate (ZOC) were synthesized by a simple deposition–precipitation method and analyzed by transmission electron microscopy to have a narrow-size distribution of predominantly 1–2 nm. The prepared Au–Pd/ZOC catalysts exhibited excellent...... activity towards 5-hydoxymethylfurfural (HMF) oxidation in water in the presence of the base NaHCO3 at benign conditions of 80 °C and 3 bar O2, resulting in quantitative yield of 2,5-furandicarboxylic acid (FDCA). The addition of base not only enhanced the yield of FDCA but also stabilized the support ZOC...

  6. Pd surface functionalization of 3D electroformed Ni and Ni-Mo alloy metallic nanofoams for hydrogen production

    Science.gov (United States)

    Petica, A.; Brincoveanu, O.; Golgovici, F.; Manea, A. C.; Enachescu, M.; Anicai, L.

    2018-03-01

    The paper presents some experimental results regarding the functionalization of 3D electroformed Ni and Ni-Mo alloy nanofoams with Pd nanoclusters, as potential cathodic materials suitable for HER during seawater electrolysis. The electrodeposition from aqueous electrolytes containing NiCl2 and NH4Cl has been applied to prepare the 3D Ni nanofoams. Ni-Mo alloys have been electrodeposited involving aqueous ammonium citrate type electrolytes. Pd surface functionalization has been performed using both electroless and electrochemical procedures. Pd content varied in the range of 0.5 – 8 wt.%, depending on the applied procedure and the operation conditions. The use of a porous structure associated with alloying element (i.e. Mo) and Pd surface functionalization facilitated enhanced performances from HER view point in seawater electrolyte (lower Tafel slopes). The determined Tafel slope values ranged from 123 to 105 mV.dec-1, suggesting the Volmer step as rate determining step. The improvement of the HER catalytic activity may be ascribed to a synergistic effect between the high real active area of the 3D electroformed metallic substrate, Ni alloying with a left transition metal and surface modification using Pd noble metal.

  7. Palladium and gold removal and recovery from precious metal solutions and electronic scrap leachates by Desulfovibrio desulfuricans.

    Science.gov (United States)

    Creamer, Neil J; Baxter-Plant, Victoria S; Henderson, John; Potter, M; Macaskie, Lynne E

    2006-09-01

    Biomass of Desulfovibrio desulfuricans was used to recover Au(III) as Au(0) from test solutions and from waste electronic scrap leachate. Au(0) was precipitated extracellularly by a different mechanism from the biodeposition of Pd(0). The presence of Cu(2+) ( approximately 2000 mg/l) in the leachate inhibited the hydrogenase-mediated removal of Pd(II) but pre-palladisation of the cells in the absence of added Cu(2+) facilitated removal of Pd(II) from the leachate and more than 95% of the Pd(II) was removed autocatalytically from a test solution supplemented with Cu(II) and Pd(II). Metal recovery was demonstrated in a gas-lift electrobioreactor with electrochemically generated hydrogen, followed by precipitation of recovered metal under gravity. A 3-stage bioseparation process for the recovery of Au(III), Pd(II) and Cu(II) is proposed.

  8. Chain formation of metal atoms

    DEFF Research Database (Denmark)

    Bahn, Sune Rastad; Jacobsen, Karsten Wedel

    2001-01-01

    The possibility of formation of single-atomic chains by manipulation of nanocontacts is studied for a selection of metals (Ni, Pd, Pt, Cu, Ag, Au). Molecular dynamics simulations show that the tendency for chain formation is strongest for Au and Pt. Density functional theory calculations indicate...... that the metals which form chains exhibit pronounced many-atom interactions with strong bonding in low coordinated systems....

  9. Manipulating the kinetics of seeded growth for edge-selective metal deposition and the formation of concave au nanocrystals.

    Science.gov (United States)

    Laskar, Moitree; Zhong, Xiaolan; Li, Zhi-Yuan; Skrabalak, Sara E

    2013-10-01

    By manipulating the kinetics of seeded growth through judicious control of reaction conditions, edge-selective metal deposition can be achieved to synthesize new Au nanostructures with face-centered concavities, referred to herein as Au overgrown trisoctahedra. These nanostructures display higher sensitivity to changes in refractive index compared to both Au traditional trisoctahedra and the Au nanocube seeds from which they are grown. Often, concave nanostructures are achieved by selective etching processes or corner-selective overgrowth and adopt a stellated profile rather than a profile with face-centered concavities. The presented results illustrate another strategy toward concave nanostructures and can facilitate the synthesis of new concave nanostructures for applications in catalysis and chemical sensing. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Colloidal Au and Au-alloy catalysts for direct borohydride fuel cells: Electrocatalysis and fuel cell performance

    Science.gov (United States)

    Atwan, Mohammed H.; Macdonald, Charles L. B.; Northwood, Derek O.; Gyenge, Elod L.

    Supported colloidal Au and Au-alloys (Au-Pt and Au-Pd, 1:1 atomic ratio) on Vulcan XC-72 (with 20 wt% metal load) were prepared by the Bönneman method. The electrocatalytic activity of the colloidal metals with respect to borohydride electro-oxidation for fuel cell applications was investigated by voltammetry on static and rotating electrodes, chronoamperometry, chronopotentiometry and fuel cell experiments. The fundamental electrochemical techniques showed that alloying Au, a metal that leads to the maximum eight-electron oxidation of BH 4 -, with Pd or Pt, well-known catalysts of dehydrogenation reactions, improved the electrode kinetics of BH 4 - oxidation. Fuel cell experiments corroborated the kinetic studies. Using 5 mg cm -2 colloidal metal load on the anode, it was found that Au-Pt was the most active catalyst giving a cell voltage of 0.47 V at 100 mA cm -2 and 333 K, while under identical conditions the cell voltage using colloidal Au was 0.17 V.

  11. Colloidal Au and Au-alloy catalysts for direct borohydride fuel cells: Electrocatalysis and fuel cell performance

    Energy Technology Data Exchange (ETDEWEB)

    Atwan, Mohammed H.; Northwood, Derek O. [Department of Mechanical, Auto and Materials Engineering, University of Windsor, Windsor (Canada N9B 3P4); Macdonald, Charles L.B. [Department of Chemistry and Biochemistry, University of Windsor, Windsor (Canada N9B 3P4); Gyenge, Elod L. [Department of Chemical and Biological Engineering, The University of British Columbia, Vancouver, BC (Canada V6T 1Z4)

    2006-07-14

    Supported colloidal Au and Au-alloys (Au-Pt and Au-Pd, 1:1 atomic ratio) on Vulcan XC-72 (with 20wt% metal load) were prepared by the Bonneman method. The electrocatalytic activity of the colloidal metals with respect to borohydride electro-oxidation for fuel cell applications was investigated by voltammetry on static and rotating electrodes, chronoamperometry, chronopotentiometry and fuel cell experiments. The fundamental electrochemical techniques showed that alloying Au, a metal that leads to the maximum eight-electron oxidation of BH{sub 4}{sup -}, with Pd or Pt, well-known catalysts of dehydrogenation reactions, improved the electrode kinetics of BH{sub 4}{sup -} oxidation. Fuel cell experiments corroborated the kinetic studies. Using 5mgcm{sup -2} colloidal metal load on the anode, it was found that Au-Pt was the most active catalyst giving a cell voltage of 0.47V at 100mAcm{sup -2} and 333K, while under identical conditions the cell voltage using colloidal Au was 0.17V. (author)

  12. Evidence of polymorphous amorphous-to-quasicrystalline phase transformation in Zr66.7Pd33.3 metallic glass

    DEFF Research Database (Denmark)

    Jiang, Jianzhong; Saksl, K.; Saida, J.

    2002-01-01

    The amorphous-to-quasicrystalline phase transformation and the pressure effect on the transformation in a Zr66.7Pd33.3 metallic glass have been investigated by in situ x-ray diffraction measurements using synchrotron radiation. It is found that the transformation is a polymorphous reaction...

  13. CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO2 Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al2O3

    Science.gov (United States)

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

    2015-01-01

    The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO2 and Pt/α-Al2O3 catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO2, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H2, while H2 combustion was activated by repeated exposure to H2 gas during the periodic gas test. Selective CO sensing of the micro-TGS against H2 was attempted using a double catalyst structure with 0.3–30 wt% Pt/α-Al2O3 as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al2O3 catalyst, by cancelling out the combustion heat from the AuPtPd/SnO2 catalyst. In addition, the AuPtPd/SnO2 and 0.3 wt% Pt/α-Al2O3 double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H2. PMID:26694397

  14. Ag Isotopic Evolution of the Mantle During Accretion: New Constraints from Pd and Ag Metal-Silicate Partitioning

    Science.gov (United States)

    Righter, K.; Schonbachler, M.

    2018-01-01

    Decay of (sup 107) Pd to (sup 107) Ag has a half-life of 6.5 times 10 (sup 6) mega-annums. Because these elements are siderophile but also volatile, they offer potential constraints on the timing of core formation as well as volatile addition. Initial modelling has shown that the Ag isotopic composition of the bulk silicate Earth (BSE) can be explained if accretion occurs with late volatile addition. These arguments were tested for sensitivity for pre-cursor Pd/Ag contents, and for a fixed Pd/Ag ratio of the BSE of 0.1. New Ag and Pd partitioning data has allowed a better understanding of the partitioning behavior of Pd and Ag during core formation. The effects of S, C and Si, and the effect of high temperature and pressure has been evaluated. We can now calculate D(Ag) and D(Pd) over the wide range of PT conditions and variable metallic liquid compositions that are known during accretion. We then use this new partitioning information to revisit the Ag isotopic composition of the BSE during accretion.

  15. A GREENER SYNTHESIS OF CORE (FE, CU)-SHELL (AU, PT, PD AND AG) NANOCRYSTALS USING AQUEOUS VITAMIN C

    Science.gov (United States)

    A greener method to fabricate the novel core (Fe and Cu)-shell (noble metals) metal nanocrystals using aqueous ascorbic acid (vitamin C) is described. Transition metal salts such as Cu and Fe were reduced using ascorbic acid, a benign naturally available antioxidant, and then add...

  16. Semiconducting La2AuP3, the metallic conductor Ce2AuP3, and other rare-earth gold phosphides Ln2AuP3 with two closely related crystal structures

    International Nuclear Information System (INIS)

    Eschen, M.; Kotzyba, G.; Kuennen, B.; Jeitschko, W.

    2001-01-01

    The compounds Ln 2 AuP 3 were synthesized by reaction of the elemental components in evacuated silica tubes. Their crystal structures were determined from single-crystal diffractometer data. The compounds with Ln = La, Ce, and Pr crystallize with an orthorhombic U 2 NiC 3 type structure (Pnma, Z = 4). The structure refinement for Ce 2 AuP 3 resulted in a = 774.14(6) pm, b = 421.11(4) pm, c = 1612.3(1) pm, R = 0.019 for 1410 structure factors and 38 variable parameters. For Pr 2 AuP 3 a residual of R = 0.024 was obtained. Nd 2 AuP 3 crystallizes with a monoclinic distortion of this structure: P2 1 /c, Z = 4, a = 416.14(4) pm, b = 768.87(6) pm, c = 1647.1(2) pm, β = 104.06(1) , R = 0.022 for 1361 F values and 56 variables. The near-neighbor coordinations of the two structures are nearly the same. In both structures the gold and phosphorus atoms form two-dimensionally infinite nets, where the gold atoms are tetrahedrally coordinated by phosphorus atoms with Au-P distances varying between 245.8 and 284.2 pm. Two thirds of the phosphorus atoms form pairs with single-bond distances varying between 217.7 and 218.9 pm. Thus, using oxidation numbers the structures can be rationalized with the formulas (Ln +3 ) 2 [AuP 3 ] -6 and (Ln +3 ) 2 Au +1 (P 2 ) -4 P -3 . Accordingly, La 2 AuP 3 is a diamagnetic semiconductor. Pr 2 AuP 3 is semi-conducting with an antiferromagnetic ground state, showing metamagnetism with a critical field of B c = 0.5(±0.1) T. In contrast, the cerium compound is a metallic conductor, even though its cell volume indicates that the cerium atoms are essentially trivalent, as is also suggested by the ferro- or ferrimagnetic behavior of the compound. (orig.)

  17. Electronic structure of Pd42.5Ni7.5Cu30P20, an excellent bulk metallic glass former: Comparison to the Pd40Ni40P20 reference glass

    International Nuclear Information System (INIS)

    Hosokawa, S.; Sato, H.; Happo, N.; Mimura, K.; Tezuka, Y.; Ichitsubo, T.; Matsubara, E.; Nishiyama, N.

    2007-01-01

    In-house photoemission and inverse-photoemission spectra (PES and IPES) were measured on Pd 42.5 Ni 7.5 Cu 30 P 20 and Pd 40 Ni 40 P 20 bulk metallic glasses in order to clarify the origin of excellent glass-forming ability from the viewpoint of electronic structure. Minima are observed for both the metallic glasses at a slightly higher energy than the Fermi level. Incident photon-energy dependent PES spectra were obtained using synchrotron radiation and the Pd 4d partial density of states (DOS) was estimated from the PES data. Soft X-ray emission spectra were also measured near the Ni and Cu 2p 3/2 absorption edges to evaluate, respectively, the Ni and Cu 3d partial DOS in the valence band. The Pd 4d and the Ni and Cu 3d partials in the conduction band were obtained from X-ray absorption spectra around the Pd 3p 3/2 and Ni and Cu 2p 3/2 absorption edges, respectively. It was found that the Pd 4d partial DOS near the Fermi energy largely decreases and becomes localized by replacing the Ni atoms with the Cu atoms, which may be closely related to the excellent glass-forming ability of the Pd 42.5 Ni 7.5 Cu 30 P 20 bulk metallic glass due to a selective formation of Pd-P covalent bonds

  18. Production of mono- and bimetallic nanoparticles of noble metals by pyrolysis of organic extracts on silicon dioxide

    International Nuclear Information System (INIS)

    Serga, V; Kulikova, L; Cvetkov, A; Krumina, A; Kodols, M; Chornaja, S; Dubencovs, K; Sproge, E

    2013-01-01

    In the present work the influence of the tri-n-octylammonium (Oct 3 NH + ) salt anion (PtCl 6 2- , PdCl 4 2- , AuCl 4 − ) nature on the phase composition and mean size of crystallites of the extract pyrolysis products on the SiO 2 nanopowder has been studied. The XRD phase analysis of the composites (metal loading 2.4 wt.%) made under the same conditions, at the pyrolysis of Pt- and Au-containing extracts has shown the formation of nanoparticles of Pt (d Pt = 15 nm) and Au (d Au = 33 nm), respectively. The end-product of the pyrolysis of the Pd-containing extract has an admixture phase of PdO along with the main metal phase (d Pd = 21 nm). At the preparation of bimetallic particles (Pt-Pd, Pt-Au, Pd-Au) on the SiO 2 nanopowder it has been found that the nanoparticles of the PtPd alloy, Pt and Au or Pd and Au nanoparticles are the products of the thermal decomposition of two-component mixtures of extracts. The investigation of catalytic properties of the produced composites in the reaction of glycerol oxidation by molecular oxygen in alkaline aqueous solutions has shown that all bimetallic composites exhibit catalytic activity in contrast to monometallic ones

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

    International Nuclear Information System (INIS)

    Ezawa, Hirokazu; Miyata, Masahiro; Tatsumi, Kohei

    2014-01-01

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

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

    Science.gov (United States)

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

    2018-03-01

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

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

    Science.gov (United States)

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

    2015-05-28

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

  2. Controlled growth of Au nanoparticles in co-evaporated metal/polymer composite films and their optical and electrical properties

    Science.gov (United States)

    Takele, H.; Schürmann, U.; Greve, H.; Paretkar, D.; Zaporojtchenko, V.; Faupel, F.

    2006-02-01

    Nanocomposite films containing Au nanoparticles embedded in a polymer matrix were prepared by vapour phase co-deposition of Au and polymers (Teflon AF and Poly(α -methylstyrene)) in high vacuum. The microstructure of the composite materials as well as metal content strongly depend on the condensation coefficient of the Au atoms, the deposition rates of the components, the substrate temperature, and the type of polymer matrix. The condensation coefficient, which varies between 0.03 and 1, was determined from energy dispersive X-ray spectrometer (EDX) and surface profilometry. It is shown that the microstructure of nanocomposites (size, size distribution, and interparticle separation of metal clusters), which was determined by transmission electron microscopy, can be controlled by the deposition parameters and the choice of polymer matrix. The optical absorption in the visible region due to the particle plasmon resonance has a strong dependence on the metal filling factor. The correlation between the microstructure of nanocomposites and optical properties, studied using UV-Vis spectroscopy, was also established. Further more, the electrical properties of the composites were studied as a function of the metal volume fraction. It was observed that the nanocomposite films exhibit a percolation threshold at a metal volume fraction of 0.43 and 0.20 for gold nanoclusters in Teflon AF and Poly(α-methylstyrene), respectively.

  3. Gold nanoparticle plasmon resonance in near-field coupled Au NPs layer/Al film nanostructure: Dependence on metal film thickness

    Science.gov (United States)

    Yeshchenko, Oleg A.; Kozachenko, Viktor V.; Naumenko, Antonina P.; Berezovska, Nataliya I.; Kutsevol, Nataliya V.; Chumachenko, Vasyl A.; Haftel, Michael; Pinchuk, Anatoliy O.

    2018-05-01

    We study the effects of coupling between plasmonic metal nanoparticles and a thin metal film by using light extinction spectroscopy. A planar monolayer of gold nanoparticles located near an aluminum thin film (thicknesses within the range of 0-62 nm) was used to analyze the coupling between the monolayer and the thin metal film. SPR peak area increase for polymer coated Au NPs, non-monotonical behavior of the peak area for bare Au NPs, as well as red shift and broadening of SPR at the increase of the Al film thickness have been observed. These effects are rationalized as a result of coupling of the layer of Au NPs with Al film through the field of localized surface plasmons in Au NPs that causes the excitation of collective plasmonic gap mode in the nanostructure. An additional mechanism for bare Au NPs is the non-radiative damping of SPR that is caused by the electrical contact between metal NPs and film.

  4. Promotion Effect of Alkali Metal Hydroxides on Polymer-Stabilized Pd Nanoparticles for Selective Hydrogenation of C–C Triple Bonds in Alkynols

    OpenAIRE

    Nikoshvili, Linda Zh.; Bykov, Alexey V.; Khudyakova, Tatiana E.; Lagrange, Thomas; Héroguel, Florent; Luterbacher, Jeremy S.; Matveeva, Valentina G.; Sulman, Esther M.; Dyson, Paul J.; Kiwi-Minsker, Lioubov

    2017-01-01

    Postimpregnation of Pd nanoparticles (NPs) stabilized within hyper-cross-linked polystyrene with sodium or potassium hydroxides of optimal concentration was found to significantly increase the catalytic activity for the partial hydrogenation of the C–C triple bond in 2-methyl-3-butyn-2-ol at ambient hydrogen pressure. The alkali metal hydroxide accelerates the transformation of the residual Pd(II) salt into Pd(0) NPs and diminishes the reaction induction period. In addition, the selectivity t...

  5. The Close Relationships between the Crystal Structures of MO and MSO 4 (M = Group 10, 11, or 12 Metal), and the Predicted Structures of AuO and PtSO 4

    KAUST Repository

    Derzsi, Mariana; Hermann, Andreas; Hoffmann, Roald; Grochala, Wojciech

    2013-01-01

    The structural relations of (and between) late transition metal monoxides, MO, and monosulfates, MSO4, are analyzed. We show that all of these late transition metal oxides, as well as 4d and 5d metal sulfates, crystallize in distorted rock salt lattices and argue that the distortions are driven by collective first- and/or second order Jahn-Teller effects. The collective Jahn-Teller deformations lead either to tetragonal contraction or (seldom) elongation of the rock salt lattice. On the basis of the rock salt representation of the oxides and sulfates, we show that PdO, CuO, and AgO are metrically related and that the 4d and 5d metal sulfates are close to isostructural with their oxides. These observations guide us towards as yet unknown AuO and PtSO4, for which we predict crystal structures from electronic structure calculations. The structural relations of (and between) late transition metal monoxides, MO, and monosulfates, MSO4, are analyzed. We show that all of these late transition metal oxides, as well as 4d and 5d metal sulfates, crystallize in distorted rock salt lattices and argue that the distortions are driven by collective first- and/or second order Jahn-Teller effects, as quantified by the c′/a′ ratio. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The Close Relationships between the Crystal Structures of MO and MSO 4 (M = Group 10, 11, or 12 Metal), and the Predicted Structures of AuO and PtSO 4

    KAUST Repository

    Derzsi, Mariana

    2013-08-21

    The structural relations of (and between) late transition metal monoxides, MO, and monosulfates, MSO4, are analyzed. We show that all of these late transition metal oxides, as well as 4d and 5d metal sulfates, crystallize in distorted rock salt lattices and argue that the distortions are driven by collective first- and/or second order Jahn-Teller effects. The collective Jahn-Teller deformations lead either to tetragonal contraction or (seldom) elongation of the rock salt lattice. On the basis of the rock salt representation of the oxides and sulfates, we show that PdO, CuO, and AgO are metrically related and that the 4d and 5d metal sulfates are close to isostructural with their oxides. These observations guide us towards as yet unknown AuO and PtSO4, for which we predict crystal structures from electronic structure calculations. The structural relations of (and between) late transition metal monoxides, MO, and monosulfates, MSO4, are analyzed. We show that all of these late transition metal oxides, as well as 4d and 5d metal sulfates, crystallize in distorted rock salt lattices and argue that the distortions are driven by collective first- and/or second order Jahn-Teller effects, as quantified by the c′/a′ ratio. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    Wang Yue; Shi Yongfang; Chen Yubiao [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Wu Liming, E-mail: liming_wu@fjirsm.ac.cn [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)

    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.

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

    International Nuclear Information System (INIS)

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

    2003-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-07-01

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

  10. Fermi surfaces of the pyrite-type cubic AuSb2 compared with split Fermi surfaces of the ullmannite-type cubic chiral NiSbS and PdBiSe

    Science.gov (United States)

    Nishimura, K.; Kakihana, M.; Nakamura, A.; Aoki, D.; Harima, H.; Hedo, M.; Nakama, T.; Ōnuki, Y.

    2018-05-01

    We grew high-quality single crystals of AuSb2 with the pyrite (FeS2)-type cubic structure by the Bridgman method and studied the Fermi surface properties by the de Haas-van Alphen (dHvA) experiment and the full potential LAPW band calculation. The Fermi surfaces of AuSb2 are found to be similar to those of NiSbS and PdBiSe with the ullmannite (NiSbS)-type cubic chiral structure because the crystal structures are similar each other and the number of valence electrons is the same between two different compounds. Note that each Fermi surface splits into two Fermi surfaces in NiSbS and PdBiSe, reflecting the non-centrosymmetric crystal structure.

  11. Study of helium diffusion, implanted at a cyclotron, in face-centered cubic metals: Au, Ag and Al

    International Nuclear Information System (INIS)

    Sciani, V.

    1985-01-01

    Helium in metals is produced by nuclear reactions of energetic particles. In nuclear technology the interest on helium in metals is import, due to its production by (n, α) reaction. Because helium has extremely low solubility in metals, the precipitation in the form of filled bubbles at elevated temperatures occurs, which have detrimental effects on mechanical properties and may limit the lifetime of structural components. One typical example is the high temperature embrittlement. The nucleation and growth of the bubbles strongly depends on the mobility of the helium. This work presents the study of helium diffusion in Au, Ag and Al at temperatures above room temperature. The helium created by (n, α) reactions has been simulated by homogeneous alpha particles implantation in cyclotron, at room temperature, in specimens of thicknesses between 5 and 50 μm and helium concentration between 10 -3 to 10 ppm. After implantation, the specimens were dropped in a furnace in a UHV-chamber and the diffusion was measured by observing the He-release during linear and isothermal annealings. The occurence of free diffusion was comparing the dependence of release kinetics on helium concentration, sample thickness, time and heating rate to diffusion theory and is clearly separeted from agglomeration process. The diffusion constants of helium in Au, Ag and Al follow an Arrhenius behavior, with: Au:D o =10 -1.0 cm 2 /s ΔH=1.70eV Ag:D 0 =10 -1.2 cm 2 /s ΔH=1.51eV Al:D o =10 +0.5 cm 2 /s ΔH=1.40eV. The results are compared to self-diffusion and to the diffusion of other gases in these metals. Comparison with theoretical estimates favours the vacancy mechanism for helium diffusion in Au, Ag and Al. (author) [pt

  12. Transition from metal-ligand bonding to halogen bonding involving a metal as halogen acceptor a study of Cu, Ag, Au, Pt, and Hg complexes

    Science.gov (United States)

    Oliveira, Vytor; Cremer, Dieter

    2017-08-01

    Utilizing all-electron Dirac-exact relativistic calculations with the Normalized Elimination of the Small Component (NESC) method and the local vibrational mode approach, the transition from metal-halide to metal halogen bonding is determined for Au-complexes interacting with halogen-donors. The local stretching force constants of the metal-halogen interactions reveal a smooth transition from weak non-covalent halogen bonding to non-classical 3-center-4-electron bonding and finally covalent metal-halide bonding. The strongest halogen bonds are found for dialkylaurates interacting with Cl2 or FCl. Differing trends in the intrinsic halogen-metal bond strength, the binding energy, and the electrostatic potential are explained.

  13. Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd

    OpenAIRE

    Duguid, J.; Bloomfield, V.A.; Benevides, J.; Thomas Jr, G.J.

    1993-01-01

    Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) ind...

  14. The mechanism of transition-metal (Cu or Pd)-catalyzed synthesis of benzimidazoles from amidines: theoretical investigation.

    Science.gov (United States)

    Li, Juan; Gu, Honghong; Wu, Caihong; Du, Lijuan

    2014-11-28

    In this study, the Cu(OAc)2- and [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines were theoretically investigated using density functional theory calculations. For the Cu-catalyzed system, our calculations supported a four-step-pathway involving C-H activation of an arene with Cu(II) via concerted metalation-deprotonation (CMD), followed by oxidation of the Cu(II) intermediate and deprotonation of the imino group by Cu(III), and finally reductive elimination from Cu(III). In our calculations, the barriers for the CMD step and the oxidation step are the same. The results are different from the ones reported by Fu et al. in which the whole reaction mechanism includes three steps and the CMD step is rate determining. On the basis of the calculation results for the [PdCl2(PhCN)2]-catalyzed system, C-H bond breaking by CMD occurs first, followed by the rate-determining C-N bond formation and N-H deprotonation. Pd(III) species is not involved in the [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines.

  15. Seed-mediated co-reduction in a large lattice mismatch system: synthesis of Pd-Cu nanostructures.

    Science.gov (United States)

    Kunz, Meredith R; McClain, Sophia M; Chen, Dennis P; Koczkur, Kallum M; Weiner, Rebecca G; Skrabalak, Sara E

    2017-06-08

    Metal nanoparticles (NPs) are of interest for applications in catalysis, electronics, chemical sensing, and more. Their utility is dictated by their composition and physical parameters such as particle size, particle shape, and overall architecture (e.g., hollow vs. solid). Interestingly, the addition of a second metal to create bimetallic NPs adds multifunctionality, with new emergent properties common. However, synthesizing structurally defined bimetallic NPs remains a great challenge. One synthetic pathway to architecturally controlled bimetallic NPs is seed-mediated co-reduction (SMCR) in which two metal precursors are simultaneously co-reduced to deposit metal onto shape-controlled metal seeds, which direct the overgrowth. Previously demonstrated in a Au-Pd system, here SMCR is applied to a system with a larger lattice mismatch between the depositing metals: Pd and Cu (7% mismatch for Pd-Cu vs. 4% for Au-Pd). Through manipulation of precursor reduction kinetics, the morphology and bimetallic distribution of the resultant NPs can be tuned to achieve eight-branched Pd-Cu heterostructures with Cu localized at the tips of the Pd nanocubes as well as branched Pd-Cu alloyed nanostructures and polyhedra. Significantly, the symmetry of the seeds can be transferred to the final nanostructures. This study expands our understanding of SMCR as a route to structurally defined bimetallic nanostructures and the synthesis of multicomponent nanomaterials more generally.

  16. Magnetism in ordered metallic perovskite compound GdPd{sub 3}B{sub x}C{sub 1-x}

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Abhishek [S.N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India)], E-mail: abhishek.phy@gmail.com; Mazumdar, Chandan [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India)], E-mail: chandan.mazumdar@saha.ac.in; Ranganathan, R. [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India); Dattagupta, S. [Indian Institute of Science Education and Research, Block-HC, Sector-III, Salt Lake, Kolkata 700106 (India)

    2009-08-15

    We report results of dc-magnetization, ac-susceptibility and magnetoresistance measurements on crystalline metallic-perovskite compounds GdPd{sub 3}B{sub x}C{sub 1-x} (x=0.25, 0.50, 0.75 and 1.00) and the parent cubic compound GdPd{sub 3}. The interest in these materials stems from the observation of negative temperature coefficient of resistance and negative thermal expansion in some of the members of this series. In the present study, we show that by substitution of non-magnetic elements, boron and carbon, the nature of the magnetic interaction can be varied from dominating ferromagnetic to antiferromagnetic and finally to a canted magnetic structure without altering the crystal symmetry of the compounds. The variation of magnetic interaction by modifying the lattice parameter resembles Ruderman-Kittel-Kasuya-Yosida (RKKY) oscillations.

  17. Structural behavior of Pd40Cu30Ni10P20 bulk metallic glass below and above the glass transition

    DEFF Research Database (Denmark)

    Mattern, N.; Hermann, H.; Roth, S.

    2003-01-01

    The thermal behavior of the structure of Pd40Cu30Ni10P20 bulk metallic glass has been investigated in situ through the glass transition by means of high-temperature x-ray synchrotron diffraction. The dependence of the x-ray structure factor S(q) of the Pd40Cu30Ni10P20 glass on temperature follows...... the Debye theory up to the glass transition with a Debye temperature theta=296 K. Above the glass transition temperature T-g, the temperature dependence of S(q) is altered, pointing to a continuous development of structural changes in the liquid with temperature. The atomic pair correlation functions g......(r) indicate changes in short-range-order parameters of the first and the second neighborhood with temperature. The temperature dependence of structural parameters is different in glass and in supercooled liquid, with a continuous behavior through the glass transition. The nearest-neighbor distance decreases...

  18. Supporting palladium metal on gold nanoparticles improves its catalysis for nitrite reduction.

    Science.gov (United States)

    Qian, Huifeng; Zhao, Zhun; Velazquez, Juan C; Pretzer, Lori A; Heck, Kimberly N; Wong, Michael S

    2014-01-07

    Nitrate (NO3(-)) and nitrite (NO2(-)) anions are often found in groundwater and surface water as contaminants globally, especially in agricultural areas due to nitrate-rich fertilizer use. One popular approach to studying the removal of nitrite/nitrate from water has been their degradation to dinitrogen via Pd-based reduction catalysis. However, little progress has been made towards understanding how the catalyst structure can improve activity. Focusing on the catalytic reduction of nitrite in this study, we report that Au NPs supporting Pd metal ("Pd-on-Au NPs") show catalytic activity that varies with volcano-shape dependence on Pd surface coverage. At room temperature, in CO2-buffered water, and under H2 headspace, the NPs were maximally active at a Pd surface coverage of 80%, with a first-order rate constant (k(cat) = 576 L g(Pd)(-1) min(-1)) that was 15x and 7.5x higher than monometallic Pd NPs (~4 nm; 40 L g(Pd)(-1) min(-1)) and Pd/Al2O3 (1 wt% Pd; 76 L g(Pd)(-1) min(-1)), respectively. Accounting only for surface Pd atoms, these NPs (576 L g(surface-Pd)(-1) min(-1)) were 3.6x and 1.6x higher than monometallic Pd NPs (160 L g(surface-Pd)(-1) min(-1)) and Pd/Al2O3 (361 L g(surface-Pd)(-1) min(-1)). These NPs retained ~98% of catalytic activity at a chloride concentration of 1 mM, whereas Pd/Al2O3 lost ~50%. The Pd-on-Au nanostructure is a promising approach to improve the catalytic reduction process for nitrite and, with further development, also for nitrate anions.

  19. Metal adsorption on monolayer blue phosphorene: A first principles study

    Science.gov (United States)

    Khan, Imran; Son, Jicheol; Hong, Jisang

    2018-01-01

    We investigated the electronic structure, adsorption energies, magnetic properties, dipole moment and work function of metal adatoms (Mg, Cr, Mo, Pd, Pt, and Au) adsorption on a blue phosphorene monolayer. For Mg, Pt and Au metals, the most stable state was found in hollow site while for Cr, Mo and Pd metals we found an adsorption in valley site. We suggest that the Pd and Pt atoms prefer 2D growth mode while the Mg, Cr, Mo and Au atoms prefer 3D island growth mode on monolayer phosphorene. The electronic band structures and magnetic properties were dependent on the doping site and dopant materials. For instance, the semiconducting features were preserved in Mg, Pd, Pt, and Au doped systems. However, the Cr and Mo doped systems displayed half-metallic band structures. The total magnetic moment of 4.05, 2.0 and 0.77 μB /impurity atom were obtained in Cr, Mo and Au doped systems whereas the Mg, Pd and Pt doped systems remained nonmagnetic. We also investigated the magnetic interaction between two transition metal impurities. We observed ferromagnetic coupling between two transition metal impurities in Cr and Mo doped systems while the Au doped system displayed almost degenerated magnetic state. For Mg, Cr, and Mo adsorptions, we found relatively large values of dipole moments compared to those in the Pd, Pt and Au adsorptions. This resulted in a significant suppression of the work function in Mg, Cr and Mo adsorptions. Overall, adsorption can tune the physical and magnetic properties of phosphorene monolayer.

  20. Au3+/Au0 Supported on Chromium(III Terephthalate Metal Organic Framework (MIL-101 as an Efficient Heterogeneous Catalystfor Three-Component Coupling Synthesis of Propargylamines

    Directory of Open Access Journals (Sweden)

    Lili Liu

    2017-01-01

    Full Text Available Post-synthesis modification is a useful method for the functionalization of metal–organic frameworks (MOFs. A novel catalyst Au@MIL-101-ED-SA (ED = ethylenediamine, SA = salicylaldehyde, containing coexisting Au3+ ions and Au0 nanoparticles, was prepared successfully by post-synthesis modification with ethylenediamine, salicylaldehyde and gold. Gold nanoparticles supported on MIL-101 (Au@MIL-101 were prepared successfully by the impregnation method. Au@MIL-101-ED-SA and Au@MIL-101 were characterized by N2 adsorption–desorption, X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and inductively coupled plasma-optical emission spectrometry. Au@MIL-101-ED-SA and Au@MIL-101 were applied as environmentally friendly catalysts in the three-component coupling reaction of aldehydes, amines, and alkynes for the preparation of diverse propargylamines. Au@MIL-101-ED-SA contained a fraction of cationic gold (Au3+/Au0 = 0.9 and showed higher catalytic activity than Au@MIL-101, which was prepared by the impregnation method. Furthermore, the reactions were performed under heterogeneous conditions and the novel catalyst was successfully recycled for four consecutive runs.

  1. Uniform formation of Au coated polystyrene core-shell structure using metallization process

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kyoungseob; Koo, Jonghyun; Roh, Yonghan, E-mail: yhroh@skku.edu

    2011-08-01

    There are several methods for the fabrication of core-shell particles, including chemical reduction and self-assembly. In this study, the chemical reduction method was used to fabricate 100 nm, Au-coated polystyrene nanoparticles. The formation of the gold layer was based on the increase of gold coverage by the reaction with aniline and HAuCl{sub 4}. This method allowed for efficient control of the gold coverage and led to relatively stable products. The formation of Au clusters on the surface of the 100 nm polystyrene beads was characterized by scanning electron microscope and high resolution tunneling electron microscope. As a result, the Au-coated nanoparticles can be used in various applications such as surface plasmon resonators, drug delivery systems and electronic optical devices.

  2. Optical characterization of broad plasmon resonances of Pd/Pt nanoparticles

    Science.gov (United States)

    Valizade-Shahmirzadi, N.; Pakizeh, T.

    2018-04-01

    In this paper, optical properties of nanoparticles (nanodisks and nanospheres) composed of photofunctional metals like palladium (Pd) and platinum (Pt) over a large dimension range are investigated using the electromagnetic simulation and quasi-static theory. These characteristics are compared with their counterparts in plasmonic gold (Au) nanoparticles. Pd/Pt-nanodisks with larger dimension have higher absorption and lower scattering efficiencies than Au-nanodisks that accompany with lower extinction efficiencies and broader resonances. Although an increment in the dimension (diameter and height) of Au/Pd/Pt-nanoparticles decreases the absorption-to-scattering ratios, these ratios are less sensitive to the height size in Au-nanodisks, which causes their LSPR spectra become much broader. It is noteworthy that the LSPR quality factor of Pd nanoparticles is improved by considering the radiative damping and depolarization in quasi-static method unlike the Au nanoparticles. The importance of the highly absorptive Pd/Pt nanoparticles can be traced in the photo-functionalized and energy applications.

  3. Noble metal abundances in komatiite suites from Alexo, Ontario and Gorgona Island, Colombia

    Science.gov (United States)

    Brügmann, G. E.; Arndt, N. T.; Hofmann, A. W.; Tobschall, H. J.

    1987-08-01

    The distribution of the chalcophile and siderophile metals Cu, Ni, Au, Pd, Ir, Os and Ru in an Archaean komatiite flow from Alexo, Ontario and in a Phanerozoic komatiitic suite of Gorgona Island, Colombia, provides new information about the geochemical behaviour of these elements. Copper, Au and Pd behave as incompatible elements during the crystallization of these ultramafic magmas. In contrast, Ni, Ir, Os and Ru concentrations systematically decrease with decreasing MgO contents, a pattern characteristic of compatible elements. These trends are most probably controlled by olivine crystallization, which implies that Ir, Os and Ru are compatible in olivine. Calculated partition coefficients for Ir, Os and Ru between olivine and the melt are about 1.8. Compared to primitive mantle, parental komatiitic liquids are enriched in (incompatible) Cu, Au and Pd and depleted in (compatible) Ir, Os and Ru. Within both Archaean and Phanerozoic komatiites, noble metal ratios such as Au/Pd, Ir/Os, Os/Ru and Ru/Ir and ratios of lithophile and siderophile elements such as Ti/Pd, Ti/Au are constant and similar to primitive mantle values. This implies that Au and Pd are moderately incompatible elements and that there has been no significant fractionation of siderophile and lithophile elements since the Archaean. Platinum-group element abundances of normal MORB are highly variable and always much lower than in komatiites, because MORB magma is saturated with sulfur and a variable but minor amount of sulfide segregated during mantle melting or during the ascent of magma to the surface. Sulfide deposits associated with komatiites display similar chalcophile element patterns to those of komatiites. Noble metal ratios such as Pd/Ir, Au/Ir, Pd/Os and Pd/Ru can be used to determine the composition of the host komatiite at the time of sulfide segregation.

  4. Theoretical studies of the work functions of Pd-based bimetallic surfaces

    International Nuclear Information System (INIS)

    Ding, Zhao-Bin; Wu, Feng; Wang, Yue-Chao; Jiang, Hong

    2015-01-01

    Work functions of Pd-based bimetallic surfaces, including mainly M/Pd(111), Pd/M, and Pd/M/Pd(111) (M = 4d transition metals, Cu, Au, and Pt), are studied using density functional theory. We find that the work function of these bimetallic surfaces is significantly different from that of parent metals. Careful analysis based on Bader charges and electron density difference indicates that the variation of the work function in bimetallic surfaces can be mainly attributed to two factors: (1) charge transfer between the two different metals as a result of their different intrinsic electronegativity, and (2) the charge redistribution induced by chemical bonding between the top two layers. The first factor can be related to the contact potential, i.e., the work function difference between two metals in direct contact, and the second factor can be well characterized by the change in the charge spilling out into vacuum. We also find that the variation in the work functions of Pd/M/Pd(111) surfaces correlates very well with the variation of the d-band center of the surface Pd atom. The findings in this work can be used to provide general guidelines to design new bimetallic surfaces with desired electronic properties

  5. Electrogenerated Chemiluminescence Behavior of Au nanoparticles-hybridized Pb (II) metal-organic framework and its application in selective sensing hexavalent chromium.

    Science.gov (United States)

    Ma, Hongmin; Li, Xiaojian; Yan, Tao; Li, Yan; Liu, Haiyang; Zhang, Yong; Wu, Dan; Du, Bin; Wei, Qin

    2016-02-23

    In this work, a novel electrochemiluminescence (ECL) sensor based on Au nanoparticles-hybridized Pb (II)-β-cyclodextrin (Pb-β-CD) metal-organic framework for detecting hexavalent chromium (Cr(VI)) was developed. Pb-β-CD shows excellent ECL behavior and unexpected reducing ability towards Au ions. Au nanoparticles could massively form on the surface of Pb-β-CD (Au@Pb-β-CD) without use of any additional reducing agent. In the presence of coreactant K2S2O8, the ECL emission of Pb-β-CD was enhanced by the formation of Au nanoparticles. Cr(VI) can collisionally quench the ECL behavior of Au@Pb-β-CD/S2O8(2-) system and the detection mechanism was investigated. This ECL sensor is found to have a linear response in the range of 0.01-100 μM and a low detection limit of 3.43 nM (S/N = 3) under the optimal conditions. These results suggest that metal-organic framework Au@Pb-β-CD has great potential in extending the application in the ECL field as an efficient luminophore.

  6. (Electronic structure and reactivities of transition metal clusters)

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

    The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

  7. Metal-semiconductor transition at a comparable resistivity level and positive magnetoresistance in Mn3Mn1-x Pd x N thin films

    Science.gov (United States)

    Xu, T.; Ji, G. P.; Cao, Z. X.; Ji, A. L.

    2018-02-01

    Thin films of antiperovskite Mn3Mn1-x Pd x N with x up to 0.36 were grown by reactive magnetron co-sputtering method. All the deposits exhibit a [1 0 0] preferential orientation, with the lattice constant slightly enlarged in samples with ever more Pd atoms partially substituting the MnI atoms in Mn3MnN matrix. The replacement of MnI atoms in antiperovskite structure by Pd atoms, besides reducing the saturation magnetization, also invokes a metal-semiconductor transition which occurs remarkably at a comparable resistivity level. Moreover, a positive magnetoresistance was observed in samples of a high Pd content. These tunable electrical and magnetic properties of ternary antiperovskite compounds might promise some ingenious applications in electronic industry.

  8. Correlations between deformations, surface state and leak rate in metal to metal contact; Correlations entre deformations, etat de surface et debit de fuite au contact metal-metal

    Energy Technology Data Exchange (ETDEWEB)

    Armand, G; Lapujoulade, J; Paigne, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1963-07-01

    The study of metal to metal contact from the stand-point of the leak rate has been carried on a copper ring located between two hard-steel flanges. The analysis of the results confirms the hysteresis phenomenon already seen. Some curves (leak rate versus force and leak rate versus true deformation) in semi-logarithmic coordinates are straight lines. Likewise some curves (electrical contact resistance versus force) in bi-logarithmic coordinates are straight lines. All these results can be understood by looking at the conductance introduced by the deformations of the micro-geometry of the surfaces in contact. Some tests carried out in rising the temperature confirm these hypothesis. (authors) [French] L'etude du contact metal-metal du point de vue debit de fuite a ete poursuivie en utilisant un anneau de cuivre place entre brides d'acier dur. L'analyse des resultats confirme le phenomene d'hysteresis deja constate, montre l'influence de l'etat de surface des brides et du joint. Certaines courbes (debit de fuite/force et debit de fuite/deformation rationnelle), en coordonnees semi-logarithmiques, sont des droites. De meme, certaines courbes (resistance de contact/force) en coordonnees bi-logarithmiques, sont des droites. Ces resultats s'interpretent en considerant la conductance produite par la deformation des microgeometries des surfaces en contact. Quelques essais d'elevation de temperature confirment ces resultats. (auteurs)

  9. An analysis of the pull strength behaviors of fine-pitch, flip chip solder interconnections using a Au-Pt-Pd thick film conductor on Low-Temperature, Co-fired Ceramic (LTCC) substrates

    International Nuclear Information System (INIS)

    Uribe, Fernando R.; Kilgo, Alice C.; Grazier, John Mark; Vianco, Paul Thomas; Zender, Gary L.; Hlava, Paul Frank; Rejent, Jerome Andrew

    2008-01-01

    The assembly of the BDYE detector requires the attachment of sixteen silicon (Si) processor dice (eight on the top side; eight on the bottom side) onto a low-temperature, co-fired ceramic (LTCC) substrate using 63Sn-37Pb (wt.%, Sn-Pb) in a double-reflow soldering process (nitrogen). There are 132 solder joints per die. The bond pads were gold-platinum-palladium (71Au-26Pt-3Pd, wt.%) thick film layers fired onto the LTCC in a post-process sequence. The pull strength and failure modes provided the quality metrics for the Sn-Pb solder joints. Pull strengths were measured in both the as-fabricated condition and after exposure to thermal cycling (-55/125 C; 15 min hold times; 20 cycles). Extremely low pull strengths--referred to as the low pull strength phenomenon--were observed intermittently throughout the product build, resulting in added program costs, schedule delays, and a long-term reliability concern for the detector. There was no statistically significant correlation between the low pull strength phenomenon and (1) the LTCC 'sub-floor' lot; (2) grit blasting the LTCC surfaces prior to the post-process steps; (3) the post-process parameters; (4) the conductor pad height (thickness); (5) the dice soldering assembly sequence; or (5) the dice pull test sequence. Formation of an intermetallic compound (IMC)/LTCC interface caused by thick film consumption during either the soldering process or by solid-state IMC formation was not directly responsible for the low-strength phenomenon. Metallographic cross sections of solder joints from dice that exhibited the low pull strength behavior, revealed the presence of a reaction layer resulting from an interaction between Sn from the molten Sn-Pb and the glassy phase at the TKN/LTCC interface. The thick film porosity did not contribute, explicitly, to the occurrence of reaction layer. Rather, the process of printing the very thin conductor pads was too sensitive to minor thixotropic changes to ink, which resulted in

  10. An analysis of the pull strength behaviors of fine-pitch, flip chip solder interconnections using a Au-Pt-Pd thick film conductor on Low-Temperature, Co-fired Ceramic (LTCC) substrates.

    Energy Technology Data Exchange (ETDEWEB)

    Uribe, Fernando R.; Kilgo, Alice C.; Grazier, John Mark; Vianco, Paul Thomas; Zender, Gary L.; Hlava, Paul Frank; Rejent, Jerome Andrew

    2008-09-01

    The assembly of the BDYE detector requires the attachment of sixteen silicon (Si) processor dice (eight on the top side; eight on the bottom side) onto a low-temperature, co-fired ceramic (LTCC) substrate using 63Sn-37Pb (wt.%, Sn-Pb) in a double-reflow soldering process (nitrogen). There are 132 solder joints per die. The bond pads were gold-platinum-palladium (71Au-26Pt-3Pd, wt.%) thick film layers fired onto the LTCC in a post-process sequence. The pull strength and failure modes provided the quality metrics for the Sn-Pb solder joints. Pull strengths were measured in both the as-fabricated condition and after exposure to thermal cycling (-55/125 C; 15 min hold times; 20 cycles). Extremely low pull strengths--referred to as the low pull strength phenomenon--were observed intermittently throughout the product build, resulting in added program costs, schedule delays, and a long-term reliability concern for the detector. There was no statistically significant correlation between the low pull strength phenomenon and (1) the LTCC 'sub-floor' lot; (2) grit blasting the LTCC surfaces prior to the post-process steps; (3) the post-process parameters; (4) the conductor pad height (thickness); (5) the dice soldering assembly sequence; or (5) the dice pull test sequence. Formation of an intermetallic compound (IMC)/LTCC interface caused by thick film consumption during either the soldering process or by solid-state IMC formation was not directly responsible for the low-strength phenomenon. Metallographic cross sections of solder joints from dice that exhibited the low pull strength behavior, revealed the presence of a reaction layer resulting from an interaction between Sn from the molten Sn-Pb and the glassy phase at the TKN/LTCC interface. The thick film porosity did not contribute, explicitly, to the occurrence of reaction layer. Rather, the process of printing the very thin conductor pads was too sensitive to minor thixotropic changes to ink, which resulted in

  11. Theoretical study of PTCDA adsorbed on the coinage metal surfaces, Ag(111), Au(111) and Cu(111)

    International Nuclear Information System (INIS)

    Romaner, L; Nabok, D; Puschnig, P; Ambrosch-Draxl, C; Zojer, E

    2009-01-01

    A thorough understanding of the adsorption of molecules on metallic surfaces is a crucial prerequisite for the development and improvement of functionalized materials. A prominent representative within the class of π-conjugated molecules is 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) which, adsorbed on the Ag(111), Au(111) or Cu(111) surfaces, shows characteristic trends for work-function modification, alignment of molecular levels with the substrate Fermi energy and binding distances. We carried out density functional theory (DFT) calculations to investigate to what extent these trends can be rationalized on a theoretical basis. We used different density functionals (DF) including a fully non-local van der Waals (vdW) DF capable of describing dispersion interactions. We show that, rather independent of the DF, the calculations yield level alignments and work-function modifications consistent with ultra-violet photoelectron spectroscopy when the monolayer is placed onto the surfaces at the experimental distances (as determined from x-ray standing wave experiments). The lowest unoccupied molecular orbital is occupied on the Ag and Cu surfaces, whereas it remains unoccupied on the Au surface. Simultaneously, the work function increases for Ag but decreases for Cu and Au. Adsorption distances and energies, on the other hand, depend very sensitively on the choice of the DF. While calculations in the local density approximation bind the monolayer consistently with the experimental trends, the generalized gradient approximation in several flavors fails to reproduce realistic distances and energies. Calculations employing the vdW-DF reveal that substantial bonding contributions arise from dispersive interactions. They yield reasonable binding energies but larger binding distances than the experiments.

  12. Strain field due to transition metal impurities in Ni and Pd

    Indian Academy of Sciences (India)

    1 2. 28 1 π. ¯h2r3 2. dH mr5. (44). In eqs (41) to (44), ∆φFE(r), ∆φc(r) and ∆φb(r) are impurity induced changes in the po- tential due to free electron, s–d hybridization and d-bandwidth contributions respectively. 3. Calculations and results. The above formalism is used to calculate the atomic displacements in Ni and Pd dilute.

  13. Ceramic Defects in Metal-Ceramic Fixed Dental Prostheses Made from Co-Cr and Au-Pt Alloys: A Retrospective Study.

    Science.gov (United States)

    Mikeli, Aikaterini; Boening, Klaus W; Lißke, Benjamin

    2015-01-01

    Ceramic defects in porcelain-fused-to-metal (PFM) restorations may depend on framework alloy type. This study assessed ceramic defects on cobalt-chromium- (Co-Cr-) and gold-platinum- (Au-Pt-) based PFM restorations. In this study, 147 Co-Cr-based and 168 Au-Pt-based PFM restorations inserted between 1998 and 2010 (139 patients) were examined for ceramic defects. Detected defects were assigned to three groups according to clinical defect relevance. Ceramic defect rates (Co-Cr-based: 12.9%; Au-Pt-based: 7.2%) revealed no significant difference but a strong statistical trend (U test, P = .082). Most defects were of little clinical relevance. Co-Cr PFM restorations may be at higher risk for ceramic defects compared to Au-Pt-based restorations.

  14. On the metal-support synergy for selective gas-phase ethanol oxidation over MgCuCr2O4 supported metal nanoparticle catalysts

    NARCIS (Netherlands)

    Liu, P.; Zhu, X.; Yang, S.; Li, T.; Hensen, E.J.M.

    2015-01-01

    Achieving high yields in the production of bulk chemicals is an important goal for the chemical industry. We investigated the influence of the metal on the catalytic performance of M/MgCuCr2O4 (M = Cu, Ag, Pd, Pt, Au) catalysts to better understand the metal-support synergy for the aerobic oxidation

  15. Spin and orbital magnetism of coinage metal trimers (Cu3, Ag3, Au3: A relativistic density functional theory study

    Directory of Open Access Journals (Sweden)

    Mahdi Afshar

    2013-11-01

    Full Text Available We have demonstrated electronic structure and magnetic properties of Cu3, Ag3 and Au3 trimers using a full potential local orbital method in the framework of relativistic density functional theory. We have also shown that the non-relativistic generalized gradient approximation for the exchange-correlation energy functional gives reliable magnetic properties in coinage metal trimers compared to experiment. In addition we have indicated that the spin-orbit coupling changes the structure and magnetic properties of gold trimer while the structure and magnetic properties of copper and silver trimers are marginally affected. A significant orbital moment of 0.21μB was found for most stable geometry of the gold trimer whereas orbital magnetism is almost quenched in the copper and silver trimers.

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

    Science.gov (United States)

    Zhao, Chunjiang; Wu, Huarui

    2018-03-01

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

  17. Ultrasound-induced crystallization around the glass transition temperature for Pd40Ni40P20 metallic glass

    International Nuclear Information System (INIS)

    Ichitsubo, Tetsu; Matsubara, Eiichiro; Kai, Satoshi; Hirao, Masahiko

    2004-01-01

    We have found that crystallization of a Pd 40 Ni 40 P 20 bulk metallic glass is accelerated in the vicinity of the glass transition temperature T g when it is subjected to sub/low-MHz frequency ultrasonic vibration. Resonance frequencies and internal frictions have been measured with the electromagnetic acoustic resonance (EMAR) technique. In the initial heating process of an as-cast glassy sample, the resonance frequencies jump up just above T g under ultrasonic excitation, which is attributed to nano-crystallization that is confirmed by the X-ray diffraction profile. However, such a notable change is not observed without ultrasonic vibration. The irregular Λ-shaped internal-friction peaks are also observed prior to the abrupt crystallization. This rapid crystallization is considered to be caused by a stochastic resonance, in which the jump frequency of atoms matches the frequency of the interatomic-potential change by the ultrasonic vibration

  18. Nanoindentation study on the characteristic of shear transformation zone in a Pd-based bulk metallic glass during serrated flow

    Science.gov (United States)

    Liao, G. K.; Long, Z. L.; Zhao, M. S. Z.; Peng, L.; Chai, W.; Ping, Z. H.

    2018-04-01

    This paper presents the research on the evolution of shear transformation zone (STZ) in a Pd-based bulk metallic glass (BMG) during serrated flow under nanoindentation. A novel method of estimating the STZ volume through statistical analysis of the serrated flow behavior was proposed for the first time. Based on the proposed method, the STZ volume of the studied BMG at various peak loads have been systematically investigated. The results indicate that the measured STZ volumes are in good agreement with that documented in literature, and the STZ size exhibits an increasing trend during indentation. Moreover, the correlation between the serrated flow dynamics and the STZ activation has also been evaluated. It is found that the STZ activation can promote the formation of self-organized critical (SOC) state during serrated flow.

  19. XRD, DRS, and SEM stundies of the effects of metal dopants (Pt and Au) on the structural and optical properties of TiO2

    CSIR Research Space (South Africa)

    Moloantoa, JR

    2011-07-01

    Full Text Available Au and Pt doped TiO2 nanocrystlas were prepared using the sol gel method. Diffuse Reflectance Spectroscopy (DRS) was used to study the characteristics of these precious metals and X-ray diffraction (XRD) with calculated lattice parameters was used...

  20. A Discovery of Strong Metal-Support Bonding in Nanoengineered Au-Fe3O4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy.

    Science.gov (United States)

    Han, Chang Wan; Choksi, Tej; Milligan, Cory; Majumdar, Paulami; Manto, Michael; Cui, Yanran; Sang, Xiahan; Unocic, Raymond R; Zemlyanov, Dmitry; Wang, Chao; Ribeiro, Fabio H; Greeley, Jeffrey; Ortalan, Volkan

    2017-08-09

    The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous "strong metal-support bonding" between gold nanoparticles and "nano-engineered" Fe 3 O 4 substrates by in situ microscopy. During in situ vacuum annealing of Au-Fe 3 O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3 O 4 on Au nanoparticles, the gold nanoparticles transform into the gold thin films and wet the surface of nano-Fe 3 O 4 , as the surface reduction of nano-Fe 3 O 4 proceeds. This phenomenon results from a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3 O 4 and the extremely strong adhesion between Au and the reduced Fe 3 O 4 . This strong metal-support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and ultimately for the development of improved catalysts and functional nanostructures.

  1. Biomolecule-coated metal nanoparticles on titanium.

    Science.gov (United States)

    Christensen, Stephen L; Chatt, Amares; Zhang, Peng

    2012-02-07

    Immobilizations of nanoparticles and biomolecules on biocompatible substrates such as titanium are two promising approaches to bringing new functionalities to Ti-based biomaterials. Herein, we used a variety of X-ray spectroscopic techniques to study and better understand metal-thiolate interactions in biofunctionalized metal nanoparticle systems supported on Ti substrates. Using a facile one-step procedure, a series of Au nanoparticle samples with varied biomolecule coatings ((2-mercatopropionyl)glycine (MPG) and bovine serum albumin (BSA)) and biomolecule concentrations are prepared. Ag and Pd systems are also studied to observe change with varying metal composition. The structure and properties of these biomolecule-coated nanoparticles are investigated with scanning electron microscopy (SEM) and element-specific X-ray techniques, including extended X-ray absorption fine structure (Au L(3)-edge), X-ray absorption near-edge structure (Au L(3), Ag L(3), Pd L(3), and S K-edge), and X-ray photoelectron spectroscopy (Au 4f, Ag 3d, Pd 3d, and S 2p core level). It was found that, by comparison of SEM and X-ray spectroscopy results, the coating of metal nanoparticles with varying model biomolecule systems can have a significant effect on both surface coverage and organization. This work offers a facile chemical method for bio- and nanofunctionalization of Ti substrates as well as provides a physical picture of the structure and bonding of biocoated metal nanoparticles, which may lead to useful applications in orthopedics and biomedicine.

  2. Influence of metal coating methods on the activity of bimetal-containing zeolite catalysts of Co, Pd-ZSM-5 in carbon monoxide oxidation

    Science.gov (United States)

    Oleksenko, L. P.; Lutsenko, L. V.; Yatsimirskii, V. K.

    2011-07-01

    It has been established that catalytic activity in the CO oxidation of bimetal-containing zeolite Co,Pd-systems based on ZSM-5 and obtained via ion exchange and impregnation at different orders of the introduction of metal cations is higher than that of monometal-containing systems Co-ZSM-5 and Pd—ZSM-5. Through TPD of NH3, it was determined that coordination-unsaturated bicationic associates are formed in Co,Pd/ZSM-5 zeolites obtained by ion exchange. It was found that the activity of bimetal-containing systems depends on the relation of the active components.

  3. [Sb{sub 4}Au{sub 4}Sb{sub 4}]{sup 2−}: A designer all-metal aromatic sandwich

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Wen-Juan; You, Xue-Rui [Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006 (China); Guo, Jin-Chang [Department of Chemistry, Xinzhou Teachers University, Xinzhou 034000 (China); Li, Da-Zhi, E-mail: hj.zhai@sxu.edu.cn, E-mail: ldz005@126.com [Department of Chemical Engineering, Binzhou University, Binzhou 256603 (China); Wang, Ying-Jin [Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006 (China); Department of Chemistry, Xinzhou Teachers University, Xinzhou 034000 (China); Sun, Zhong-Ming [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Zhai, Hua-Jin, E-mail: hj.zhai@sxu.edu.cn, E-mail: ldz005@126.com [Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006 (China); State Key Laboratory of Quantum Optics and Quantum Optics Devices, Shanxi University, Taiyuan 030006 (China)

    2016-07-28

    We report on the computational design of an all-metal aromatic sandwich, [Sb{sub 4}Au{sub 4}Sb{sub 4}]{sup 2−}. The triple-layered, square-prismatic sandwich complex is the global minimum of the system from Coalescence Kick and Minima Hopping structural searches. Following a standard, qualitative chemical bonding analysis via canonical molecular orbitals, the sandwich complex can be formally described as [Sb{sub 4}]{sup +}[Au{sub 4}]{sup 4−}[Sb{sub 4}]{sup +}, showing ionic bonding characters with electron transfers in between the Sb{sub 4}/Au{sub 4}/Sb{sub 4} layers. For an in-depth understanding of the system, one needs to go beyond the above picture. Significant Sb → Au donation and Sb ← Au back-donation occur, redistributing electrons from the Sb{sub 4}/Au{sub 4}/Sb{sub 4} layers to the interlayer Sb–Au–Sb edges, which effectively lead to four Sb–Au–Sb three-center two-electron bonds. The complex is a system with 30 valence electrons, excluding the Sb 5s and Au 5d lone-pairs. The two [Sb{sub 4}]{sup +} ligands constitute an unusual three-fold (π and σ) aromatic system with all 22 electrons being delocalized. An energy gap of ∼1.6 eV is predicted for this all-metal sandwich. The complex is a rare example for rational design of cluster compounds and invites forth-coming synthetic efforts.

  4. Effect of the strong metal-support interaction on hydrogen sorption kinetics of Pd-capped switchable mirrors

    NARCIS (Netherlands)

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

    2004-01-01

    The morphology and electronic structure of Pd clusters grown on oxidized yttrium surfaces are investigated by scanning tunneling microscopy and ultraviolet photoelectron spectroscopy. The hydrogen sorption mediated by the Pd clusters is determined from the optically monitored switching kinetics of

  5. Photoemission studies of zinc-noble metal alloys: Zn--Cu, Zn--Ag, and Zn--Au films on Ru(001)

    International Nuclear Information System (INIS)

    Rodriguez, J.A.; Hrbek, J.

    1993-01-01

    Zn and the noble metals alloy when coadsorbed on Ru(001). The properties of Zn--Cu, Zn--Ag, and Zn--Au alloys have been studied using core- and valence-level photoemission and temperature programmed desorption. Alloy formation induces only small shifts (-0.2 to -0.3 eV) in the position of the Zn 2p, 3s, and 3d levels. In contrast, the core and valence levels of the noble metals show large shifts toward higher binding energy. For small amounts of Cu, Ag, and Au dissolved in Zn multilayers, the shifts in the core levels of the nobel metals follow the sequence: Cu(2p 3/2 ), 0.8 eV∼Ag(3d 5/2 ), 0.8 eV 7/2 ), 1.4 eV. The magnitude of the shift increases as the Pauling electronegativity of the noble metal increases. However, the sign of the shifts for the Cu(2p 3/2 ), Ag(3d 5/2 ), or Au(4f 7/2 ) levels is not directly determined by the direction of charge transfer within the corresponding Zn-noble metal bond

  6. Multi-metallic Nanomaterials From Ni, Ag, Pd With Pt's Catalytic Activity

    KAUST Repository

    Huang, Kuo-Wei

    2015-06-04

    A trimetallic catalyst that is a combination of nickel, silver and palladium metal is described. The trimetallic catalyst can be used to produce hydrogen and is useful as a replacement for platinum in hydrogenation reactions.

  7. Multi-metallic Nanomaterials From Ni, Ag, Pd With Pt's Catalytic Activity

    KAUST Repository

    Huang, Kuo-Wei; Lai, Zhiping; Hu, Lei

    2015-01-01

    A trimetallic catalyst that is a combination of nickel, silver and palladium metal is described. The trimetallic catalyst can be used to produce hydrogen and is useful as a replacement for platinum in hydrogenation reactions.

  8. Metal Nanoparticles Covered with a Metal-Organic Framework: From One-Pot Synthetic Methods to Synergistic Energy Storage and Conversion Functions.

    Science.gov (United States)

    Kobayashi, Hirokazu; Mitsuka, Yuko; Kitagawa, Hiroshi

    2016-08-01

    Hybrid materials composed of metal nanoparticles and metal-organic frameworks (MOFs) have attracted much attention in many applications, such as enhanced gas storage and catalytic, magnetic, and optical properties, because of the synergetic effects between the metal nanoparticles and MOFs. In this Forum Article, we describe our recent progress on novel synthetic methods to produce metal nanoparticles covered with a MOF (metal@MOF). We first present Pd@copper(II) 1,3,5-benzenetricarboxylate (HKUST-1) as a novel hydrogen-storage material. The HKUST-1 coating on Pd nanocrystals results in a remarkably enhanced hydrogen-storage capacity and speed in the Pd nanocrystals, originating from charge transfer from Pd nanocrystals to HKUST-1. Another material, Pd-Au@Zn(MeIM)2 (ZIF-8, where HMeIM = 2-methylimidazole), exhibits much different catalytic activity for alcohol oxidation compared with Pd-Au nanoparticles, indicating a design guideline for the development of composite catalysts with high selectivity. A composite material composed of Cu nanoparticles and Cr3F(H2O)2O{C6H3(CO2)3}2 (MIL-100-Cr) demonstrates higher catalytic activity for CO2 reduction into methanol than Cu/γ-Al2O3. We also present novel one-pot synthetic methods to produce composite materials including Pd/ZIF-8 and Ni@Ni2(dhtp) (MOF-74, where H4dhtp = 2,5-dihydroxyterephthalic acid).

  9. Formation of Mixed-Ligand Complexes of Pd2+ with Nucleoside 5'-Monophosphates and Some Metal-Ion-Binding Nucleoside Surrogates

    Directory of Open Access Journals (Sweden)

    Oleg Golubev

    2014-10-01

    Full Text Available Formation of mixed-ligand Pd2+ complexes between canonical nucleoside 5'-monophosphates and five metal-ion-binding nucleoside analogs has been studied by 1H-NMR spectroscopy to test the ability of these nucleoside surrogates to discriminate between unmodified nucleobases by Pd2+-mediated base pairing. The nucleoside analogs studied included 2,6-bis(3,5-dimethylpyrazol-1-yl-, 2,6-bis(1-methylhydrazinyl- and 6-(3,5-dimethylpyrazol-1-yl-substituted 9-(β-d-ribofuranosylpurines 1–3, and 2,4-bis(3,5-dimethylpyrazol-1-yl- and 2,4-bis(1-methylhydrazinyl-substituted 5-(β-d-ribofuranosyl-pyrimidines 4–5. Among these, the purine derivatives 1-3 bound Pd2+ much more tightly than the pyrimidine derivatives 4, 5 despite apparently similar structures of the potential coordination sites. Compounds 1 and 2 formed markedly stable mixed-ligand Pd2+ complexes with UMP and GMP, UMP binding favored by 1 and GMP by 2. With 3, formation of mixed-ligand complexes was retarded by binding of two molecules of 3 to Pd2+.

  10. Preparation of carbon-free TEM microgrids by metal sputtering

    International Nuclear Information System (INIS)

    Janbroers, S.; Kruijff, T.R. de; Xu, Q.; Kooyman, P.J.; Zandbergen, H.W.

    2009-01-01

    A new method for preparing carbon-free, temperature-stable Transmission Electron Microscope (TEM) grids is presented. An 80% Au/20% Pd metal film is deposited onto a 'holey' microgrid carbon supported on standard mixed-mesh Au TEM grids. Subsequently, the carbon film is selectively removed using plasma cleaning. In this way, an all-metal TEM film is made containing the 'same' microgrid as the original carbon film. Although electron transparency of the foil is reduced significantly, the open areas for TEM inspection of material over these areas are maintained. The metal foil can be prepared with various thicknesses and ensures good electrical conductivity. The new Au/Pd grids are stable to at least 775 K under vacuum conditions.

  11. Preparation of carbon-free TEM microgrids by metal sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Janbroers, S., E-mail: stephan.janbroers@albemarle.com [Albemarle Catalysts B.V., Nieuwendammerkade 1-3, 1030 BE, Amsterdam (Netherlands); Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft (Netherlands); Kruijff, T.R. de; Xu, Q. [Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft (Netherlands); Kooyman, P.J. [DelftChemTech, Delft University of Technology, Julianalaan 136, 2628 BL, Delft (Netherlands); Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft (Netherlands); Zandbergen, H.W. [Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft (Netherlands)

    2009-08-15

    A new method for preparing carbon-free, temperature-stable Transmission Electron Microscope (TEM) grids is presented. An 80% Au/20% Pd metal film is deposited onto a 'holey' microgrid carbon supported on standard mixed-mesh Au TEM grids. Subsequently, the carbon film is selectively removed using plasma cleaning. In this way, an all-metal TEM film is made containing the 'same' microgrid as the original carbon film. Although electron transparency of the foil is reduced significantly, the open areas for TEM inspection of material over these areas are maintained. The metal foil can be prepared with various thicknesses and ensures good electrical conductivity. The new Au/Pd grids are stable to at least 775 K under vacuum conditions.

  12. Preparation of carbon-free TEM microgrids by metal sputtering.

    Science.gov (United States)

    Janbroers, S; de Kruijff, T R; Xu, Q; Kooyman, P J; Zandbergen, H W

    2009-08-01

    A new method for preparing carbon-free, temperature-stable Transmission Electron Microscope (TEM) grids is presented. An 80% Au/20% Pd metal film is deposited onto a 'holey' microgrid carbon supported on standard mixed-mesh Au TEM grids. Subsequently, the carbon film is selectively removed using plasma cleaning. In this way, an all-metal TEM film is made containing the 'same' microgrid as the original carbon film. Although electron transparency of the foil is reduced significantly, the open areas for TEM inspection of material over these areas are maintained. The metal foil can be prepared with various thicknesses and ensures good electrical conductivity. The new Au/Pd grids are stable to at least 775K under vacuum conditions.

  13. Calculated stacking-fault energies of elemental metals

    DEFF Research Database (Denmark)

    Rosengaard, N. M.; Skriver, Hans Lomholt

    1993-01-01

    -sphere approximations. The results are in excellent agreement with recent layer Korringa-Kohn-Rostoker Green's-function calculations where stacking-fault energies for Ni, Cu, Rh, Pd, Ag, Ir, and Au were found by means of the the so-called force theorem. We find that the self-consistent fault energies for all the metals...

  14. An investigation of the mimetic enzyme activity of two-dimensional Pd-based nanostructures

    Science.gov (United States)

    Wei, Jingping; Chen, Xiaolan; Shi, Saige; Mo, Shiguang; Zheng, Nanfeng

    2015-11-01

    In this work, we investigated the mimetic enzyme activity of two-dimensional (2D) Pd-based nanostructures (e.g. Pd nanosheets, Pd@Au and Pd@Pt nanoplates) and found that they possess intrinsic peroxidase-, oxidase- and catalase-like activities. These nanostructures were able to activate hydrogen peroxide or dissolved oxygen for catalyzing the oxidation of organic substrates, and decompose hydrogen peroxide to generate oxygen. More systematic investigations revealed that the peroxidase-like activities of these Pd-based nanomaterials were highly structure- and composition-dependent. Among them, Pd@Pt nanoplates displayed the highest peroxidase-like activity. Based on these findings, Pd-based nanostructures were applied for the colorimetric detection of H2O2 and glucose, and also the electro-catalytic reduction of H2O2. This work offers a promising prospect for the application of 2D noble metal nanostructures in biocatalysis.In this work, we investigated the mimetic enzyme activity of two-dimensional (2D) Pd-based nanostructures (e.g. Pd nanosheets, Pd@Au and Pd@Pt nanoplates) and found that they possess intrinsic peroxidase-, oxidase- and catalase-like activities. These nanostructures were able to activate hydrogen peroxide or dissolved oxygen for catalyzing the oxidation of organic substrates, and decompose hydrogen peroxide to generate oxygen. More systematic investigations revealed that the peroxidase-like activities of these Pd-based nanomaterials were highly structure- and composition-dependent. Among them, Pd@Pt nanoplates displayed the highest peroxidase-like activity. Based on these findings, Pd-based nanostructures were applied for the colorimetric detection of H2O2 and glucose, and also the electro-catalytic reduction of H2O2. This work offers a promising prospect for the application of 2D noble metal nanostructures in biocatalysis. Electronic supplementary information (ESI) available: TEM images, EDX and dispersion stability of Pd-based nanomaterials

  15. Memory Effect of Metal-Oxide-Silicon Capacitors with Self-Assembly Double-Layer Au Nanocrystals Embedded in Atomic-Layer-Deposited HfO2 Dielectric

    International Nuclear Information System (INIS)

    Yue, Huang; Hong-Yan, Gou; Qing-Qing, Sun; Shi-Jin, Ding; Wei, Zhang; Shi-Li, Zhang

    2009-01-01

    We report the chemical self-assembly growth of Au nanocrystals on atomic-layer-deposited HfO 2 films aminosilanized by (3-Aminopropyl)-trimethoxysilane aforehand for memory applications. The resulting Au nanocrystals show a density of about 4 × 10 11 cm −2 and a diameter range of 5–8nm. The metal-oxide-silicon capacitor with double-layer Au nanocrystals embedded in HfO 2 dielectric exhibits a large C – V hysteresis window of 11.9V for ±11 V gate voltage sweeps at 1 MHz, a flat-band voltage shift of 1.5 V after the electrical stress under 7 V for 1 ms, a leakage current density of 2.9 × 10 −8 A/cm −2 at 9 V and room temperature. Compared to single-layer Au nanocrystals, the double-layer Au nanocrystals increase the hysteresis window significantly, and the underlying mechanism is thus discussed

  16. Thermodynamic Constraints in Using AuM (M = Fe, Co, Ni, and Mo) Alloys as N₂ Dissociation Catalysts: Functionalizing a Plasmon-Active Metal.

    Science.gov (United States)

    Martirez, John Mark P; Carter, Emily A

    2016-02-23

    The Haber-Bosch process for NH3 synthesis is arguably one of the greatest inventions of the 20th century, with a massive footprint in agriculture and, historically, warfare. Current catalysts for this reaction use Fe for N2 activation, conducted at high temperatures and pressures to improve conversion rate and efficiency. A recent finding shows that plasmonic metal nanoparticles can either generate highly reactive electrons and holes or induce resonant surface excitations through plasmonic decay, which catalyze dissociation and redox reactions under mild conditions. It is therefore appealing to consider AuM (M = Fe, Co, Ni, and Mo) alloys to combine the strongly plasmonic nature of Au and the catalytic nature of M metals toward N2 dissociation, which together might facilitate ammonia production. To this end, through density functional theory, we (i) explore the feasibility of forming these surface alloys, (ii) find a pathway that may stabilize/deactivate surface M substituents during fabrication, and (iii) define a complementary route to reactivate them under operational conditions. Finally, we evaluate their reactivity toward N2, as well as their ability to support a pathway for N2 dissociation with a low thermodynamic barrier. We find that AuFe possesses similar appealing qualities, including relative stability with respect to phase separation, reversibility of Fe oxidation and reduction, and reactivity toward N2. While AuMo achieves the best affinity toward N2, its strong propensity toward oxidation could greatly limit its use.

  17. Relativity-Induced Bonding Pattern Change in Coinage Metal Dimers M2 (M = Cu, Ag, Au, Rg).

    Science.gov (United States)

    Li, Wan-Lu; Lu, Jun-Bo; Wang, Zhen-Ling; Hu, Han-Shi; Li, Jun

    2018-05-07

    The periodic table provides a fundamental protocol for qualitatively classifying and predicting chemical properties based on periodicity. While the periodic law of chemical elements had already been rationalized within the framework of the nonrelativistic description of chemistry with quantum mechanics, this law was later known to be affected significantly by relativity. We here report a systematic theoretical study on the chemical bonding pattern change in the coinage metal dimers (Cu 2 , Ag 2 , Au 2 , Rg 2 ) due to the relativistic effect on the superheavy elements. Unlike the lighter congeners basically demonstrating ns- ns bonding character and a 0 g + ground state, Rg 2 shows unique 6d-6d bonding induced by strong relativity. Because of relativistic spin-orbit (SO) coupling effect in Rg 2 , two nearly degenerate SO states, 0 g + and 2 u , exist as candidate of the ground state. This relativity-induced change of bonding mechanism gives rise to various unique alteration of chemical properties compared with the lighter dimers, including higher intrinsic bond energy, force constant, and nuclear shielding. Our work thus provides a rather simple but clear-cut example, where the chemical bonding picture is significantly changed by relativistic effect, demonstrating the modified periodic law in heavy-element chemistry.

  18. Observation of Au + AuAu + Au + ρ0 and Au + AuAu* + Au* + ρ0 with STAR

    International Nuclear Information System (INIS)

    Spencer, K.

    2002-01-01

    First observation of the reactions Au + AuAu + Au + ρ 0 and Au + AuAu* + Au* + ρ 0 with the STAR detector are reported. The ρ are produced at small perpendicular momentum, as expected if they couple coherently to both nuclei. Models of vector meson production and the correlation with nuclear breakup are discussed, as well as a fundamental test of quantum mechanics that is possible with the system. (author)

  19. α-Alkylation of ketones with primary alcohols driven by visible light and bimetallic gold and palladium nanoparticles supported on transition metal oxide

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Meifen; Xin, Hui; Guo, Zhi; Guo, Dapeng; Wang, Yan; Zhao, Peng; Li, Jingyi, E-mail: lijingyicn@163.com

    2017-01-01

    Highlights: • The catalysts were prepared by reduction method at room temperature. • α-Alkylation of ketones and primary alcohols occurred on Au-Pd/CeO{sub 2} in visible light. • Superior catalytic activities were shown on bimetallic Au-Pd/CeO{sub 2} catalysts. • The catalyst can be reused for 4 times. • The mechanism of the synthesis for ketones was proposed. - Abstract: The direct α-alkylation of ketones with primary alcohols to obtain the corresponding saturated coupled ketones was achieved with bimetallic gold(Au)-palladium(Pd) nanoparticles(NPs) supported on a transition metal oxide (such as CeO{sub 2}). This system demonstrated a higher catalytic property than Au/CeO{sub 2} and Pd/CeO{sub 2} under visible light irradiation at 40 ± 3 °C in an Ar atmosphere. Such phenomenon was caused by the synergistic effect between Au and Pd. Isopropyl alcohol was used as the solvent and CH{sub 3}ONa as the base. The effect of the bimetallic Au-Pd mass ratio and the two different transition metal oxide supports (such as CeO{sub 2} or ZrO{sub 2}) during the reaction process was studied. The highest catalytic activity of those examined happened with the 1.5 wt% Au-1.5 wt% Pd (Au and Pd mass ratio 1:1)/CeO{sub 2} photo-catalyst. The intensity and wavelength of the visible light had a strong influence on the system. The catalyst can be reused for four times. A reaction mechanism was proposed for the α-alkylation of ketones with primary alcohols.

  20. Metallization of DNA hydrogel: application of soft matter host for preparation and nesting of catalytic nanoparticles

    Science.gov (United States)

    Zinchenko, Anatoly; Che, Yuxin; Taniguchi, Shota; Lopatina, Larisa I.; G. Sergeyev, Vladimir; Murata, Shizuaki

    2016-07-01

    Nanoparticles (NPs) of Au, Ag, Pt, Pd, Cu and Ni of 2-3 nm average-size and narrow-size distributions were synthesized in DNA cross-linked hydrogels by reducing corresponding metal precursors by sodium borohydride. DNA hydrogel plays a role of a universal reactor in which the reduction of metal precursor results in the formation of 2-3 nm ultrafine metal NPs regardless of metal used. Hydrogels metallized with various metals showed catalytic activity in the reduction of nitroaromatic compounds, and the catalytic activity of metallized hydrogels changed as follows: Pd > Ag ≈ Au ≈ Cu > Ni > Pt. DNA hydrogel-based "soft catalysts" elaborated in this study are promising for green organic synthesis in aqueous media as well as for biomedical in vivo applications.

  1. Plasmonic percolation: Plasmon-manifested dielectric-to-metal transition

    KAUST Repository

    Chen, Huanjun

    2012-08-28

    Percolation generally refers to the phenomenon of abrupt variations in electrical, magnetic, or optical properties caused by gradual volume fraction changes of one component across a threshold in bicomponent systems. Percolation behaviors have usually been observed in macroscopic systems, with most studies devoted to electrical percolation. We report on our observation of plasmonic percolation in Au nanorod core-Pd shell nanostructures. When the Pd volume fraction in the shell consisting of palladium and water approaches the plasmonic percolation threshold, ∼70%, the plasmon of the nanostructure transits from red to blue shifts with respect to that of the unshelled Au nanorod. This plasmonic percolation behavior is also confirmed by the scattering measurements on the individual core-shell nanostructures. Quasistatic theory and numerical simulations show that the plasmonic percolation originates from a positive-to-negative transition in the real part of the dielectric function of the shell as the Pd volume fraction is increased. The observed plasmonic percolation is found to be independent of the metal type in the shell. Moreover, compared to the unshelled Au nanorods with similar plasmon wavelengths, the Au nanorod core-Pd shell nanostructures exhibit larger refractive index sensitivities, which is ascribed to the expulsion of the electric field intensity from the Au nanorod core by the adsorbed Pd nanoparticles. © 2012 American Chemical Society.

  2. Plasmonic percolation: Plasmon-manifested dielectric-to-metal transition

    KAUST Repository

    Chen, Huanjun; Wang, Feng; Li, Kun; Woo, Katchoi; Wang, Jianfang; Li, Quan; Sun, Ling Dong; Zhang, Xixiang; Lin, Haiqing; YAN, Chunhua

    2012-01-01

    Percolation generally refers to the phenomenon of abrupt variations in electrical, magnetic, or optical properties caused by gradual volume fraction changes of one component across a threshold in bicomponent systems. Percolation behaviors have usually been observed in macroscopic systems, with most studies devoted to electrical percolation. We report on our observation of plasmonic percolation in Au nanorod core-Pd shell nanostructures. When the Pd volume fraction in the shell consisting of palladium and water approaches the plasmonic percolation threshold, ∼70%, the plasmon of the nanostructure transits from red to blue shifts with respect to that of the unshelled Au nanorod. This plasmonic percolation behavior is also confirmed by the scattering measurements on the individual core-shell nanostructures. Quasistatic theory and numerical simulations show that the plasmonic percolation originates from a positive-to-negative transition in the real part of the dielectric function of the shell as the Pd volume fraction is increased. The observed plasmonic percolation is found to be independent of the metal type in the shell. Moreover, compared to the unshelled Au nanorods with similar plasmon wavelengths, the Au nanorod core-Pd shell nanostructures exhibit larger refractive index sensitivities, which is ascribed to the expulsion of the electric field intensity from the Au nanorod core by the adsorbed Pd nanoparticles. © 2012 American Chemical Society.

  3. Atomic Structure of Au−Pd Bimetallic Alloyed Nanoparticles

    KAUST Repository

    Ding, Yong

    2010-09-08

    Using a two-step seed-mediated growth method, we synthesized bimetallic nanoparticles (NPs) having a gold octahedron core and a palladium epitaxial shell with controlled Pd-shell thickness. The mismatch-release mechanism between the Au core and Pd shell of the NPs was systematically investigated by high-resolution transmission electron microscopy. In the NPs coated with a single atomic layer of Pd, the strain between the surface Pd layer and the Au core is released by Shockley partial dislocations (SPDs) accompanied by the formation of stacking faults. For NPs coated with more Pd (>2 nm), the stacking faults still exist, but no SPDs are found. This may be due to the diffusion of Au atoms into the Pd shell layers to eliminate the SPDs. At the same time, a long-range ordered L11 AuPd alloy phase has been identified in the interface area, supporting the assumption of the diffusion of Au into Pd to release the interface mismatch. With increasing numbers of Pd shell layers, the shape of the Au-Pd NP changes, step by step, from truncated-octahedral to cubic. After the bimetallic NPs were annealed at 523 K for 10 min, the SPDs at the surface of the NPs coated with a single atomic layer of Pd disappeared due to diffusion of the Au atoms into the surface layer, while the stacking faults and the L11 Au-Pd alloyed structure remained. When the annealing temperature was increased to 800 K, electron diffraction patterns and diffraction contrast images revealed that the NPs became a uniform Au-Pd alloy, and most of the stacking faults disappeared as a result of the annealing. Even so, some clues still support the existence of the L11 phase, which suggests that the L11 phase is a stable, long-range ordered structure in Au-Pd bimetallic NPs. © 2010 American Chemical Society.

  4. Processes and procedures for a thin film multilevel hybrid circuit metallization system based on W--Au/SiO2/Al/SiO2

    International Nuclear Information System (INIS)

    Hampy, R.E.; Knauss, G.L.; Komarek, E.E.; Kramer, D.K.; Villanueva, J.

    1976-04-01

    The processes and procedures developed for the deposition and photodefinition of a W-Au/SiO 2 /Al/SiO 2 hybrid circuit metallization system for the SLL Micro Actuator are described. The metallization system affords a high degree of miniaturization and permits effective interconnection of a mixture of semiconductor devices and passive components with both gold and aluminum terminations without creating undesirable gold-aluminum interfaces. Sputtered tungsten-gold is the first level conductor except at crossovers where tungsten only is used and aluminum is the second level conductor. Silicon dioxide serves as an insulator between the tungsten and aluminum for crossovers. Vias in the insulating layer permit tungsten-aluminum interconnections where desired. A second layer of silicon dioxide is deposited over the metallization and opened for all gold and aluminum bonding pads. Substrates used were polished sapphire and fine grained alumina. The metallization is capable of withstanding processing temperatures up to 400 0 C for short times

  5. Structural stability of Pd40Cu30Ni10P20 metallic glass in supercooled liquid region

    International Nuclear Information System (INIS)

    Jiang, J.Z.; Saksl, K.

    2004-01-01

    Phase separation of bulk and ribbon Pd 40 Cu 30 Ni 10 P 20 glasses, annealed in the supercooled liquid region at ambient pressure and high pressures, has been studied by means of differential scanning calorimetry (DSC) and X-ray diffraction techniques. DSC measurements show only one glass transition event in all annealed samples, indicating that no phase separation occurs in the alloy annealed in the supercooled liquid region. Phase analyses reveal at least six crystalline phases in the crystallized sample: monoclinic, tetragonal Cu 3 Pd-like, rhombohedral, fcc-Ni 2 Pd 2 P, fcc-(Ni, Pd) solid solution, and body-centered tetragonal (bct) Ni 3 P-like phases. Annealing treatments under external pressures in the vicinity of the glass transition temperature neither induce phase separation nor alter the glass transition temperature of the Pd 40 Cu 30 Ni 10 P 20 bulk glass

  6. Metallic double shell hollow nanocages: the challenges of their synthetic techniques.

    Science.gov (United States)

    Mahmoud, M A; El-Sayed, M A

    2012-03-06

    Hollow metallic nanoparticles have been attracting the attention of many researchers in the past five years due to their new properties and potential applications. The unique structure of the hollow nanoparticles; presence of two surfaces (internal and external), and the presence of both cavities and pores in the wall surfaces of these nanoparticles are responsible for their unique properties and applications. Here the galvanic replacement technique is used to prepare nanocages made of gold, platinum, and palladium. In addition, hollow double shell nanoparticles are made of two metal shells like Au-Pt, Pt-Au, Au-Pd, Pd-Au, Pd-Pt, and Pt-Pd. Silver nanocubes are used as templates during the synthesis of hollow nanoparticles with single metal shell or double shell nanocages. Most of the problems that could affect the synthesis of solid Silver nanocubes used as template as well as the double shell nanocages and their possible solutions are discussed in a detail. The sizes and shapes of the single-shell and double-shell nanocages were characterized by a regular and high-resolution TEM. A SEM mapping technique is also used to image the surface atoms for the double shell hollow nanoparticles in order to determine the thickness of the two metal shells. In addition, optical studies are used to monitor the effect of the dielectric properties of the other metals on the plasmonic properties of the gold nanoshell in these mixed nanoparticles.

  7. Comparative study of post-growth annealing of Cu(hfac)2, Co2(CO)8 and Me2Au(acac) metal precursors deposited by FEBID.

    Science.gov (United States)

    Puydinger Dos Santos, Marcos Vinicius; Szkudlarek, Aleksandra; Rydosz, Artur; Guerra-Nuñez, Carlos; Béron, Fanny; Pirota, Kleber Roberto; Moshkalev, Stanislav; Diniz, José Alexandre; Utke, Ivo

    2018-01-01

    Non-noble metals, such as Cu and Co, as well as noble metals, such as Au, can be used in a number modern technological applications, which include advanced scanning-probe systems, magnetic memory and storage, ferroelectric tunnel junction memristors, metal interconnects for high performance integrated circuits in microelectronics and nano-optics applications, especially in the areas of plasmonics and metamaterials. Focused-electron-beam-induced deposition (FEBID) is a maskless direct-write tool capable of defining 3-dimensional metal deposits at nanometre scale for above applications. However, codeposition of organic ligands when using organometallic precursors is a typical problem that limits FEBID of pure metal nanostructures. In this work, we present a comparative study using a post-growth annealing protocol at 100, 200, and 300 °C under high vacuum on deposits obtained from Co 2 (CO) 8 , Cu(II)(hfac) 2 , and Me 2 Au(acac) to study improvements on composition and electrical conductivity. Although the as-deposited material was similar for all precursors, metal grains embedded in a carbonaceous matrix, the post-growth annealing results differed. Cu-containing deposits showed the formation of pure Cu nanocrystals at the outer surface of the initial deposit for temperatures above 100 °C, due to the migration of Cu atoms from the carbonaceous matrix containing carbon, oxygen, and fluorine atoms. The average size of the Cu crystals doubles between 100 and 300 °C of annealing temperature, while the composition remains constant. In contrast, for Co-containing deposits oxygen release was observed upon annealing, while the carbon content remained approximately constant; the cobalt atoms coalesced to form a metallic film. The as-deposited Au-containing material shows subnanometric grains that coalesce at 100 °C, maintaining the same average size at annealing temperatures up to 300 °C. Raman analysis suggests that the amorphous carbonaceous matrix of the as-written Co

  8. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne

    2007-01-01

    Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...... with particle size. We find that the fraction of low-coordinated Au atoms scales approximately with the catalytic activity, suggesting that atoms on the corners and edges of Au nanoparticles are the active sites. This effect is explained using density functional calculations....

  9. A Au82Si18 liquid metal field-ion emitter for the production of Si ions: fundamental properties and mechanisms

    International Nuclear Information System (INIS)

    Bischoff, L.; Mair, G.L.R.; Aidinis, C.J.; Londos, C.A.; Akhmadaliev, C.; Ganetsos, Th.

    2004-01-01

    Focused silicon beams are useful for direct write applications, e.g., lithography on silicon without the undesirable effect of substrate contamination. However, since pure silicon is not amenable to liquid metal ion source (LMIS) manufacture, a suitable alloy containing silicon has to be produced. This paper covers almost all fundamental aspects of a Au 82 Si 18 eutectic, including the most detailed beam mass spectra reported to date of a AuSi source. A finding worthy of note in this investigation, manifested in the behaviour of the ion extraction voltage with temperature, is the abnormal behaviour of the surface tension coefficient of the alloy with temperature. An important deduction from this work, however, concerns the mechanisms responsible for the creation of doubly charged ions: reasons of self-consistency indicate that while Si 2+ is directly field evaporated, Au 2+ must form by the post-ionization of Au + . Finally, two different mechanisms seem to co-exist, as far as the production of cluster ions is concerned. While for cluster ions containing only a few atoms some sort of surface field-ionization mechanism might be responsible for their creation, for larger clusters, a droplet break-up mechanism, possibly by ion capture, seems very likely

  10. One-step synthesis of graphene-Au nanoparticle hybrid materials from metal salt-loaded micelles

    International Nuclear Information System (INIS)

    Liu, X; Zhang, X W; Meng, J H; Wang, H L; Yin, Z G; Wu, J L; Gao, H L

    2014-01-01

    In this study, we present a facile one-step method to synthesize graphene-Au nanoparticle (NP) hybrid materials by using HAuCl 4 -loaded poly(styrene)-block-poly(2-vinylpyridine) (PS-P2VP) micelles as solid carbon sources. N-doped graphene with controllable thickness can be grown from PS-P2VP micelles covered by a Ni capping layer by an annealing process; simultaneously, the HAuCl 4 in the micelles were reduced into Au NPs under a reductive atmosphere to form Au NPs on graphene. The decoration of Au NPs leads to an obviously enhanced electrical conductivity and a slightly increased work function of graphene due to the electron transfer effect. The graphene-Au NP hybrid materials also exhibit a localized surface plasmon resonance feature of Au NPs. This work provides a novel and accessible route for the one-step synthesis of graphene-Au NP hybrid materials with high quality, which might be useful for future applications in optoelectronic devices. (paper)

  11. Luminescent Metal Nanoclusters for Potential Chemosensor Applications

    Directory of Open Access Journals (Sweden)

    Muthaiah Shellaiah

    2017-12-01

    Full Text Available Studies of metal nanocluster (M-NCs-based sensors for specific analyte detection have achieved significant progress in recent decades. Ultra-small-size (<2 nm M-NCs consist of several to a few hundred metal atoms and exhibit extraordinary physical and chemical properties. Similar to organic molecules, M-NCs display absorption and emission properties via electronic transitions between energy levels upon interaction with light. As such, researchers tend to apply M-NCs in diverse fields, such as in chemosensors, biological imaging, catalysis, and environmental and electronic devices. Chemo- and bio-sensory uses have been extensively explored with luminescent NCs of Au, Ag, Cu, and Pt as potential sensory materials. Luminescent bi-metallic NCs, such as Au-Ag, Au-Cu, Au-Pd, and Au-Pt have also been used as probes in chemosensory investigations. Both metallic and bi-metallic NCs have been utilized to detect various analytes, such as metal ions, anions, biomolecules, proteins, acidity or alkalinity of a solution (pH, and nucleic acids, at diverse detection ranges and limits. In this review, we have summarized the chemosensory applications of luminescent M-NCs and bi-metallic NCs.

  12. Ni-Based Catalysts for Low Temperature Methane Steam Reforming: Recent Results on Ni-Au and Comparison with Other Bi-Metallic Systems

    Directory of Open Access Journals (Sweden)

    Anna M. Venezia

    2013-06-01

    Full Text Available Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside of the carbon-forming regime. Reactivity and deactivation by carbon formation can be tuned by modifying Ni surfaces with a second metal, such as Au through alloy formation. In the present review, we summarize the very recent progress in the design, synthesis, and characterization of supported bimetallic Ni-based catalysts for steam reforming. The progress in the modification of Ni with noble metals (such as Au and Ag is discussed in terms of preparation, characterization and pretreatment methods. Moreover, the comparison with the effects of other metals (such as Sn, Cu, Co, Mo, Fe, Gd and B is addressed. The differences of catalytic activity, thermal stability and carbon species between bimetallic and monometallic Ni-based catalysts are also briefly shown.

  13. Perpendicular magnetic anisotropy in granular multilayers of CoPd alloyed nanoparticles

    Science.gov (United States)

    Vivas, L. G.; Rubín, J.; Figueroa, A. I.; Bartolomé, F.; García, L. M.; Deranlot, C.; Petroff, F.; Ruiz, L.; González-Calbet, J. M.; Pascarelli, S.; Brookes, N. B.; Wilhelm, F.; Chorro, M.; Rogalev, A.; Bartolomé, J.

    2016-05-01

    Co-Pd multilayers obtained by Pd capping of pre-deposited Co nanoparticles on amorphous alumina are systematically studied by means of high-resolution transmission electron microscopy, x-ray diffraction, extended x-ray absorption fine structure, SQUID-based magnetometry, and x-ray magnetic circular dichroism. The films are formed by CoPd alloyed nanoparticles self-organized across the layers, with the interspace between the nanoparticles filled by the non-alloyed Pd metal. The nanoparticles show atomic arrangements compatible with short-range chemical order of L 10 strucure type. The collective magnetic behavior is that of ferromagnetically coupled particles with perpendicular magnetic anisotropy, irrespective of the amount of deposited Pd. For increasing temperature three magnetic phases are identified: hard ferromagnetic with strong coercive field, soft-ferromagnetic as in an amorphous asperomagnet, and superparamagnetic. Increasing the amount of Pd in the system leads to both magnetic hardness increment and higher transition temperatures. Magnetic total moments of 1.77(4) μB and 0.45(4) μB are found at Co and Pd sites, respectively, where the orbital moment of Co, 0.40(2) μB, is high, while that of Pd is negligible. The effective magnetic anisotropy is the largest in the capping metal series (Pd, Pt, W, Cu, Ag, Au), which is attributed to the interparticle interaction between de nanoparticles, in addition to the intraparticle anisotropy arising from hybridization between the 3 d -4 d bands associated to the Co and Pd chemical arrangement in a L 10 structure type.

  14. The effect of noble metal additives on the optimum operating temperature of SnO2 gas sensors

    Science.gov (United States)

    Mohammad-Yousefi, S.; Rahbarpour, S.; Ghafoorifard, H.

    2017-12-01

    The effect of Pd and Au additives on gas sensing properties of SnO2 was investigated. SnO2 pallets were fabricated and sintered at 900 °C for 90 minutes. Several nanometer layers of Pd and Au were deposited on separate SnO2 pallets and were intentionally dispersed into the SnO2 pallets by long heat treatment (400 °C for 1 Day). All metal loaded samples showed significant enhancement in response level and optimum operating temperature compare to pure SnO2 gas sensors. The amount of enhancement was strongly dependent on the material and the thickness of deposited metal layer. Studying butanol response showed that increasing the thickness of metal causes the response level to increase. Further thickness increase caused contrary effect and decreased the performance of sensors. Best results were achieved at 10 nm-thick Au and 7 nm-thick Pd. Generally, Pd-SnO2 samples demonstrated better performance than Au-SnO2 ones, however, Au-SnO2 samples were proved to be good candidate to sense reducing gases with lower hydrogen atoms in their formula. Given experimental results were also good evidence of chemical activity of gold and simply confirms the relation between chemical activity and gold particle size. Results were qualitatively described by gas diffusion theory and surface reactions take place on metal particles.The first section in your paper

  15. Effect of an in-plane ligand on the electronic structures of bromo-bridged nano-wire Ni-Pd mixed-metal complexes, [Ni(1-x)Pd(x)(bn)2Br]Br2 (bn = 2S,3S-diaminobutane).

    Science.gov (United States)

    Sasaki, Mari; Wu, Hashen; Kawakami, Daisuke; Takaishi, Shinya; Kajiwara, Takashi; Miyasaka, Hitoshi; Breedlove, Brian K; Yamashita, Masahiro; Kishida, Hideo; Matsuzaki, Hiroyuki; Okamoto, Hiroshi; Tanaka, Hisaaki; Kuroda, Shinichi

    2009-08-03

    Single crystals of quasi-one-dimensional bromo-bridged Ni-Pd mixed-metal complexes with 2S,3S-diaminobutane (bn) as an in-plane ligand, [Ni(1-x)Pd(x)(bn)(2)Br]Br(2), were obtained by using an electrochemical oxidation method involving mixed methanol/2-propanol (1:1) solutions containing different ratios of [Ni(II)(bn)(2)]Br(2) and [Pd(II)(bn)(2)]Br(2). To investigate the competition between the electron-correlation of the Ni(III) states, or Mott-Hubbard states (MH), and the electron-phonon interaction of the Pd(II)-Pd(IV) mixed valence states, or charge-density-wave states (CDW), in the Ni-Pd mixed-metal compounds, X-ray structure analyses, X-ray oscillation photograph, and Raman, IR, ESR, and single-crystal reflectance spectra were analyzed. In addition, the local electronic structures of Ni-Pd mixed-metal single crystals were directly investigated by using scanning tunneling microscopy (STM) at room temperature and ambient pressure. The oxidation states of [Ni(1-x)Pd(x)(bn)(2)Br]Br(2) changed from a M(II)-M(IV) mixed valence state to a M(III) MH state at a critical mixing ratio (x(c)) of approximately 0.8, which is lower than that of [Ni(1-x)Pd(x)(chxn)(2)Br]Br(2) (chxn = 1R,2R-diaminocyclohexane) (x(c) approximately 0.9) reported previously. The lower value of x(c) for [Ni(1-x)Pd(x)(bn)(2)Br]Br(2) can be explained by the difference in their CDW dimensionalities because the three-dimensional CDW ordering in [Pd(bn)(2)Br]Br(2) observed by using X-ray diffuse scattering stabilizes the Pd(II)-Pd(IV) mixed valence state more than two-dimensional CDW ordering in [Pd(chxn)(2)Br]Br(2) does, which has been reported previously.

  16. Semiconducting La{sub 2}AuP{sub 3}, the metallic conductor Ce{sub 2}AuP{sub 3}, and other rare-earth gold phosphides Ln{sub 2}AuP{sub 3} with two closely related crystal structures

    Energy Technology Data Exchange (ETDEWEB)

    Eschen, M.; Kotzyba, G.; Kuennen, B.; Jeitschko, W. [Anorganisch-Chemisches Inst. der Westfaelischen Wilhelms-Univ., Muenster (Germany)

    2001-07-01

    The compounds Ln{sub 2}AuP{sub 3} were synthesized by reaction of the elemental components in evacuated silica tubes. Their crystal structures were determined from single-crystal diffractometer data. The compounds with Ln = La, Ce, and Pr crystallize with an orthorhombic U{sub 2}NiC{sub 3} type structure (Pnma, Z = 4). The structure refinement for Ce{sub 2}AuP{sub 3} resulted in a = 774.14(6) pm, b = 421.11(4) pm, c = 1612.3(1) pm, R = 0.019 for 1410 structure factors and 38 variable parameters. For Pr{sub 2}AuP{sub 3} a residual of R = 0.024 was obtained. Nd{sub 2}AuP{sub 3} crystallizes with a monoclinic distortion of this structure: P2{sub 1}/c, Z = 4, a = 416.14(4) pm, b = 768.87(6) pm, c = 1647.1(2) pm, {beta} = 104.06(1) , R = 0.022 for 1361 F values and 56 variables. The near-neighbor coordinations of the two structures are nearly the same. In both structures the gold and phosphorus atoms form two-dimensionally infinite nets, where the gold atoms are tetrahedrally coordinated by phosphorus atoms with Au-P distances varying between 245.8 and 284.2 pm. Two thirds of the phosphorus atoms form pairs with single-bond distances varying between 217.7 and 218.9 pm. Thus, using oxidation numbers the structures can be rationalized with the formulas (Ln{sup +3}){sub 2}[AuP{sub 3}]{sup -6} and (Ln{sup +3}){sub 2}Au{sup +1}(P{sub 2}){sup -4}P{sup -3}. Accordingly, La{sub 2}AuP{sub 3} is a diamagnetic semiconductor. Pr{sub 2}AuP{sub 3} is semi-conducting with an antiferromagnetic ground state, showing metamagnetism with a critical field of B{sub c} = 0.5({+-}0.1) T. In contrast, the cerium compound is a metallic conductor, even though its cell volume indicates that the cerium atoms are essentially trivalent, as is also suggested by the ferro- or ferrimagnetic behavior of the compound. (orig.)

  17. Memory characteristics of Au nanocrystals embedded in metal-oxide-semiconductor structure by using atomic-layer-deposited Al2O3 as control oxide

    International Nuclear Information System (INIS)

    Wang, C.-C.; Chiou, Y.-K.; Chang, C.-H.; Tseng, J.-Y.; Wu, L.-J.; Chen, C.-Y.; Wu, T.-B.

    2007-01-01

    The nonvolatile memory characteristics of metal-oxide-semiconductor (MOS) structures containing Au nanocrystals in the Al 2 O 3 /SiO 2 matrix were studied. In this work, we have demonstrated that the use of Al 2 O 3 as control oxide prepared by atomic-layer-deposition enhances the erase speed of the MOS capacitors. A giant capacitance-voltage hysteresis loop and a very short erase time which is lower than 1 ms can be obtained. Compared with the conventional floating-gate electrically erasable programmable read-only memories, the erase speed was promoted drastically. In addition, very low leakage current and large turn-around voltage resulting from electrons or holes stored in the Au nanocrystals were found in the current-voltage relation of the MOS capacitors

  18. Tunable reactivity of supported single metal atoms by impurity engineering of the MgO(001) support.

    Science.gov (United States)

    Pašti, Igor A; Johansson, Börje; Skorodumova, Natalia V

    2018-02-28

    Development of novel materials may often require a rational use of high price components, like noble metals, in combination with the possibility to tune their properties in a desirable way. Here we present a theoretical DFT study of Au and Pd single atoms supported by doped MgO(001). By introducing B, C and N impurities into the MgO(001) surface, the interaction between the surface and the supported metal adatoms can be adjusted. Impurity atoms act as strong binding sites for Au and Pd adatoms and can help to produce highly dispersed metal particles. The reactivity of metal atoms supported by doped MgO(001), as probed by CO, is altered compared to their counterparts on pristine MgO(001). We find that Pd atoms on doped MgO(001) are less reactive than on perfect MgO(001). In contrast, Au adatoms bind CO much more strongly when placed on doped MgO(001). In the case of Au on N-doped MgO(001) we find that charge redistribution between the metal atom and impurity takes place even when not in direct contact, which enhances the interaction of Au with CO. The presented results suggest possible ways for optimizing the reactivity of oxide supported metal catalysts through impurity engineering.

  19. Enhancement of chitosan-graphene oxide SPR sensor with a multi-metallic layers of Au–Ag–Au nanostructure for lead(II) ion detection

    Energy Technology Data Exchange (ETDEWEB)

    Kamaruddin, Nur Hasiba [Department of Electric, Electronic and Systems Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Bakar, Ahmad Ashrif A., E-mail: ashrif@ukm.edu.my [Department of Electric, Electronic and Systems Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Yaacob, Mohd Hanif; Mahdi, Mohd Adzir [Wireless and Photonic Network Research Centre, Faculty of Engineering, Universiti Putra Malaysia, 43400 Serdang, Selangor (Malaysia); Zan, Mohd Saiful Dzulkefly [Department of Electric, Electronic and Systems Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia); Shaari, Sahbudin [Institute of Microengineering and Nanoelectronics, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia)

    2016-01-15

    Highlights: • Tri-metallic Au–Ag–Au CS-GO SPR sensor was fabricated for the first time. • The tri-metallic nanostructure provided an enhanced evanescent field. • Successful functionalization of the CS-GO sensing layer. • Superior performance for lead(II) ion detection. - Abstract: We demonstrate the enhancement of surface plasmon resonance (SPR) technique by implementing a multi-metallic layers of Au–Ag–Au nanostructure in the chitosan-graphene oxide (CS-GO) SPR sensor for lead(II) ion detection. The performance of the sensor is analyzed via SPR measurements, from which the sensitivity, signal-to-noise ratio and repeatability are determined. The nanostructure layers are characterized using field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). We showed that the proposed structure has increased the shift in the SPR angle up to 3.5° within the range of 0.1–1 ppm due to the enhanced evanescent field at the sensing layer-analyte interface. This sensor also exhibits great repeatability which benefits from the stable multi-metallic nanostructure. The SNR value of 0.92 for 5 ppm lead(II) ion solution and reasonable linearity range up to that concentration shows that the tri-metallic CS-GO SPR sensor gives a good response towards the lead(II) ion solution. The CS-GO SPR sensor is also sensitive to at least a 10{sup −5} change in the refractive index. The results prove that our proposed tri-metallic CS-GO SPR sensor demonstrates a strong performance and reliability for lead(II) ion detection in accordance with the standardized lead safety level for wastewater.

  20. Interfacial properties of stanene-metal contacts

    Science.gov (United States)

    Guo, Ying; Pan, Feng; Ye, Meng; Wang, Yangyang; Pan, Yuanyuan; Zhang, Xiuying; Li, Jingzhen; Zhang, Han; Lu, Jing

    2016-09-01

    Recently, two-dimensional buckled honeycomb stanene has been manufactured by molecular beam epitaxy growth. Free-standing stanene is predicted to have a sizable opened band gap of 100 meV at the Dirac point due to spin-orbit coupling (SOC), resulting in many fascinating properties such as quantum spin Hall effect, quantum anomalous Hall effect, and quantum valley Hall effect. In the first time, we systematically study the interfacial properties of stanene-metal interfaces (metals = Ag, Au, Cu, Al, Pd, Pt, Ir, and Ni) by using ab initio electronic structure calculations considering the SOC effects. The honeycomb structure of stanene is preserved on the metal supports, but the buckling height is changed. The buckling of stanene on the Au, Al, Ag, and Cu metal supports is higher than that of free-standing stanene. By contrast, a planar graphene-like structure is stabilized for stanene on the Ir, Pd, Pt, and Ni metal supports. The band structure of stanene is destroyed on all the metal supports, accompanied by a metallization of stanene because the covalent bonds between stanene and the metal supports are formed and the structure of stanene is distorted. Besides, no tunneling barrier exists between stanene and the metal supports. Therefore, stanene and the eight metals form a good vertical Ohmic contact.

  1. Effect of Ni and noble metals (Ru, Pd and Pt) on performance of bifunctional MoP/SiO2 for hydroconversion of methyl laurate

    Science.gov (United States)

    Nie, Ziyang; Zhang, Zhena; Chen, Jixiang

    2017-10-01

    SiO2 supported bifunctional MoP catalysts modified with different metal promoters (Ni, Ru, Pd, Pt), where Mo/Ni and Mo/M(M = Ru, Pd and Pt) atomic ratios was respectively 10 and 40, were prepared by TPR method from the phosphate precursors. It was found that the introduction of metal promoters facilitated the reduction of phosphate precursor and enhanced the dispersion of MoP. However, the MoP catalyst acidity was scarcely influenced by the small amount of metal promoters. In the hydroconversion of methyl laurate, the promoters enhanced the MoP catalyst activity for conversion of methyl laurate and hydrogenation of alkenes (intermediate), but reduced isomerization ability. Among the promoters, Ru was an optimum to decrease selectivity to alkenes while maintain high selectivity to iso-alkanes, and Mo40RuP showed better stability than MoP. At 380 °C and 3.0 MPa, the conversion of methyl laurate, the total selectivity to C11 and C12 hydrocarbons and the selectivity to iso-alkanes maintained at 100%, ∼94% and ∼30% on Mo40RuP during 102 h, respectively. The good stability of Mo40RuP is ascribed to that the presence of Ru prevented the sintering of MoP particles and suppressed carbon deposition.

  2. PHENIX measurements of open and hidden heavy flavor in p+p, p+Al, and p/d/3He+Au collisions across a wide range of rapidity

    Science.gov (United States)

    Lim, Sanghoon; Phenix Collaboration

    2017-11-01

    Despite intense theoretical and experimental investigation, the physical mechanisms governing the suppression of bound quark-antiquark states in nuclear collisions are not yet fully understood. While color screening in a plasma phase is expected to play a role, there are numerous other possible suppression mechanisms that do not require deconfinement, as well as effects on the heavy quark initial state in the nucleus which can also play a role. To study these effects, the PHENIX collaboration has used the flexibility of the RHIC accelerator complex to observe the evolution of open heavy flavor and quarkonia dynamics as both the projectile and target nuclei size are varied. Open heavy flavor in small collision systems can serve as the baseline for interpreting quarkonia production in the nuclear environment, and comparisons of the ψ (2 S) with the ψ (1 S) show that in rapidity regions with relatively high hadron density, the larger 2S state is preferentially more suppressed than the more tightly bound ψ (1 S). This suggests that late-stage mechanisms may be at least partially responsible for quarkonia suppression in nuclear collisions. In this talk, we will present results on excited-state quarkonia in p+p, p+Al, and p/d/3He+Au collisions and open heavy flavor in small systems, and discuss how these measurements impact our understanding of heavy quark behavior in the quark-gluon plasma.

  3. Expeditious Synthesis of Noble Metal Nanoparticles Using Vitamin B12 under Microwave Irradiation

    Directory of Open Access Journals (Sweden)

    Changseok Han

    2015-08-01

    Full Text Available A greener synthesis protocol for noble nanometals is developed using vitamin B12 as a reducing and capping agent in conjunction with the use of microwaves. Successful assembly of nanoparticles or microparticles with varied shapes and sizes have been demonstrated. The synthesized Ag, Au, and Pd samples were thoroughly characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high resolution transmission microscopy, and UV-visible spectrophotometry, confirming that metallic Ag, Au, and Pd were synthesized by the green chemistry method.

  4. Metal-assisted chemical etch porous silicon formation method

    Science.gov (United States)

    Li, Xiuling; Bohn, Paul W.; Sweedler, Jonathan V.

    2004-09-14

    A thin discontinuous layer of metal such as Au, Pt, or Au/Pd is deposited on a silicon surface. The surface is then etched in a solution including HF and an oxidant for a brief period, as little as a couple seconds to one hour. A preferred oxidant is H.sub.2 O.sub.2. Morphology and light emitting properties of porous silicon can be selectively controlled as a function of the type of metal deposited, Si doping type, silicon doping level, and/or etch time. Electrical assistance is unnecessary during the chemical etching of the invention, which may be conducted in the presence or absence of illumination.

  5. Effect of different surface treatments and retainer designs on the retention of posterior Pd-Ag porcelain-fused-to-metal resin-bonded fixed partial dentures.

    Science.gov (United States)

    Chen, Xiwen; Zhang, Yixin; Zhou, Jinru; Chen, Chenfeng; Zhu, Zhimin; Li, Lei

    2018-02-01

    The aim of this study was to investigate the adhesive property of palladium-silver alloy (Pd-Ag) and the simulated clinical performance of Pd-Ag porcelain-fused-to-metal (PFM), resin-bonded, fixed partial dentures (RBFPDs). A total of 40 Pd-Ag discs (diameter=5 mm) were prepared and divided into the following four groups (n=10): a) No sandblasting, used as a control; and b, 50 µm; c, 110 µm; and d, 250 µm aluminum oxide (Al 2 O 3 ) particles, respectively. Another 50 discs were pre-sandblasted and divided into five groups (n=10) subjected to different treatments: e) Sandblasting, used as a control; f) silane; g) alloy primer; h) silica coating + silane and i) silica coating + alloy primer. All 90 discs were bonded to enamel with Panavia F 2.0 and then subjected to shear bond strength (SBS) testing. The fracture surfaces were examined by scanning electron microscopy. Next, 40 missing maxillary second premolar models were restored with one of the four following RBFPD designs (n=10): I) A premolar occlusal bar combined with molar double rests (MDR); II) both occlusal bars with a wing (OBB); III) a premolar occlusal bar combined with a molar dental band (MDB); and IV) two single rests adjacent to the edentulous space with a wing (SRB) used as a control. All specimens were aged with thermal cycling and mechanical loading. Subsequently, they were loaded until broken. The data were analyzed by one-way analysis of variance. Al 2 O 3 (250 µm) abrasion provided the highest SBS (P<0.05). The alloy primer and silica + silane exhibited increased SBS. Furthermore, fracture analysis revealed that the failure mode varied among the different treatments. Whereas MDB exhibited the highest retention (P<0.05), that of OBB was greater than that of MDR (P<0.05), and the control exhibited the lowest retention. Abrasion with Al 2 O 3 (250 µm) effectively increased the adhesive property of Pd-Ag. Additionally, treatment with the alloy primer and silica coating + silane was able to

  6. Multiple crossovers between positive and negative magnetoresistance versus field due to fragile spin structure in metallic GdPd3

    Science.gov (United States)

    Pandey, Abhishek; Mazumdar, Chandan; Ranganathan, R.; Johnston, D. C.

    2017-01-01

    Studies on the phenomenon of magnetoresistance (MR) have produced intriguing and application-oriented outcomes for decades–colossal MR, giant MR and recently discovered extremely large MR of millions of percents in semimetals can be taken as examples. We report here the discovery of novel multiple sign changes versus applied magnetic field of the MR in the cubic intermetallic compound GdPd3. Our study shows that a very strong correlation between magnetic, electrical and magnetotransport properties is present in this compound. The magnetic structure in GdPd3 is highly fragile since applied magnetic fields of moderate strength significantly alter the spin arrangement within the system–a behavior that manifests itself in the oscillating MR. Intriguing magnetotransport characteristics of GdPd3 are appealing for field-sensitive device applications, especially if the MR oscillation could materialize at higher temperature by manipulating the magnetic interaction through perturbations caused by chemical substitutions. PMID:28211520

  7. Quantification of elemental area densities in multiple metal layers (Au/Ni/Cu) on a Cr-coated quartz glass substrate for certification of NMIJ CRM 5208-a.

    Science.gov (United States)

    Ariga, Tomoko; Zhu, Yanbei; Ito, Mika; Takatsuka, Toshiko; Terauchi, Shinya; Kurokawa, Akira; Inagaki, Kazumi

    2018-04-01

    Area densities of Au/Ni/Cu layers on a Cr-coated quartz substrate were characterized to certify a multiple-metal-layer certified reference material (NMIJ CRM5208-a) that is intended for use in the analysis of the layer area density and the thickness by an X-ray fluorescence spectrometer. The area densities of Au/Ni/Cu layers were calculated from layer mass amounts and area. The layer mass amounts were determined by using wet chemical analyses, namely inductively coupled plasma mass spectrometry (ICP-MS), isotope-dilution (ID-) ICP-MS, and inductively coupled plasma optical emission spectrometry (ICP-OES) after dissolving the layers with diluted mixture of HCl and HNO 3 (1:1, v/v). Analytical results of the layer mass amounts obtained by the methods agreed well with each another within their uncertainty ranges. The area of the layer was determined by using a high-resolution optical scanner calibrated by Japan Calibration Service System (JCSS) standard scales. The property values of area density were 1.84 ± 0.05 μg/mm 2 for Au, 8.69 ± 0.17 μg/mm 2 for Ni, and 8.80 ± 0.14 μg/mm 2 for Cu (mean ± expanded uncertainty, coverage factor k = 2). In order to assess the reliability of these values, the density of each metal layer calculated from the property values of the area density and layer thickness measured by using a scanning electron microscope were compared with available literature values and good agreement between the observed values and values obtained in previous studies.

  8. Electronic structure and electron dynamics at an organic molecule/metal interface: interface states of tetra-tert-butyl-imine/Au(111)

    International Nuclear Information System (INIS)

    Hagen, Sebastian; Wolf, Martin; Tegeder, Petra; Luo Ying; Haag, Rainer

    2010-01-01

    Time- and angle-resolved two-photon photoemission (2PPE) spectroscopies have been used to investigated the electronic structure, electron dynamics and localization at the interface between tetra-tert-butyl imine (TBI) and Au(111). At a TBI coverage of one monolayer (ML), the two highest occupied molecular orbitals, HOMO and HOMO-1, are observed at an energy of -1.9 and -2.6 eV below the Fermi level (E F ), respectively, and coincide with the d-band features of the Au substrate. In the unoccupied electronic structure, the lowest unoccupied molecular orbital (LUMO) has been observed at 1.6 eV with respect to E F . In addition, two delocalized states that arise from the modified image potential at the TBI/metal interface have been identified. Their binding energies depend strongly on the adsorption structure of the TBI adlayer, which is coverage dependent in the submonolayer (≤1 ML) regime. Thus the binding energy of the lower interface state (IS) shifts from 3.5 eV at 1.0 ML to 4.0 eV at 0.5 ML, which is accompanied by a pronounced decrease in its lifetime from 100 fs to below 10 fs. This is a result of differences in the wave function overlap with electronic states of the Au(111) substrate at different binding energies. This study shows that in order to fully understand the electronic structure of organic adsorbates at metal surfaces, not only adsorbate- and substrate-induced electronic states have to be considered but also ISs, which are the result of a potential formed by the interaction between the adsorbate and the substrate.

  9. Heterocycles by Transition Metals Catalyzed Intramolecular Cyclization of Acetylene Compounds

    International Nuclear Information System (INIS)

    Vizer, S.A.; Yerzhanov, K.B.; Dedeshko, E.C.

    2003-01-01

    Review shows the new strategies in the synthesis of heterocycles, having nitrogen, oxygen and sulfur atoms, via transition metals catalyzed intramolecular cyclization of acetylenic compounds on the data published at the last 30 years, Unsaturated heterocyclic compounds (pyrroles and pyrroline, furans, dihydro furans and benzofurans, indoles and iso-indoles, isoquinolines and isoquinolinones, aurones, iso coumarins and oxazolinone, lactams and lactones with various substitutes in heterocycles) are formed by transition metals, those salts [PdCl 2 , Pd(OAc) 2 , HgCl 2 , Hg(OAc) 2 , Hg(OCOCF 3 ) 2 , AuCl 3 ·2H 2 O, NaAuCl 4 ·2H 2 O, CuI, CuCl], oxides (HgO) and complexes [Pd(OAc) 2 (PPh 3 )2, Pd(PPh 3 ) 4 , PdCl 2 (MeCN) 2 , Pd(OAc ) 2 /TPPTS] catalyzed intramolecular cyclization of acetylenic amines, amides, ethers, alcohols, acids, ketones and βdiketones. More complex hetero polycyclic systems typical for natural alkaloids can to obtain similar. Proposed mechanisms of pyrroles, isoquinolines, iso indoles and indoles, benzofurans and iso coumarins, thiazolopyrimidinones formation are considered. (author)

  10. Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd.

    Science.gov (United States)

    Duguid, J; Bloomfield, V A; Benevides, J; Thomas, G J

    1993-11-01

    Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) induce the greatest structural changes in B-DNA. The Raman (vibrational) band differences are extensive and indicate partial disordering of the B-form backbone, reduction in base stacking, reduction in base pairing, and specific metal interaction with acceptor sites on the purine (N7) and pyrimidine (N3) rings. Many of the observed spectral changes parallel those accompanying thermal denaturation of B-DNA and suggest that the metals link the bases of denatured DNA. While exocyclic carbonyls of dT, dG, and dC may stabilize metal ligation, correlation plots show that perturbations of the carbonyls are mainly a consequence of metal-induced denaturation of the double helix. Transition metal interactions with the DNA phosphates are weak in comparison to interactions with the bases, except in the case of Cu2+, which strongly perturbs both base and phosphate group vibrations. On the other hand, the Raman signature of B-DNA is largely unperturbed by Mg2+, Ca2+, Sr2+, and Ba2+, suggesting much weaker interactions of the alkaline earth metals with both base and phosphate sites. A notable exception is a moderate perturbation by alkaline earths of purine N7 sites in 160-base pair DNA, with Ca2+ causing the greatest effect. Correlation plots demonstrate a strong interrelationship between perturbations of Raman bands assigned to ring vibrations of the bases and those of bands assigned to exocyclic carbonyls and backbone phosphodiester groups. However, strong correlations do not occur between

  11. Density functional theory based study of chlorine doped WS2-metal interface

    International Nuclear Information System (INIS)

    Chanana, Anuja; Mahapatra, Santanu

    2016-01-01

    Investigation of a transition metal dichalcogenide (TMD)-metal interface is essential for the effective functioning of monolayer TMD based field effect transistors. In this work, we employ the Density Functional Theory calculations to analyze the modulation of the electronic structure of monolayer WS 2 with chlorine doping and the relative changes in the contact properties when interfaced with gold and palladium. We initially examine the atomic and electronic structures of pure and doped monolayer WS 2 supercell and explore the formation of midgap states with band splitting near the conduction band edge. Further, we analyze the contact nature of the pure supercell with Au and Pd. We find that while Au is physiosorbed and forms n-type contact, Pd is chemisorped and forms p-type contact with a higher valence electron density. Next, we study the interface formed between the Cl-doped supercell and metals and observe a reduction in the Schottky barrier height (SBH) in comparison to the pure supercell. This reduction found is higher for Pd in comparison to Au, which is further validated by examining the charge transfer occurring at the interface. Our study confirms that Cl doping is an efficient mechanism to reduce the n-SBH for both Au and Pd, which form different types of contact with WS 2 .

  12. Density functional theory based study of chlorine doped WS{sub 2}-metal interface

    Energy Technology Data Exchange (ETDEWEB)

    Chanana, Anuja; Mahapatra, Santanu, E-mail: santanu@dese.iisc.ernet.in [NanoScale Device Research Laboratory, Department of Electronic Systems Engineering, Indian Institute of Science, Bengaluru, Karnataka 560012 (India)

    2016-03-07

    Investigation of a transition metal dichalcogenide (TMD)-metal interface is essential for the effective functioning of monolayer TMD based field effect transistors. In this work, we employ the Density Functional Theory calculations to analyze the modulation of the electronic structure of monolayer WS{sub 2} with chlorine doping and the relative changes in the contact properties when interfaced with gold and palladium. We initially examine the atomic and electronic structures of pure and doped monolayer WS{sub 2} supercell and explore the formation of midgap states with band splitting near the conduction band edge. Further, we analyze the contact nature of the pure supercell with Au and Pd. We find that while Au is physiosorbed and forms n-type contact, Pd is chemisorped and forms p-type contact with a higher valence electron density. Next, we study the interface formed between the Cl-doped supercell and metals and observe a reduction in the Schottky barrier height (SBH) in comparison to the pure supercell. This reduction found is higher for Pd in comparison to Au, which is further validated by examining the charge transfer occurring at the interface. Our study confirms that Cl doping is an efficient mechanism to reduce the n-SBH for both Au and Pd, which form different types of contact with WS{sub 2}.

  13. Experimental Determination of Spinel/Melt, Olivine/Melt, and Pyroxene/Melt Partition Coefficients for Re, Ru, Pd, Au, and Pt

    Science.gov (United States)

    Righter, K.; Campbell, A. J.; Humayun, M.

    2003-01-01

    Experimental studies have identified spinels as important hosts phases for many of the highly siderophile elements (HSE). Yet experimental studies involving chromite or Cr-rich spinel have been lacking. Experimental studies of partitioning of HSEs between silicate, oxides and silicate melt are plagued by low solubilities and the presence of small metallic nuggets at oxygen fugacities relevant to magmas, which interfere with analysis of the phases of interest. We have circumvented these problems in two ways: 1) performing experiments at oxidized conditions, which are still relevant to natural systems but in which nuggets are not observed, and 2) analysis of run products with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), allowing a combination of high sensitivity and good spatial resolution.

  14. Ion-beam-mixing in metal-metal systems and metal-silicon systems

    International Nuclear Information System (INIS)

    Hung, L.

    1984-01-01

    The influence of energetic ion bombardment on the composition and structure of thin film materials and utilization of ion-beam-mixing techniques to modify interfacial reactions are reported in this thesis. The phase formation in metals by using ion mixing techniques has been studied. Upon ion irradiation of Al/Pt, Al/Pd and Al/Ni thin films, only the simplest intermetallic compounds of PdAl and NiAl were formed in crystalline structure, while the amorphous phase has been observed over a large range of composition. Ion mixing of Au/Cu bilayers resulted in the formation of substitutional solid solutions with no trace of ordered compounds. The formation of the ordered compound CuAu was achieved either by irradiation of bilayers with Ar ions at elevated substrate temperature or by irradiation of the mixed layers with He ions at relatively low temperature. In the Au/Al system several crystal compounds existed in the as-deposited samples. These phases remained crystalline or transformed into other equilibrium compounds upon ion irradiation. The results suggest that the phase formation by ion mixing is dependent on the high quench rate in the collision cascade region and the atomic mobility at the irradiation temperature. The argument can be applied to silicide forming systems. With near-noble metals, the mixed atoms are mobile and form metallurgically distinct phases. With refractory metals, amorphous phases are formed due to lack of atomic mobility

  15. Noble metals can have different effects on photocatalysis over metal-organic frameworks (MOFs): a case study on M/NH₂-MIL-125(Ti) (M=Pt and Au).

    Science.gov (United States)

    Sun, Dengrong; Liu, Wenjun; Fu, Yanghe; Fang, Zhenxing; Sun, Fangxiang; Fu, Xianzhi; Zhang, Yongfan; Li, Zhaohui

    2014-04-14

    M-doped NH2-MIL-125(Ti) (M=Pt and Au) were prepared by using the wetness impregnation method followed by a treatment with H2 flow. The resultant samples were characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analyses, N2-sorption BET surface area, and UV/Vis diffuse reflectance spectroscopy (DRS). The photocatalytic reaction carried out in saturated CO2 with triethanolamine (TEOA) as sacrificial agent under visible-light irradiations showed that the noble metal-doping on NH2-MIL-125(Ti) promoted the photocatalytic hydrogen evolution. Unlike that over pure NH2-MIL-125(Ti), in which only formate was produced, both hydrogen and formate were formed over Pt- and Au-loaded NH2-MIL-125(Ti). However, Pt and Au have different effects on the photocatalytic performance for formate production. Compared with pure NH2-MIL-125(Ti), Pt/NH2-MIL-125(Ti) showed an enhanced activity for photocatalytic formate formation, whereas Au has a negative effect on this reaction. To elucidate the origin of the different photocatalytic performance, electron spin resonance (ESR) analyses and density functional theory (DFT) calculations were carried out over M/NH2-MIL-125(Ti).The photocatalytic mechanisms over M/NH2-MIL-125(Ti) (M=Pt and Au) were proposed. For the first time, the hydrogen spillover from the noble metal Pt to the framework of NH2-MIL-125(Ti) and its promoting effect on the photocatalytic CO2 reduction is revealed. The elucidation of the mechanism on the photocatalysis over M/NH2-MIL-125(Ti) can provide some guidance in the development of new photocatalysts based on MOF materials. This study also demonstrates the potential of using noble metal-doped MOFs in photocatalytic reactions involving hydrogen as a reactant, like hydrogenation reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Separation and Recovery of Precious Metals from Leach Liquors of Spent Electronic Wastes by Solvent Extraction

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Thi Hong; Wang, Lingyun; Lee, Man Seung [Mokpo National University, Mokpo (Korea, Republic of)

    2017-04-15

    Solvent extraction was employed to recover precious metals (Au (III), Pd (II) and Pt (IV)) from the leach solution of spent electronic wastes containing Cu (II), Cr (III) and Fe (III). First, pure Fe (III) and Au (III) were recovered by simultaneous extraction with Cyanex 923 followed by selective stripping with HCl and Na{sub 2}S{sub 2}O{sub 3}. Second, Pt (IV), Pd (II) and Cu (II) were extracted by Alamine 336 from the raffinate. After the removal of Cu (II) by stripping with weak HCl, Pd (II) and Pt (IV) were separately stripped by controlling the concentration of thiourea in the mixture with HCl. A process flow sheet for the separation of precious metals was proposed.

  17. Magnetism and transport studies in off-stoichiometric metallic perovskite compounds GdPd{sub 3}B{sub x} (x=0.25, 0.50 and 0.75)

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Abhishek, E-mail: abhishek.phy@gmail.co [S. N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India); Mazumdar, Chandan, E-mail: chandan.mazumdar@saha.ac.i [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India); Ranganathan, R. [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India)

    2010-12-15

    We report the magnetic and transport properties of the off-stoichiometric metallic perovskite like compounds GdPd{sub 3}B{sub x} (x=0.25, 0.50 and 0.75). Our results show that doping with boron in the lattice of parent binary-compound GdPd{sub 3} leads to lattice expansion. Which in turn manifests in contrasting magnetic and transport behaviors of the doped compounds in comparison with the undoped GdPd{sub 3}. An attempt has been made to compare and correlate the results of magnetic and transport measurements of GdPd{sub 3}B{sub x} with that of stoichiometric compositions GdPd{sub 3}B{sub x}C{sub 1-x}. The comparative study of GdPd{sub 3}B{sub x} and GdPd{sub 3}B{sub x}C{sub 1-x} confirms that there is a strong correlations between the structural, magnetic and transport properties of these compounds.

  18. O{sub 2} adsorption and dissociation on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Li, Sha; Yang, Yongpeng; Huang, Shiping, E-mail: huangsp@mail.buct.edu.cn

    2017-07-15

    Highlights: • O{sub 2} adsorption and dissociation on Pd{sub 13-n}Ni{sub n}@Pt{sub 42} NPs are performed by DFT. • Adsorption energies of O{sub 2} and O are strongly affected by the coordination number. • Adsorption energy and d-band center displays the opposite change tendency. • Ni{sub 13}@Pt{sub 42} is the most active catalyst among Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) NPs. - Abstract: Density functional theory calculations are performed to investigate O{sub 2} adsorption and dissociation on the icosahedral Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles. The parallel adsorption of O{sub 2} on Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) is stronger than the vertical adsorption. The adsorption of O{sub 2} on the bridge site (B1) is favorable in the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) nanoparticles, while the adsorption of O atom on the hollow site (H1) is preferred. The adsorption energies of O{sub 2} and O are strongly affected by the coordination number. Low coordination site shows strong adsorption of O{sub 2} and O on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) nanoparticles. The adsorption energies of O{sub 2} and O atoms are found to be correlated well with the d-band center of surface Pt. For the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and13) nanoparticles catalysts, the ORR activity follows the order of Ni{sub 13}@Pt{sub 42} > Pd{sub 13}@Pt{sub 42} > Pd{sub 12}Ni{sub 1}@Pt{sub 42} > Pd{sub 1}Ni{sub 12}@Pt{sub 42}, illustrating that the Ni{sub 13}@Pt{sub 42} is the strongest ORR activity among the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and13) nanoparticles catalysts. Our results have important significance to understand the mechanism of O{sub 2} dissociation on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles.

  19. Ion-stimulated gas desorption yields of coated (Au, Ag, Pd) stainless steel vacuum chambers irradiated with 4.2 MeV/u lead ions

    CERN Document Server

    Mahner, E; Küchler, D; Malabaila, M; Taborelli, M

    2005-01-01

    The ion-induced desorption experiment, installed in the CERN Heavy Ion Accelerator (LINAC 3), has been used to measure molecular desorption yields for 4.2 MeV/u lead ions impacting on different accelerator-type vacuum chambers. In order to study the effect of the surface oxide layer on the gas desorption, gold-, silver-, and palladium-coated 316LN stainless steel chambers and similarly prepared samples were tested for desorption at LINAC 3 and analysed for chemical composition by X-ray Photoemission Spectroscopy (XPS). The large effective desorption yield of 2 x 10**4 molecules/ion, previously measured for uncoated, vacuum fired stainless steel, was reduced after noble metal coating by up to 2 orders of magnitude. In addition, the effectiveness of beam scrubbing with heavy ions and the consequence of a subsequent venting on the desorption yields of a beam-scrubbed vacuum chamber are described. Practical consequences for the vacuum system of the future Low Energy Ion Ring (LEIR) are discussed.

  20. Activation of charcoal made from japanese cypress as oxygen electrode in fuel cell by deposition of Pd-metal/Heteropolyacids of the micropores; Kinzokuparajiumu-heteroporisan no bunsan tanzi niyoru hinoki mokutan no nenryo denchisansokyoku to shiteno kinouka

    Energy Technology Data Exchange (ETDEWEB)

    Yumine, Takuya.; Kominami, Hiroshi.; Kera, Yoshiya. [Kinki University, osaka (Japan); Abe, Ikuo. [Osaka Municipal Technology Research Institute, Osaka (Japan)

    1998-12-31

    Pd- and Pt-metal were observed by TEM to be highly disperdsed on charcoal prepared from Japanese Cypress [Hinoki] at 900degreeC (Pd, Pt/H2). Nafion-sheet was hot-pressed with Pd/H2 and Pt/H2 disc-pellets placed in the other sides to make a fuel cell-electrode unit. The 1-V curve in the H{sub 2}-O{sub 2} fuel were measured : The voltage certainly grew with increase in the amount of Pd-metal (1{yields}13wt%) and with a mixing of [Nafion] powder (11wt%). The discharge character was greatly improved with the addition of heteropolyacid (H{sub 3}PMo{sub 11}VO{sub 42};PVMo{sub 11}). When a charcoal prepared from Hinoki at 2400degreeC (HG) was used, the inner resistivity was about 10-times lower than the case of H2 used, although the dispersed states of Pd-metal became considerably poor on HG rather than H2. The actuvuty also increased further with the addition of Nafion and PVMo{sub 11}. (author)

  1. Au-Interaction of Slp1 Polymers and Monolayer from Lysinibacillus sphaericus JG-B53 - QCM-D, ICP-MS and AFM as Tools for Biomolecule-metal Studies

    Science.gov (United States)

    Suhr, Matthias; Raff, Johannes; Pollmann, Katrin

    2016-01-01

    In this publication the gold sorption behavior of surface layer (S-layer) proteins (Slp1) of Lysinibacillus sphaericus JG-B53 is described. These biomolecules arrange in paracrystalline two-dimensional arrays on surfaces, bind metals, and are thus interesting for several biotechnical applications, such as biosorptive materials for the removal or recovery of different elements from the environment and industrial processes. The deposition of Au(0) nanoparticles on S-layers, either by S-layer directed synthesis 1 or adsorption of nanoparticles, opens new possibilities for diverse sensory applications. Although numerous studies have described the biosorptive properties of S-layers 2-5, a deeper understanding of protein-protein and protein-metal interaction still remains challenging. In the following study, inductively coupled mass spectrometry (ICP-MS) was used for the detection of metal sorption by suspended S-layers. This was correlated to measurements of quartz crystal microbalance with dissipation monitoring (QCM-D), which allows the online detection of proteinaceous monolayer formation and metal deposition, and thus, a more detailed understanding on metal binding. The ICP-MS results indicated that the binding of Au(III) to the suspended S-layer polymers is pH dependent. The maximum binding of Au(III) was obtained at pH 4.0. The QCM-D investigations enabled the detection of Au(III) sorption as well as the deposition of Au(0)-NPs in real-time during the in situ experiments. Further, this method allowed studying the influence of metal binding on the protein lattice stability of Slp1. Structural properties and protein layer stability could be visualized directly after QCM-D experiment using atomic force microscopy (AFM). In conclusion, the combination of these different methods provides a deeper understanding of metal binding by bacterial S-layer proteins in suspension or as monolayers on either bacterial cells or recrystallized surfaces. PMID:26863150

  2. Effect of annealing temperature on the electrical properties of Au/Ta{sub 2}O{sub 5}/n-GaN metal-insulator-semiconductor (MIS) structure

    Energy Technology Data Exchange (ETDEWEB)

    Prasanna Lakshmi, B.; Rajagopal Reddy, V.; Janardhanam, V. [Sri Venkateswara University, Department of Physics, Tirupati (India); Siva Pratap Reddy, M.; Lee, Jung-Hee [Kyungpook National University, School of Electrical Engineering and Computer Science, Daegu (Korea, Republic of)

    2013-11-15

    We report on the effect of an annealing temperature on the electrical properties of Au/Ta{sub 2}O{sub 5}/n-GaN metal-insulator-semiconductor (MIS) structure by current-voltage (I-V) and capacitance-voltage (C-V) measurements. The measured Schottky barrier height ({Phi} {sub bo}) and ideality factor n values of the as-deposited Au/Ta{sub 2}O{sub 5}/n-GaN MIS structure are 0.93 eV (I-V) and 1.19. The barrier height (BH) increases to 1.03 eV and ideality factor decreases to 1.13 upon annealing at 500 {sup circle} C for 1 min under nitrogen ambient. When the contact is annealed at 600 {sup circle} C, the barrier height decreases and the ideality factor increases to 0.99 eV and 1.15. The barrier heights obtained from the C-V measurements are higher than those obtained from I-V measurements, and this indicates the existence of spatial inhomogeneity at the interface. Cheung's functions are also used to calculate the barrier height ({Phi} {sub bo}), ideality factor (n), and series resistance (R{sub s}) of the Au/Ta{sub 2}O{sub 5}/n-GaN MIS structure. Investigations reveal that the Schottky emission is the dominant mechanism and the Poole-Frenkel emission occurs only in the high voltage region. The energy distribution of interface states is determined from the forward bias I-V characteristics by taking into account the bias dependence of the effective barrier height. It is observed that the density value of interface states for the annealed samples with interfacial layer is lower than that of the density value of interface states of the as-deposited sample. (orig.)

  3. New experimental set-up and procedure for analyzing the dynamics of permeation of H2(g) across Pd-based metallic membranes

    International Nuclear Information System (INIS)

    Decaux, C.; Millet, P.; Decaux, C.

    2006-01-01

    . Impedances of the sorbing (permeating) membrane materials are then calculated using the theory of linear and time-invariant systems, by numerically Fourier-transforming the discretely sampled pressure signals. Using appropriate initial and boundary conditions, it is shown that the rate constants of the two major steps of the sorption (permeation) mechanisms can be separately accessed, i.e. surface resistances related to hydrogen dissociation (upstream side) and recombination (downstream side) processes, and bulk diffusion impedance. This experimental equipment and this treatment procedure therefore provide a new tool for analyzing the dynamics of hydrogen permeation across metallic membranes. This tool can be used for diagnosis purposes and for optimizing the structure and composition of permeation membranes. Results obtained with Pd and Pd 77 Ag 23 foils are presented and discussed. (authors)

  4. Electro-catalytic activity of multiwall carbon nanotube-metal (Pt or Pd) nanohybrid materials synthesized using microwave-induced reactions and their possible use in fuel cells.

    Science.gov (United States)

    V, Lakshman Kumar; Ntim, Susana Addo; Sae-Khow, Ornthida; Janardhana, Chelli; Lakshminarayanan, V; Mitra, Somenath

    2012-11-30

    Microwave induced reactions for immobilizing platinum and palladium nanoparticles on multiwall carbon nanotubes are presented. The resulting hybrid materials were used as catalysts for direct methanol, ethanol and formic acid oxidation in acidic as well as alkaline media. The electrodes are formed by simply mixing the hybrids with graphite paste, thus using a relatively small quantity of the precious metal. We report Tafel slopes and apparent activation energies at different potentials and temperatures. Ethanol electro-oxidation with the palladium hybrid showed an activation energy of 7.64 kJmol(-1) which is lower than those observed for other systems. This system is economically attractive because Pd is significantly less expensive than Pt and ethanol is fast evolving as a commercial biofuel.

  5. Electro-catalytic activity of multiwall carbon nanotube-metal (Pt or Pd) nanohybrid materials synthesized using microwave-induced reactions and their possible use in fuel cells

    Science.gov (United States)

    V, Lakshman Kumar; Ntim, Susana Addo; Sae-Khow, Ornthida; Janardhana, Chelli; Lakshminarayanan, V.; Mitra, Somenath

    2012-01-01

    Microwave induced reactions for immobilizing platinum and palladium nanoparticles on multiwall carbon nanotubes are presented. The resulting hybrid materials were used as catalysts for direct methanol, ethanol and formic acid oxidation in acidic as well as alkaline media. The electrodes are formed by simply mixing the hybrids with graphite paste, thus using a relatively small quantity of the precious metal. We report Tafel slopes and apparent activation energies at different potentials and temperatures. Ethanol electro-oxidation with the palladium hybrid showed an activation energy of 7.64 kJmol−1 which is lower than those observed for other systems. This system is economically attractive because Pd is significantly less expensive than Pt and ethanol is fast evolving as a commercial biofuel. PMID:23118490

  6. Improvement on the electrical characteristics of Pd/HfO2/6H-SiC MIS capacitors using post deposition annealing and post metallization annealing

    Science.gov (United States)

    Esakky, Papanasam; Kailath, Binsu J.

    2017-08-01

    HfO2 as a gate dielectric enables high electric field operation of SiC MIS structure and as gas sensor HfO2/SiC capacitors offer higher sensitivity than SiO2/SiC capacitors. The issue of higher density of oxygen vacancies and associated higher leakage current necessitates better passivation of HfO2/SiC interface. Effect of post deposition annealing in N2O plasma and post metallization annealing in forming gas on the structural and electrical characteristics of Pd/HfO2/SiC MIS capacitors are reported in this work. N2O plasma annealing suppresses crystallization during high temperature annealing thereby improving the thermal stability and plasma annealing followed by rapid thermal annealing in N2 result in formation of Hf silicate at the HfO2/SiC interface resulting in order of magnitude lower density of interface states and gate leakage current. Post metallization annealing in forming gas for 40 min reduces interface state density by two orders while gate leakage current density is reduced by thrice. Post deposition annealing in N2O plasma and post metallization annealing in forming gas are observed to be effective passivation techniques improving the electrical characteristics of HfO2/SiC capacitors.

  7. Improvement on the electrical characteristics of Pd/HfO{sub 2}/6H-SiC MIS capacitors using post deposition annealing and post metallization annealing

    Energy Technology Data Exchange (ETDEWEB)

    Esakky, Papanasam, E-mail: papanasamte@gmail.com; Kailath, Binsu J

    2017-08-15

    Highlights: • Post deposition annealing (PDA) and post metallization annealing (PMA) on the electrical characteristics of Pd/HfO{sub 2}/6H-SiC MIS capacitors. • Post deposition N{sub 2}O plasma annealing inhibits crystallization of HfO{sub 2} during high temperature annealing. • Plasma annealing followed by RTA in N{sub 2} results in formation of hafnium silicate at the HfO{sub 2}-SiC interface. • PDA reduces interface state density (D{sub it}) and gate leakage current density (J{sub g}) by order. • PMA in forming gas for 40 min results in better passivation and reduces D{sub it} by two orders and J{sub g} by thrice. - Abstract: HfO{sub 2} as a gate dielectric enables high electric field operation of SiC MIS structure and as gas sensor HfO{sub 2}/SiC capacitors offer higher sensitivity than SiO{sub 2}/SiC capacitors. The issue of higher density of oxygen vacancies and associated higher leakage current necessitates better passivation of HfO{sub 2}/SiC interface. Effect of post deposition annealing in N{sub 2}O plasma and post metallization annealing in forming gas on the structural and electrical characteristics of Pd/HfO{sub 2}/SiC MIS capacitors are reported in this work. N{sub 2}O plasma annealing suppresses crystallization during high temperature annealing thereby improving the thermal stability and plasma annealing followed by rapid thermal annealing in N{sub 2} result in formation of Hf silicate at the HfO{sub 2}/SiC interface resulting in order of magnitude lower density of interface states and gate leakage current. Post metallization annealing in forming gas for 40 min reduces interface state density by two orders while gate leakage current density is reduced by thrice. Post deposition annealing in N{sub 2}O plasma and post metallization annealing in forming gas are observed to be effective passivation techniques improving the electrical characteristics of HfO{sub 2}/SiC capacitors.

  8. Dissolving, trapping and detrapping mechanisms of hydrogen in bcc and fcc transition metals

    Directory of Open Access Journals (Sweden)

    Yu-Wei You

    2013-01-01

    Full Text Available First-principles calculations are performed to investigate the dissolving, trapping and detrapping of H in six bcc (V, Nb, Ta, Cr, Mo, W and six fcc (Ni, Pd, Pt, Cu, Ag, Au metals. We find that the zero-point vibrations do not change the site-preference order of H at interstitial sites in these metals except Pt. One vacancy could trap a maximum of 4 H atoms in Au and Pt, 6 H atoms in V, Nb, Ta, Cr, Ni, Pd, Cu and Ag, and 12 H atoms in Mo and W. The zero-point vibrations never change the maximum number of H atoms trapped in a single vacancy in these metals. By calculating the formation energy of vacancy-H (Vac-Hn complex, the superabundant vacancy in V, Nb, Ta, Pd and Ni is demonstrated to be much more easily formed than in the other metals, which has been found in many metals including Pd, Ni and Nb experimentally. Besides, we find that it is most energetically favorable to form Vac-H1 complex in Pt, Cu, Ag and Au, Vac-H4 in Cr, Mo and W, and Vac-H6 in V, Nb, Ta, Pd and Ni. At last, we examine the detrapping behaviors of H atoms in a single vacancy and find that with the heating rate of 10 K/min a vacancy could accommodate 4, 5 and 6 H atoms in Cr, Mo and W at room temperature, respectively. The detrapping temperatures of all H atoms in a single vacancy in V, Nb, Ta, Ni, Pd, Cu and Ag are below room temperature.

  9. Refractometers for different refractive index range by surface plasmon resonance sensors in multimode optical fibers with different metals

    Science.gov (United States)

    Zuppella, P.; Corso, Alain J.; Pelizzo, Maria G.; Cennamo, N.; Zeni, L.

    2016-09-01

    We have realized a plasmonic sensor based on Au/Pd metal bilayer in a multimode plastic optical fiber. This metal bilayer, based on a metal with high imaginary part of the refractive index and gold, shows interesting properties in terms of sensitivity and performances, in different refractive index ranges. The development of highly sensitive platforms for high refractive index detection (higher than 1.38) is interesting for chemical applications based on molecularly imprinted polymer as receptors, while the aqueous medium is the refractive index range of biosensors based on bio-receptors. In this work we have presented an Au/Pd metal bilayer optimized for 1.38-1.42 refractive index range.

  10. Magma Fertility is the First-Order Factor for the Formation of Porphyry Cu±Au Deposits

    Science.gov (United States)

    Park, J. W.; Campbell, I. H.; Malaviarachchi, S. P. K.; Cocker, H.; Nakamura, E.; Kay, S. M.

    2017-12-01

    Magma fertility, the metal abundance in magma, has been considered to be one of the key factors for the formation of porphyry Cu±Au deposits. In this study we provide clear evidence to support the hypothesis that the platinum group element (PGE) can be used to distinguish barren from ore-bearing Cu±Au felsic suites. We determined the PGE contents of three barren volcanic and subvolcanic suites from Argentina and Japan, and compare the results with two porphyry Cu-bearing subvolcanic suites from Chile and two porphyry Cu-Au-bearing suites from Australia. The barren suites are significantly depleted in PGE abundances by the time of fluid exsolution, which is attributed to early sulfide saturation at mid to lower crust depths or assimilation of chalcophile element-poor crustal materials. Barren magma, produced by melting continental crust, may have been initially deficient in chalcophile elements. In contrast, the Cu±Au ore-bearing suites contain at least an order of magnitude higher PGE contents than those of the barren suites by the time of fluid saturation. They are characterized by late sulfide saturation in a shallow magma chamber, which allows the chalcophile elements to concentrate in the fractionating magma from which they are sequestered by ore-forming fluids. We suggest the Pd/MgO and Pd/Pt ratios of igneous rocks can be used as magma fertility indicators, and to distinguish between barren, porphyry Cu and porphyry Cu-Au magmatic systems.

  11. Growth of vertically aligned single-walled carbon nanotubes with metallic chirality through faceted FePt-Au catalysts

    Science.gov (United States)

    Ohashi, Toshiyuki; Iwama, Hiroki; Shima, Toshiyuki

    2016-02-01

    Direct synthesis of vertically aligned metallic single-walled carbon nanotubes (m-SWCNT forests) is a difficult challenge. We have successfully synthesized m-SWCNT forests using faceted iron platinum-gold catalysts epitaxially grown on a single crystalline magnesium oxide substrate. The metallic content of the forests estimated by Raman spectroscopy reaches 90%. From the standpoint of growth rate of the forests, the growth mechanism is probably based on the catalyst of solid state. It is suggested that preferential growth of m-SWCNTs is achieved when both factors are satisfied, namely, {111} dominant octahedral facet and ideal size (fine particles) of FePt particles.

  12. Fabricating a Homogeneously Alloyed AuAg Shell on Au Nanorods to Achieve Strong, Stable, and Tunable Surface Plasmon Resonances

    KAUST Repository

    Huang, Jianfeng

    2015-08-13

    Colloidal metal nanocrystals with strong, stable, and tunable localized surface plasmon resonances (SPRs) can be useful in a corrosive environment for many applications including field-enhanced spectroscopies, plasmon-mediated catalysis, etc. Here, a new synthetic strategy is reported that enables the epitaxial growth of a homogeneously alloyed AuAg shell on Au nanorod seeds, circumventing the phase segregation of Au and Ag encountered in conventional synthesis. The resulting core–shell structured bimetallic nanorods (AuNR@AuAg) have well-mixed Au and Ag atoms in their shell without discernible domains. This degree of mixing allows AuNR@AuAg to combine the high stability of Au with the superior plasmonic activity of Ag, thus outperforming seemingly similar nanostructures with monometallic shells (e.g., Ag-coated Au NRs (AuNR@Ag) and Au-coated Au NRs (AuNR@Au)). AuNR@AuAg is comparable to AuNR@Ag in plasmonic activity, but that it is markedly more stable toward oxidative treatment. Specifically, AuNR@AuAg and AuNR@Ag exhibit similarly strong signals in surface-enhanced Raman spectroscopy that are some 30-fold higher than that of AuNR@Au. When incubated with a H2O2 solution (0.5 m), the plasmonic activity of AuNR@Ag immediately and severely decayed, whereas AuNR@AuAg retained its activity intact. Moreover, the longitudinal SPR frequency of AuNR@AuAg can be tuned throughout the red wavelengths (≈620–690 nm) by controlling the thickness of the AuAg alloy shell. The synthetic strategy is versatile to fabricate AuAg alloyed shells on different shaped Au, with prospects for new possibilities in the synthesis and application of plasmonic nanocrystals.

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

    International Nuclear Information System (INIS)

    Diak, Magdalena; Grabowska, Ewelina; Zaleska, Adriana

    2015-01-01

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

  14. On new ternary equiatomic scandium transition metal aluminum compounds ScTAl with T = Cr, Ru, Ag, Re, Pt, and Au

    Energy Technology Data Exchange (ETDEWEB)

    Radzieowski, Mathis; Janka, Oliver [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Benndorf, Christopher [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Haverkamp, Sandra [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; University of Sao Paulo, Sao Carlos, SP (Brazil). Inst. of Physics

    2016-08-01

    The new equiatomic scandium transition metal aluminides ScTAl for T = Cr, Ru, Ag, Re, Pt, and Au were obtained by arc-melting of the elements followed by subsequent annealing for crystal growth. The samples were studied by powder and single crystal X-ray diffraction. The structures of three compounds were refined from single crystal X-ray diffractometer data: ScCrAl, MgZn{sub 2} type, P6{sub 3}/mmc, a = 525.77(3), c = 858.68(5) pm, R{sub 1} = 0.0188, wR{sub 2} = 0.0485, 204 F{sup 2} values, 13 variables, ScPtAl, TiNiSi type, Pnma, a = 642.83(4), b = 428.96(2), c = 754.54(5) pm, R{sub 1} = 0.0326, wR{sub 2} = 0.0458, 448 F{sup 2} values, 20 variables and ScAuAl, HfRhSn type, P anti 62c, a = 722.88(4), c = 724.15(4) pm, R{sub 1} = 0.0316, wR{sub 2} = 0.0653, 512 F{sup 2} values, 18 variables. Phase pure samples of all compounds were furthermore investigated by magnetic susceptibility measurements, and Pauli-paramagnetism but no superconductivity was observed down to 2.1 K for all of them. The local structural features and disordering phenomena have been characterized by {sup 27}Al and {sup 45}Sc magic angle spinning (MAS) and static NMR spectroscopic investigations.

  15. Synthesis of Hydrophilic Sulfur-Containing Adsorbents for Noble Metals Having Thiocarbonyl Group Based on a Methacrylate Bearing Dithiocarbonate Moieties

    Directory of Open Access Journals (Sweden)

    Haruki Kinemuchi

    2018-01-01

    Full Text Available Novel hydrophilic sulfur-containing adsorbents for noble metals were prepared by the radical terpolymerization of a methacrylate bearing dithiocarbonate moieties (DTCMMA, hydrophilic monomers, and a cross-linker. The resulting adsorbents efficiently and selectively adsorbed noble metals (Au, Ag, and Pd from various multielement aqueous solutions at room temperature owing to the thiocarbonyl group having high affinity toward noble metals. The metal adsorption by the adsorbents was proceeded by simple mixing followed by filtration. The noble metal selectivity of the adsorbent obtained from DTCMMA and N-isopropylacrylamide was higher than that of the adsorbent obtained from DTCMMA and N,N-dimethylacrylamide due to the lower nonspecific adsorption.

  16. PD Lab

    NARCIS (Netherlands)

    Bilow, Marcel; Entrop, Alexis Gerardus; Lichtenberg, Jos; Stoutjesdijk, Pieter

    2015-01-01

    PD Lab explores the applications of building sector related product development. PD lab investigates and tests digital production technologies like CNC milled wood connections. It will also act as a platform in its wider meaning to investigate the effects and influences of file to factory

  17. Noble metal (Pt or Au)-doped monolayer MoS2 as a promising adsorbent and gas-sensing material to SO2, SOF2 and SO2F2: a DFT study

    Science.gov (United States)

    Chen, Dachang; Zhang, Xiaoxing; Tang, Ju; Cui, Hao; Li, Yi

    2018-02-01

    We explored the adsorption of SO2, SOF2, and SO2F2 on Pt- or Au-doped MoS2 monolayer based on density functional theory. The adsorption energy, adsorption distance, charge transfer as well as density of states were discussed. SO2 and SOF2 exhibit strong chemical interactions with Pt-doped MoS2 based on large adsorption energy, charge transfer, and changes of electron orbitals in gas molecule. SO2 also shows obvious chemisorption on Au-doped MoS2 with apparent magnetism transfer from Au to gas molecules. The adsorption of SO2F2 on Pt-MoS2 and SOF2 on Au-MoS2 exhibits weaker chemical interactions and SO2F2 losses electrons when adsorbed on Pt-MoS2 which is different from other gas adsorption. The adsorption of SO2F2 on Au-MoS2 represents no obvious chemical interaction but physisorption. The gas-sensing properties are also evaluated based on DFT results. This work could provide prospects and application value for typical noble metal-doped MoS2 as gas-sensing materials.

  18. Temperature dependent current-voltage characteristics of Au/n-Si Schottky barrier diodes and the effect of transition metal oxides as an interface layer

    Science.gov (United States)

    Mahato, Somnath; Puigdollers, Joaquim

    2018-02-01

    Temperature dependent current-voltage (I‒V) characteristics of Au/n-type silicon (n-Si) Schottky barrier diodes have been investigated. Three transition metal oxides (TMO) are used as an interface layer between gold and silicon. The basic Schottky diode parameters such as ideality factor (n), barrier height (ϕb 0) and series resistance (Rs) are calculated and successfully explained by the thermionic emission (TE) theory. It has been found that ideality factor decreased and barrier height increased with increased of temperature. The conventional Richardson plot of ln(I0/T2) vs. 1000/T is determined the activation energy (Ea) and Richardson constant (A*). Whereas value of 'A*' is much smaller than the known theoretical value of n-type Si. The temperature dependent I-V characteristics obtained the mean value of barrier height (ϕb 0 bar) and standard deviation (σs) from the linear plot of ϕap vs. 1000/T. From the modified Richardson plot of ln(I0/T2) ˗ (qσ)2/2(kT)2 vs. 1000/T gives Richardson constant and homogeneous barrier height of Schottky diodes. Main observation in this present work is the barrier height and ideality factor shows a considerable change but the series resistance value exhibits negligible change due to TMO as an interface layer.

  19. Steady-State Spectroscopic Analysis of Proton-Dependent Electron Transfer on Pyrazine-Appended Metal Dithiolenes [Ni(pdt)2], [Pd(pdt)2], and [Pt(pdt)2] (pdt = 2,3-Pyrazinedithiol).

    Science.gov (United States)

    Kennedy, Steven R; Kozar, Morgan N; Yennawar, Hemant P; Lear, Benjamin J

    2016-09-06

    We report the structural, electronic, and acid/base properties of a series of ML2 metal dithiolene complexes, where M = Ni, Pd, Pt and L = 2,3-pyrazinedithiol. These complexes are non-innocent and possess strong electronic coupling between ligands across the metal center. The electronic coupling can be readily quantified in the monoanionic mixed valence state using Marcus-Hush theory. Analysis of the intervalence charge transfer (IVCT) band reveals that that electronic coupling in the mixed valence state is 5800, 4500, and 5700 cm(-1) for the Ni, Pd, and Pt complexes, respectively. We then focus on their response to acid titration in the mixed valence state, which generates the asymmetrically protonated mixed valence mixed protonated state. For all three complexes, protonation results in severe attenuation of the electronic coupling, as measured by the IVCT band. We find nearly 5-fold decreases in electronic coupling for both Ni and Pt, while, for the Pd complex, the electronic coupling is reduced to the point that the IVCT band is no longer observable. We ascribe the reduction in electronic coupling to charge pinning induced by asymmetric protonation. The more severe reduction in coupling for the Pd complex is a result of greater energetic mismatch between ligand and metal orbitals, reflected in the smaller electronic coupling for the pure mixed valence state. This work demonstrates that the bridging metal center can be used to tune the electronic coupling in both the mixed valence and mixed valence mixed protonated states, as well as the magnitude of change of the electronic coupling that accompanies changes in protonation state.

  20. Ni-free Zr-Cu-Al-Nb-Pd bulk metallic glasses with different Zr/Cu ratios for biomedical applications.

    Science.gov (United States)

    Huang, Lu; Yokoyama, Yoshihiko; Wu, Wei; Liaw, Peter K; Pang, Shujie; Inoue, Akihisa; Zhang, Tao; He, Wei

    2012-08-01

    Zr-based bulk metallic glasses (BMGs) possess attractive properties for prospective biomedical applications. The present study designs Ni-free Zr-Cu-Al-Nb-Pd BMGs and investigates their in vitro biocompatibility by studying mechanical properties, bio-corrosion resistance, and cellular responses. The Ti-6Al-4V alloy is used as a reference material. It is found that the Zr-based BMGs exhibit good mechanical properties, including high strengths above 1600 MPa, high hardness over 4700 MPa, and low elastic moduli of 85-90 GPa. The Zr-based BMGs are corrosion resistant in a simulated body environment, as revealed by wide passive regions, low passive current densities, and high pitting overpotentials. The formation of ZrO(2)-rich surface passive films of the Zr-based BMGs contributes to their high corrosion resistance, whereas their pitting corrosion in the phosphate buffered saline solution can be attributed to the sensitivity of the ZrO(2) films to the chloride ion. The general biosafety of the Zr-based BMGs is revealed by normal cell adhesions and cell morphologies. Moreover, the Zr/Cu content ratio in the alloy composition affects the biocompatibility of the Zr-based BMGs, by increasing their corrosion resistance and surface wettability with the increase of the Zr/Cu ratio. Effects of Zr/Cu ratios can be used to guide the future design of biocompatible Zr-based BMGs. Copyright © 2012 Wiley Periodicals, Inc.

  1. On the Potential of Bulk Metallic Glasses for Dental Implantology: Case Study on Ti40Zr10Cu36Pd14.

    Science.gov (United States)

    Liens, Alethea; Etiemble, Aurélien; Rivory, Pascaline; Balvay, Sandra; Pelletier, Jean-Marc; Cardinal, Sandrine; Fabrègue, Damien; Kato, Hidemi; Steyer, Philippe; Munhoz, Tais; Adrien, Jerome; Courtois, Nicolas; Hartmann, Daniel J; Chevalier, Jérôme

    2018-02-06

    Ti 40 Zr 10 Cu 36 Pd 14 Bulk Metallic Glass (BMG) appears very attractive for future biomedical applications thanks to its high glass forming ability, the absence of toxic elements such as Ni, Al or Be and its good mechanical properties. For the first time, a complete and exhaustive characterization of a unique batch of this glassy alloy was performed, together with ISO standard mechanical tests on machined implant-abutment assemblies. The results were compared to the benchmark Ti-6Al-4V ELI (Extra-Low-Interstitial) to assess its potential in dental implantology. The thermal stability, corrosion and sterilization resistance, cytocompatibility and mechanical properties were measured on samples with a simple geometry, but also on implant-abutment assemblies' prototypes. Results show that the glassy alloy exhibits a quite high thermal stability, with a temperature range of 38 °C between the glass transition and crystallization, a compressive strength of 2 GPa, a certain plastic deformation (0.7%), a hardness of 5.5 GPa and a toughness of 56 MPa.√m. Moreover, the alloy shows a relatively lower Young's modulus (96 GPa) than the Ti-6Al-4V alloy (110-115 GPa), which is beneficial to limit bone stress shielding. The BMG shows a satisfactory cytocompatibility, a high resistance to sterilization and a good corrosion resistance (corrosion potential of -0.07 V/SCE and corrosion current density of 6.0 nA/cm²), which may ensure its use as a biomaterial. Tests on dental implants reveal a load to failure 1.5-times higher than that of Ti-6Al-4V and a comparable fatigue limit. Moreover, implants could be machined and sandblasted by methods usually conducted for titanium implants, without significant degradation of their amorphous nature. All these properties place this metallic glass among a promising class of materials for mechanically-challenging applications such as dental implants.

  2. On the Potential of Bulk Metallic Glasses for Dental Implantology: Case Study on Ti40Zr10Cu36Pd14

    Directory of Open Access Journals (Sweden)

    Alethea Liens

    2018-02-01

    Full Text Available Ti40Zr10Cu36Pd14 Bulk Metallic Glass (BMG appears very attractive for future biomedical applications thanks to its high glass forming ability, the absence of toxic elements such as Ni, Al or Be and its good mechanical properties. For the first time, a complete and exhaustive characterization of a unique batch of this glassy alloy was performed, together with ISO standard mechanical tests on machined implant-abutment assemblies. The results were compared to the benchmark Ti-6Al-4V ELI (Extra-Low-Interstitial to assess its potential in dental implantology. The thermal stability, corrosion and sterilization resistance, cytocompatibility and mechanical properties were measured on samples with a simple geometry, but also on implant-abutment assemblies’ prototypes. Results show that the glassy alloy exhibits a quite high thermal stability, with a temperature range of 38 °C between the glass transition and crystallization, a compressive strength of 2 GPa, a certain plastic deformation (0.7%, a hardness of 5.5 GPa and a toughness of 56 MPa.√m. Moreover, the alloy shows a relatively lower Young’s modulus (96 GPa than the Ti-6Al-4V alloy (110–115 GPa, which is beneficial to limit bone stress shielding. The BMG shows a satisfactory cytocompatibility, a high resistance to sterilization and a good corrosion resistance (corrosion potential of −0.07 V/SCE and corrosion current density of 6.0 nA/cm2, which may ensure its use as a biomaterial. Tests on dental implants reveal a load to failure 1.5-times higher than that of Ti-6Al-4V and a comparable fatigue limit. Moreover, implants could be machined and sandblasted by methods usually conducted for titanium implants, without significant degradation of their amorphous nature. All these properties place this metallic glass among a promising class of materials for mechanically-challenging applications such as dental implants.

  3. PD Lab

    Directory of Open Access Journals (Sweden)

    Marcel Bilow

    2015-08-01

    Full Text Available PD Lab explores the applications of building sector related product development.  PD lab investigates and tests digital production technologies like CNC milled wood connections. It will also act as a platform in its wider meaning to investigate the effects and influences of file to factory production, to explore the potential in the field of sustainability, material use, logistics and the interaction of stakeholders within the chain of the building process.

  4. Sum-frequency generation spectroscopy on metals, oxides, and oxide-supported metal particles; Summenfrequenzerzeugungsspektroskopie an Metallen, Oxiden und oxidgetraegerten Metallpartikeln

    Energy Technology Data Exchange (ETDEWEB)

    Aumer, Andreas

    2010-06-21

    This thesis focuses on 4 different model systems of surface science. The experimental techniques used for the measurements include sum frequency generation (SFG), thermal desorption spectroscopy (TDS), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), infrared adsorption spectrosocopy (IRAS) and scanning tunneling microscopy (STM). By using SFG, measurements could be performed up to a pressure of 50 mbar. The systems under investigation were: CO on Pt(111), water on Ag(001) and on MgO/Ag(001), CO on Au/MgO/Ag(001), and CO on Au-Pd/MgO/Ag(001). The system of CO on Pt(111) exhibits a two peak-pattern under certain pressure and temperature conditions which has not been studied so far. Various experiments helped to elucidate the origin of this distinct behaviour. The measurements of water on Ag(001) and MgO/Ag(001) show that on MgO, water first adsorbs as a monolayer with a following multilayer, whereas on Ag(001) it adsorbs as a multilayer from the beginning. The monolayer can be studied below the multilayer and some resonances can be identified. For the case of Au/MgO/Ag(001), STM shows that the growth mode of Au depends on the thickness of the supporting MgO film, which can not be seen with spectroscopic methods. For mixed Au-Pd particles on MgO/Ag(001) a clear difference in the adsorption behaviour between pure metal particles and mixed particles can be seen, which is explained by an interaction between these metals. Annealing the mixed particles to 600 K leads to a segregation of the metals, where the Au atoms diffuse to the shell and the Pd atoms make up the core. The results of all these measurements are discussed in the light of recent publications. (orig.)

  5. Atomic Structure of Au−Pd Bimetallic Alloyed Nanoparticles

    KAUST Repository

    Ding, Yong; Fan, Fengru; Tian, Zhongqun; Wang, Zhong Lin

    2010-01-01

    shell of the NPs was systematically investigated by high-resolution transmission electron microscopy. In the NPs coated with a single atomic layer of Pd, the strain between the surface Pd layer and the Au core is released by Shockley partial dislocations

  6. For cermet inert anode containing oxide and metal phases useful for the electrolytic production of metals

    Science.gov (United States)

    Ray, Siba P.; Liu, Xinghua; Weirauch, Douglas A.

    2002-01-01

    A cermet inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode comprises a ceramic phase including an oxide of Ni, Fe and M, where M is at least one metal selected from Zn, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mo, Hf and rare earths, preferably Zn and/or Co. Preferred ceramic compositions comprise Fe.sub.2 O.sub.3, NiO and ZnO or CoO. The cermet inert anode also comprises a metal phase such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. A preferred metal phase comprises Cu and Ag. The cermet inert anodes may be used in electrolytic reduction cells for the production of commercial purity aluminum as well as other metals.

  7. Distinct metal-exchange pathways of doped Ag25 nanoclusters

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2016-09-09

    Atomically precise metal nanoclusters (NCs) containing more than one type of metal atom (i.e., doped or alloyed), due to synergistic effects, open new avenues for engineering the catalytic and optical properties of NCs in a manner that homometal NCs cannot. Unfortunately, it is still a major challenge to controllably introduce multimetallic dopants in NCs, understanding the dopants\\' positions, mechanism, and synergistic effects. To overcome these challenges, we designed a metal-exchange approach involving NCs as molecular templates and metal ions as the source of the incoming dopant. In particular, two structurally similar monodoped silver-rich NCs, [MAg24(SR)(18)](2-) (M = Pd/Pt and SR: thiolate), were synthesized as templates to study their mechanistic transformation in response to the introduction of gold atoms. The controllable incorporation of Au atoms into the MAg24 framework facilitated the elucidation of distinct doping pathways through high-resolution mass spectrometry, optical spectroscopy and elemental analysis. Interestingly, gold replaced the central Pd atom of [PdAg24(SR)(18)](2-) clusters to produce predominantly bimetallic [AuAg24(SR)(18)](-) clusters along with a minor product of an [Au2Ag23(SR)(18)](-) cluster. In contrast, the central Pt atom remained intact in [PtAg24(SR)(18)](2-) clusters, and gold replaced the noncentral Ag atoms to form trimetallic [AuxPtAg24-x(SR)(18)](2-) NCs, where x = 1-2, with a portion of the starting [PtAg24(SR)(18)](2-) NCs remaining. This study reveals some of the unusual metal-exchange pathways of doped NCs and the important role played by the initial metal dopant in directing the position of a second dopant in the final product.

  8. Novel Metal Nanomaterials and Their Catalytic Applications

    Directory of Open Access Journals (Sweden)

    Jiaqing Wang

    2015-09-01

    Full Text Available In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe2O3 nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts and their new catalytic applications in our group, to establish heterogeneous catalytic system in “green” environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials’ development that leads to new opportunities in nanocatalysis.

  9. Layer-by-Layer-Assembled AuNPs-Decorated First-Generation Poly(amidoamine) Dendrimer with Reduced Graphene Oxide Core as Highly Sensitive Biosensing Platform with Controllable 3D Nanoarchitecture for Rapid Voltammetric Analysis of Ultratrace DNA Hybridization.

    Science.gov (United States)

    Jayakumar, Kumarasamy; Camarada, María Belén; Dharuman, Venkataraman; Rajesh, Rajendiran; Venkatesan, Rengarajan; Ju, Huangxian; Maniraj, Mahalingam; Rai, Abhishek; Barman, Sudipta Roy; Wen, Yangping

    2018-06-12

    The structure and electrochemical properties of layer-by-layer-assembled gold nanoparticles (AuNPs)-decorated first-generation (G1) poly(amidoamine) dendrimer (PD) with reduced graphene oxide (rGO) core as a highly sensitive and label-free biosensing platform with a controllable three-dimensional (3D) nanoarchitecture for the rapid voltammetric analysis of DNA hybridization at ultratrace levels were characterized. Mercaptopropinoic acid (MPA) was self-assembled onto Au substrate, then GG1PD formed by the covalent functionalization between the amino terminals of G1PD and carboxyl terminals of rGO was covalently linked onto MPA, and finally AuNPs were decorated onto GG1PD by strong physicochemical interaction between AuNPs and -OH of rGO in GG1PD, which was characterized through different techniques and confirmed by computational calculation. This 3D controllable thin-film electrode was optimized and evaluated using [Fe(CN) 6 ] 3-/4- as the redox probe and employed to covalently immobilize thiol-functionalized single-stranded DNA as biorecognition element to form the DNA nanobiosensor, which achieved fast, ultrasensitive, and high-selective differential pulse voltammetric analysis of DNA hybridization in a linear range from 1 × 10 -6 to 1 × 10 -13 g m -1 with a low detection limit of 9.07 × 10 -14 g m -1 . This work will open a new pathway for the controllable 3D nanoarchitecture of the layer-by-layer-assembled metal nanoparticles-functionalized lower-generation PD with two-dimensional layered nanomaterials as cores that can be employed as ultrasensitive and label-free nanobiodevices for the fast diagnosis of specific genome diseases in the field of biomedicine.

  10. Nanocomposite films containing Au nanoparticles formed by electrochemical reduction of metal ions in the multilayer films as electrocatalyst for dioxygen reduction

    International Nuclear Information System (INIS)

    Huang Minghua; Shen Yan; Cheng Wenlong; Shao Yong; Sun Xuping; Liu Baifeng; Dong Shaojun

    2005-01-01

    Through electrostatic layer-by-layer assembly, AuCl 4 - anions and [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) cations were alternately deposited on indium tin oxide (ITO) substrates, and 4-aminobenzoic acid modified glassy carbon electrode. Electrochemical reduction of AuCl 4 - anions sandwiched between CoTMPyP layers leads to the in situ formation of Au nanoparticles in the multilayer films. Regular growth of the multilayer films is monitored by UV-vis spectroscopy. UV-vis spectroscopy, X-ray photoelectron spectroscopy and cyclic voltammetry confirm the formation of Au nanoparticles in the multilayer films after electrochemical reduction of AuCl 4 - anions. Atomic force spectroscopy verifies that the as-prepared Au nanoparticles are uniformly distributed with average particles diameters of 20-25 nm. The resulting composite films containing Au nanoparticles with high stability exhibit high electrocatalytic activity for the reduction of dioxygen. Rotating disk electrode voltammetry and rotating ring-disk electrode voltammetry demonstrate the Au nanoparticles-containing films can catalyze two-electron reduction of O 2 to H 2 O 2 in O 2 -saturated 0.1 M H 2 SO 4 solution

  11. Current-voltage curves of atomic-sized transition metal contacts: An explanation of why Au is ohmic and Pt is not

    DEFF Research Database (Denmark)

    Nielsen, S.K.; Brandbyge, Mads; Hansen, K.

    2002-01-01

    We present an experimental study of current-voltage (I-V) curves on atomic-sized Au and Pt contacts formed under cryogenic vacuum (4.2 K). Whereas I-V curves for Au are almost Ohmic, the conductance G=I/V for Pt decreases with increasing voltage, resulting in distinct nonlinear I-V behavior...

  12. Exploring the metal coordination properties of the pyrimidine part of purine nucleobases: isomerization reactions in heteronuclear Pt(II)/Pd(II) of 9-methyladenine.

    Science.gov (United States)

    Ibáñez, Susana; Albertí, Francisca M; Sanz Miguel, Pablo J; Lippert, Bernhard

    2011-10-17

    The synthesis and characterization of three heteronuclear Pt(2)Pd(2) (4, 5) and PtPd(2) (6) complexes of the model nucleobase 9-methyladenine (9-MeA) is reported. The compounds were prepared by reacting [Pt(NH(3))(3)(9-MeA-N7)](ClO(4))(2) (1) with [Pd(en)(H(2)O)(2)](ClO(4))(2) at different ratios r between Pt and Pd, with the goal to probe Pd(II) binding to any of the three available nitrogen atoms, N1, N3, N6 or combinations thereof. Pd(II) coordination occurs at N1 and at the deprotonated N6 positions, yet not at N3. 4 and 5 are isomers of [{(en)Pd}(2){N1,N6-9-MeA(-)-N7)Pt(NH(3))(3)}(2)](ClO(4))(6)·nH(2)O, with a head-head orientation of the two bridging 9-MeA(-) ligands in 4 and a head-tail orientation in 5. 6 is [{(en)Pd}(2)(OH)(N1,N6-9MeA(-)-N7)Pt(NH(3))(3)](ClO(4))(4)·4H(2)O, hence a condensation product between [Pt(NH(3))(3)(9-MeA-N7)](2+) and a μ-OH bridged dinuclear (en)Pd-OH-Pd(en) unit, which connects the N1 and N6 positions of 9-MeA(-) in an intramolecular fashion. 4 and 5, which slowly interconvert in aqueous solution, display distinct structural differences such as significantly different intramolecular Pd···Pd contacts (3.124 0(16) Å in 4; 2.986 6(14) Å in 5), among others. Binding of (en)Pd(II) to the exocyclic N6 atom in 4 and 5 is accompanied by a large movement of Pd(II) out of the 9-MeA(-) plane and a trend to a further shortening of the C6-N6 bond as compared to free 9-MeA. The packing patterns of 4 and 5 reveal substantial anion-π interactions.

  13. On the role of metal particle size and surface coverage for photo-catalytic hydrogen production; a case study of the Au/CdS system

    KAUST Repository

    Majeed, I.

    2015-09-25

    Photo-catalytic hydrogen production has been studied on Au supported CdS catalysts under visible light irradiation in order to understand the effect of Au particle size as well as the reaction medium properties. Au nanoparticles of size about 2-5 nm were deposited over hexagonal CdS particles using a new simple method involving reduction of Au3+ ions with iodide ions. Within the investigated range of Au (between 1 and 5 wt. %) fresh particles with mean size of 4 nm and XPS Au4f/Cd3d surface ratio of 0.07 showed the highest performance (ca. 1 molecule of H2 / Auatom s−1) under visible light irradiation (>420 nm and a flux of 35 mW/cm2). The highest hydrogen production rate was obtained from water (92%)-ethanol (8%) in an electrolyte medium (Na2S-Na2SO3). TEM studies of fresh and used catalysts showed that Au particle size increases (almost 5 fold) with increasing photo-irradiation time due to photo-agglomeration effect yet no sign of deactivation was observed. A mechanism for hydrogen production from ethanol-water electrolyte mixture is presented and discussed.

  14. Noble metal alloys for metal-ceramic restorations.

    Science.gov (United States)

    Anusavice, K J

    1985-10-01

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

  15. Cation-Poor Complex Metallic Alloys in Ba(Eu)-Au-Al(Ga) Systems: Identifying the Keys that Control Structural Arrangements and Atom Distributions at the Atomic Level.

    Science.gov (United States)

    Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav; Pecharsky, Vitalij; Miller, Gordon J; Mudring, Anja-Verena

    2015-11-02

    Four complex intermetallic compounds BaAu(6±x)Ga(6±y) (x = 1, y = 0.9) (I), BaAu(6±x)Al(6±y) (x = 0.9, y = 0.6) (II), EuAu6.2Ga5.8 (III), and EuAu6.1Al5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn13-type structure (cF104-112, Fm3̅c), III (tP52, P4/nbm) is derived from the tetragonal Ce2Ni17Si9-type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupation by Au and triel (Tr = Al, Ga) atoms, while a successive decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution ("coloring scheme"). Chemical bonding analyses for two different "EuAu6Tr6" models reveal maximization of the number of heteroatomic Au-Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the "EuAu6Tr6" models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu6.2Ga5.8 (III) and EuAu6.1Al5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at TC = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. The effective moments of 8.3 μB/f.u., determined from Curie-Weiss fits, point to divalent oxidation states for europium in both III and IV.

  16. Pressure dependence of the elastic constants and vibrational anharmonicity of Pd sub 3 sub 9 Ni sub 1 sub 0 Cu sub 3 sub 0 P sub 2 sub 1 bulk metallic glass

    CERN Document Server

    Wang Li; Sun, L L; Wang, W H; Wang, W K

    2003-01-01

    The pressure dependence of the acoustic velocities of a Pd sub 3 sub 9 Ni sub 1 sub 0 Cu sub 3 sub 0 P sub 2 sub 1 bulk metallic glass have been investigated up to 0.5 GPa at room temperature with the pulse echo overlap method. Two independent second-order elastic coefficients C sub 1 sub 1 and C sub 4 sub 4 and their pressure derivatives are yielded. The vibrational anharmonicity is shown by calculating both the acoustic mode Grueneisen parameters in the long-wavelength limit and the thermal Grueneisen parameter, and this result is compared with that for the Pd sub 4 sub 0 Ni sub 4 sub 0 P sub 2 sub 0 bulk glass.

  17. Transition metal-centered trigonal prisms as building units in RE{sub 14}T{sub 3}In{sub 3} (RE = Y, Ho, Er, Tm, Lu; T = Pd, Ir, Pt) and Y{sub 4}IrIn

    Energy Technology Data Exchange (ETDEWEB)

    Zaremba, R.; Rodewald, U.C.; Poettgen, R. [Inst. fuer Anorganische und Analytische Chemie, Univ. Muenster (Germany)

    2007-12-15

    The indides RE{sub 14}T{sub 3}In{sub 3} (RE = Y, Ho, Er, Tm, Lu; T = Pd, Ir, Pt) and Y{sub 4}IrIn were synthesized from the elements by are-melting and subsequent annealing for crystal growth. Their structures were characterized on the basis of X-ray powder and single crystal data: Lu{sub 14}Co{sub 3}In{sub 3}-type, space group P4{sub 2}/nmc, a = 970.2(1), c = 2340.7(5) pm for Y{sub 13.95}Pd{sub 3}In{sub 3.05}, a = 959.7(1), c = 2309.0(5) pm for Ho{sub 14}Pd{sub 2.95}In{sub 3}, a = 955.5(1), c = 2305.1(5) pm for Er{sub 14}Pd{sub 3}In{sub 3}, a = 950.9(1), c = 2291.6(5) pm for Tm{sub 13.90}Pd{sub 3}In{sub 3.10}, a = 944.4(1), c = 2275.5(5) pm for Lu{sub 13.93}Pd{sub 3}In{sub 3.07}, a = 962.9(1), c = 2343.0(5) pm for Y{sub 13.86}Ir{sub 2.97}In{sub 3.02}, a = 967.6(1), c = 2347.8(5) pm for Y{sub 13.92}Pt{sub 3.05}In{sub 2.91}, and Gd{sub 4}RhIn-type, space group F anti 43m, a = 1368.6(2) pm for Y{sub 4}IrIn. The main structural motifs are transition metal-centered trigonal prisms of the rare Earth elements which are condensed to two-dimensional networks in the RE{sub 14}T{sub 3}In{sub 3} indides and to a three-dimensional one in Y{sub 4}IrIn. The indium atoms in both structure types show segregation in the metal-rich matrix, i.e. In{sub 2} dumbbells in the RE{sub 14}T{sub 3}In{sub 3} indides (309 pm In2-In2 in Y{sub 13.86}Ir{sub 2.97}In{sub 3.02}) and In{sub 4} tetrahedra (322 pm In-In) in Y{sub 4}IrIn. The crystal chemical peculiarities of both structure types are discussed. (orig.)

  18. Generation and oxidation of aerosol deposited PdAg nanoparticles

    Science.gov (United States)

    Blomberg, S.; Gustafson, J.; Martin, N. M.; Messing, M. E.; Deppert, K.; Liu, Z.; Chang, R.; Fernandes, V. R.; Borg, A.; Grönbeck, H.; Lundgren, E.

    2013-10-01

    PdAg nanoparticles with a diameter of 10 nm have been generated by an aerosol particle method, and supported on a silica substrate. By using a combination of X-ray Energy Dispersive Spectroscopy and X-ray Photoelectron Spectroscopy it is shown that the size distribution of the particles is narrow and that the two metals form an alloy with a mixture of 75% Pd and 25% Ag. Under oxidizing conditions, Pd is found to segregate to the surface and a thin PdO like oxide is formed similar to the surface oxide previously reported on extended PdAg and pure Pd surfaces.

  19. Metal-support interaction: The key factor governing activity of Pd/SnO2 catalyst for denitration of ground water

    Directory of Open Access Journals (Sweden)

    Bošković Goran C.

    2008-01-01

    Full Text Available Two mesoporous nanocristalline Pd/SnO2 catalysts were prepared by modified solgel technique differing in the pH conditions (pH = 2 and 9.5 of the synthesis of their supports. Samples achieved different activity and selectivity in water denitration reaction using hydrogen. XPS results of reduced samples indicate a strong interaction between the Pd and the Sn possibly as a result of electron shift from Sn to Pd. The solid solution of Pd2+ and SnO2 is formed by taking O from the surface of the support. In such a way some SnO2-X species may stay onto the surface and be responsible for its pronounced activity.

  20. MIS gas sensors based on porous silicon with Pd and WO{sub 3}/Pd electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Solntsev, V.S. [Institute of Semiconductor Physics, National Academy of Science of Ukraine, 03028, Kiev (Ukraine); Gorbanyuk, T.I., E-mail: tatyanagor@mail.r [Institute of Semiconductor Physics, National Academy of Science of Ukraine, 03028, Kiev (Ukraine); Litovchenko, V.G.; Evtukh, A.A. [Institute of Semiconductor Physics, National Academy of Science of Ukraine, 03028, Kiev (Ukraine)

    2009-09-30

    Pd and WO{sub 3}/Pd gate metal-oxide-semiconductor (MIS) gas sensitive structures based on porous silicon layers are studied by the high frequency C(V) method. The chemical compositions of composite WO{sub 3}/Pd electrodes are characterized by secondary-ion mass spectrometry (SIMS). The atomic force microscopy (AFM) was used for morphologic studies of WO{sub 3}/Pd films. As shown in the experiments, WO{sub 3}/Pd structures are more sensitive and selective to the adsorption of hydrogen sulphide compared to Pd gate. The analyses of kinetic characteristics allow us to determine the response and characteristic times for these structures. The response time of MIS-structures with thin composite WO{sub 3}/Pd electrodes (the thickness of Pd is about 50 nm with WO{sub 3} clusters on its surface) is slower compared to the structures with Pd electrodes. Slower sensor responses of WO{sub 3}-based gas sensors may be associated with different mechanism of gas sensitivity of given structures. The enhanced sensitivity and selectivity to H{sub 2}S action of WO{sub 3}/Pd MIS-structures can also be explained by the chemical reaction that occurs at the catalytic active surface of gate electrodes. The possible mechanisms of enhanced sensitivity and selectivity to H{sub 2}S adsorption of MIS gas sensors with WO{sub 3}/Pd composite gate electrodes compared to pure Pd have been analyzed.

  1. Metallic Magnetic Nanoparticles

    Directory of Open Access Journals (Sweden)

    A. Hernando

    2005-01-01

    Full Text Available In this paper, we reviewed some relevant aspects of the magnetic properties of metallic nanoparticles with small size (below 4 nm, covering the size effects in nanoparticles of magnetic materials, as well as the appearance of magnetism at the nanoscale in materials that are nonferromagnetic in bulk. These results are distributed along the text that has been organized around three important items: fundamental magnetic properties, different fabrication procedures, and characterization techniques. A general introduction and some experimental results recently obtained in Pd and Au nanoparticles have also been included. Finally, the more promising applications of magnetic nanoparticles in biomedicine are indicated. Special care was taken to complete the literature available on the subject.

  2. An unsaturated metal site-promoted approach to construct strongly coupled noble metal/HNb3O8 nanosheets for efficient thermo/photo-catalytic reduction.

    Science.gov (United States)

    Shen, Lijuan; Xia, Yuzhou; Lin, Sen; Liang, Shijing; Wu, Ling

    2017-10-05

    Creating two-dimensional (2D) crystal-metal heterostructures with an ultrathin thickness has spurred increasing research endeavors in catalysis because of its fascinating opportunities in tuning the electronic state at the surface and enhancing the chemical reactivity. Here we report a novel and facile Nb 4+ -assisted strategy for the in situ growth of highly dispersed Pd nanoparticles (NPs) on monolayer HNb 3 O 8 nanosheets (HNb 3 O 8 NS) constituting a 2D Pd/HNb 3 O 8 NS heterostructure composite without using extra reducing agents and stabilizing agents. The Pd NP formation is directed via a redox reaction between an oxidative Pd salt precursor (H 2 PdCl 4 ) and reductive unsaturated surface metal (Nb 4+ ) sites induced by light irradiation on monolayer HNb 3 O 8 NS. The periodic arrangement of metal Nb nodes on HNb 3 O 8 NS leads to a homogeneous distribution of Pd NPs. Density functional theory (DFT) calculations reveal that the direct redox reaction between the Nb 4+ and Pd 2+ ions leads to a strong chemical interaction between the formed Pd metal NPs and the monolayer HNb 3 O 8 support. Consequently, the as-obtained Pd/HNb 3 O 8 composite serves as a highly efficient bifunctional catalyst in both heterogeneous thermocatalytic and photocatalytic selective reduction of aromatic nitro compounds in water under ambient conditions. The achieved high activity originates from the unique 2D nanosheet configuration and in situ Pd incorporation, which leads to a large active surface area, strong metal-support interaction and enhanced charge transport capability. Moreover, this facile Nb 4+ -assisted synthetic route has demonstrated to be general, which can be applied to load other metals such as Au and Pt on monolayer HNb 3 O 8 NS. It is anticipated that this work can extend the facile preparation of noble metal/nanosheet 2D heterostructures, as well as promote the simultaneous capture of duple renewable thermal and photon energy sources to drive an energy efficient

  3. Metallization of Kevlar fibers with gold.

    Science.gov (United States)

    Little, Brian K; Li, Yunfeng; Cammarata, V; Broughton, R; Mills, G

    2011-06-01

    Electrochemical gold plating processes were examined for the metallization of Kevlar yarn. Conventional Sn(2+)/Pd(2+) surface activation coupled with electroless Ni deposition rendered the fibers conductive enough to serve as cathodes for electrochemical plating. The resulting coatings were quantified gravimetrically and characterized via adhesion tests together with XRD, SEM, TEM; the coatings effect on fiber strength was also probed. XRD data showed that metallic Pd formed during surface activation whereas amorphous phases and trace amounts of pure Ni metal were plated via the electroless process. Electrodeposition in a thiosulfate bath was the most efficient Au coating process as compared with the analogous electroless procedure, and with electroplating using a commercial cyanide method. Strongly adhering coatings resulted upon metallization with three consecutive electrodepositions, which produced conductive fibers able to sustain power outputs in the range of 1 W. On the other hand, metallization affected the tensile strength of the fiber and defects present in the metal deposits make questionable the effectiveness of the coatings as protective barriers. © 2011 American Chemical Society

  4. Adsorption of volatile metals on metal surfaces and the possibilities of its application in nuclear chemistry

    International Nuclear Information System (INIS)

    Eichler, B.; Huebener, S.; Rossbach, H.

    1985-08-01

    Using an empiric model partial molar enthalpies of adsorption of the rare earth metals at zero coverage have been calculated for the adsorbent metals Ti, Fe, Ni, Cu, Zr, Nb, Mo, Rh, Pd, Ag, Ta, W, Re, Ir, Pt, Au as well as Al, Si, Zn, Ge, Cd, and Pb. The electron densities at the boundary of the Wigner-Seitz cells in the rare earth metals, necessary for the calculations, have been derived from the crystal entropies. In some cases the magnetic entropy was considered too. The calculated enthalpies of adsorption are compared with experimental data taken from the literature. The valence state of adsorbed europium and ytterbium is discussed in relation to the nature of the adsorbent metal. (author)

  5. Unravelling Thiol’s Role in Directing Asymmetric Growth of Au Nanorod–Au Nanoparticle Dimers

    KAUST Repository

    Huang, Jianfeng

    2015-12-15

    Asymmetric nanocrystals have practical significance in nanotechnologies but present fundamental synthetic challenges. Thiol ligands have proven effective in breaking the symmetric growth of metallic nanocrystals but their exact roles in the synthesis remain elusive. Here, we synthesized an unprecedented Au nanorod-Au nanoparticle (AuNR-AuNP) dimer structure with the assistance of a thiol ligand. On the basis of our experimental observations, we unraveled for the first time that the thiol could cause an inhomogeneous distribution of surface strains on the seed crystals as well as a modulated reduction rate of metal precursors, which jointly induced the asymmetric growth of monometallic dimers. © 2015 American Chemical Society.

  6. Indolenine meso-substituted dibenzotetraaza[14]annulene and its coordination chemistry toward the transition metal ions Mn(III), Fe(III), Co(II), Ni(II), Cu(II), and Pd(II).

    Science.gov (United States)

    Khaledi, Hamid; Olmstead, Marilyn M; Ali, Hapipah Mohd; Thomas, Noel F

    2013-02-18

    A new dibenzotetraaza[14]annulene bearing two 3,3-dimethylindolenine fragments at the meso positions (LH(2)), has been synthesized through a nontemplate method. X-ray crystallography shows that the whole molecule is planar. The basicity of the indolenine ring permits the macrocycle to be protonated external to the core and form LH(4)(2+)·2Cl(-). Yet another structural modification having strong C-H···π interactions was found in the chloroform solvate of LH(2). The latter two modifications are accompanied by a degree of nonplanar distortion. The antiaromatic core of the macrocycle can accommodate a number of metal ions, Mn(III), Fe(III), Co(II), Ni(II) and Cu(II), to form complexes of [Mn(L)Br], [Mn(L)Cl], [Fe(LH(2))Cl(2)](+)·Cl(-), [Co(L)], [Ni(L)], and [Cu(L)]. In addition, the reaction of LH(2) with the larger Pd(II) ion leads to the formation of [Pd(2)(LH(2))(2)(OAc)(4)] wherein the macrocycle acts as a semiflexible ditopic ligand to coordinate pairs of metal ions via its indolenine N atoms into dinuclear metallocycles. The compounds LH(2), [Co(L)], and [Ni(L)] are isostructural and feature close π-stacking as well as linear chain arrangements in the case of the metal complexes. Variable temperature magnetic susceptibility measurements showed thermally induced paramagnetism in [Ni(L)].

  7. Fusion of 110Pd with 110Pd

    International Nuclear Information System (INIS)

    Morawek, W.

    1991-07-01

    In the framework of this thesis the excitation functions of the systems 110 Pd + 110 Pd and 110 Pd + 104 Ru could be measured. The evaporation-residual-nucleus cross sections is deviating from lighter systems dominated by channels, which arise from evaporation of α particles. In the reaction 110 Pd + 110 Pd no xn channels were observed. In comparison to other reactions qualitatively a strong fusion hindrance of this system is shown. (orig./HSI) [de

  8. Photoelectron diffraction study of Rh nanoparticles growth on Fe3O4/Pd(111) ultrathin film

    International Nuclear Information System (INIS)

    Abreu, G. J. P.; Pancotti, A; Lima, L. H. de; Landers, R.; Siervo, A. de

    2013-01-01

    Metallic nanoparticles (NPs) supported on oxides thin films are commonly used as model catalysts for studies of heterogeneous catalysis. Several 4d and 5d metal NPs (for example, Pd, Pt and Au) grown on alumina, ceria and titania have shown strong metal support interaction (SMSI), for instance the encapsulation of the NPs by the oxide. The SMSI plays an important role in catalysis and is very dependent on the support oxide used. The present work investigates the growth mechanism and atomic structure of Rh NPs supported on epitaxial magnetite Fe 3 O 4 (111) ultrathin films prepared on Pd(111) using the Molecular Beam Epitaxy (MBE) technique. The iron oxide and the Rh NPs were characterized using X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction and photoelectron diffraction (PED). The combined XPS and PED results indicate that Rh NPs are metallic, cover approximately 20 % of the iron oxide surface and show height distribution ranging 3–5 ML (monolayers) with essentially a bulk fcc structure.

  9. Thickness engineering of atomic layer deposited Al2O3 films to suppress interfacial reaction and diffusion of Ni/Au gate metal in AlGaN/GaN HEMTs up to 600 °C in air

    Science.gov (United States)

    Suria, Ateeq J.; Yalamarthy, Ananth Saran; Heuser, Thomas A.; Bruefach, Alexandra; Chapin, Caitlin A.; So, Hongyun; Senesky, Debbie G.

    2017-06-01

    In this paper, we describe the use of 50 nm atomic layer deposited (ALD) Al2O3 to suppress the interfacial reaction and inter-diffusion between the gate metal and semiconductor interface, to extend the operation limit up to 600 °C in air. Suppression of diffusion is verified through Auger electron spectroscopy (AES) depth profiling and X-ray diffraction (XRD) and is further supported with electrical characterization. An ALD Al2O3 thin film (10 nm and 50 nm), which functions as a dielectric layer, was inserted between the gate metal (Ni/Au) and heterostructure-based semiconductor material (AlGaN/GaN) to form a metal-insulator-semiconductor high electron mobility transistor (MIS-HEMT). This extended the 50 nm ALD Al2O3 MIS-HEMT (50-MIS) current-voltage (Ids-Vds) and gate leakage (Ig,leakage) characteristics up to 600 °C. Both, the 10 nm ALD Al2O3 MIS-HEMT (10-MIS) and HEMT, failed above 350 °C, as evidenced by a sudden increase of approximately 50 times and 5.3 × 106 times in Ig,leakage, respectively. AES on the HEMT revealed the formation of a Ni-Au alloy and Ni present in the active region. Additionally, XRD showed existence of metal gallides in the HEMT. The 50-MIS enables the operation of AlGaN/GaN based electronics in oxidizing high-temperature environments, by suppressing interfacial reaction and inter-diffusion of the gate metal with the semiconductor.

  10. PEROXOTITANATE- AND MONOSODIUM METAL-TITANATE COMPOUNDS AS INHIBITORS OF BACTERIAL GROWTH

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, D.

    2011-01-19

    Sodium titanates are ion-exchange materials that effectively bind a variety of metal ions over a wide pH range. Sodium titanates alone have no known adverse biological effects but metal-exchanged titanates (or metal titanates) can deliver metal ions to mammalian cells to alter cell processes in vitro. In this work, we test a hypothesis that metal-titanate compounds inhibit bacterial growth; demonstration of this principle is one prerequisite to developing metal-based, titanate-delivered antibacterial agents. Focusing initially on oral diseases, we exposed five species of oral bacteria to titanates for 24 h, with or without loading of Au(III), Pd(II), Pt(II), and Pt(IV), and measuring bacterial growth in planktonic assays through increases in optical density. In each experiment, bacterial growth was compared with control cultures of titanates or bacteria alone. We observed no suppression of bacterial growth by the sodium titanates alone, but significant (p < 0.05, two-sided t-tests) suppression was observed with metal-titanate compounds, particularly Au(III)-titanates, but with other metal titanates as well. Growth inhibition ranged from 15 to 100% depending on the metal ion and bacterial species involved. Furthermore, in specific cases, the titanates inhibited bacterial growth 5- to 375-fold versus metal ions alone, suggesting that titanates enhanced metal-bacteria interactions. This work supports further development of metal titanates as a novel class of antibacterials.

  11. The Electrochemical Atomic Layer Deposition of Pt and Pd nanoparticles on Ni foam for the electrooxidation of alcohols

    CSIR Research Space (South Africa)

    Modibedi, RM

    2012-10-01

    Full Text Available Electrodeposition of Pt and Pd metal by surface limited redox replacement reactions was performed using the electrochemical atomic layer deposition. Carbon paper and Ni foam were used as substrates for metal deposition. Supported Pt and Pd...

  12. Determination of the equilibrium miscibility gap in the Pd-Rh alloy system using metal nanopowders obtained by decomposition of coordination compounds

    Energy Technology Data Exchange (ETDEWEB)

    Shubin, Yu.V., E-mail: shubin@niic.nsc.ru; Plyusnin, P.E.; Korenev, S.V.

    2015-02-15

    Highlights: • The Pd-Rh phase diagram has been experimentally reinvestigated. • The true equilibrium was achieved with the two-way approach. • The critical point of the miscibility gap lie at 58 at.% Rh and 820 °C. - Abstract: The Pd-Rh phase diagram has been reinvestigated in the subsolidus region using X-ray diffraction, scanning and transmission electron microscopy. The true equilibrium at the miscibility boundary was achieved with the two-way approach. Nanosized powders of metastable solid solutions and two-phase palladium-rhodium mixtures were used to shorten the time required to equilibrate the system. The initial samples were prepared by decomposition of coordination compounds [Pd(NH{sub 3}){sub 2}Cl{sub 2}], [Rh(NH{sub 3}){sub 5}Cl]Cl{sub 2}, [Pd(NH{sub 3}){sub 4}]{sub 3}[Rh(NO{sub 2}){sub 6}]{sub 2} and [Pd(NH{sub 3}){sub 4}][Rh(NH{sub 3})(NO{sub 2}){sub 5}]. The obtained phase diagram exhibits miscibility gap wider than generally accepted with the critical point of solubility at 58 at.% Rh and 820 °C.

  13. New organometallic salts as precursors for the functionalization of carbon nanotubes with metallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Alonso-Nunez, G., E-mail: galonso@cnyn.unam.mx; Garza, L. Morales de la; Rogel-Hernandez, E.; Reynoso, E. [Universidad Nacional Autonoma de Mexico, Centro de Nanociencias y Nanotecnologia (Mexico); Licea-Claverie, A.; Felix-Navarro, R. M. [Instituto Tecnologico de Tijuana, Centro de Graduados e Investigacion (Mexico); Berhault, G. [UMR 5256 CNRS-Universite de Lyon, Institut de Recherches sur la Catalyse et l' Environnement de Lyon (France); Paraguay-Delgado, F. [Centro de Investigacion en Materiales Avanzados S. C. (Mexico)

    2011-09-15

    New organometallic salts were synthesized in aqueous solution and were used as precursors for the functionalization of carbon nanotubes (CNT) by metallic nanoparticles. The precursors were obtained by reaction between HAuCl{sub 4}, (NH{sub 4}){sub 2}PtCl{sub 6}, (NH{sub 4}){sub 2}PdCl{sub 6}, or (NH{sub 4}){sub 3}RhCl{sub 6} with cetyltrimethylammonium bromide (CTAB). The as-obtained (CTA){sub n}Me{sub x}Cl{sub y} salts (with Me = Au, Pt, Pd, Rh) were characterized by Fourier-transform infra-red (FTIR) spectroscopy, {sup 1}H nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis. These precursors were then used to synthesize metallic nanoparticles of Au, Pt, Pd, and Rh over multiwalled carbon nanotubes (MWCNT). Characterization by scanning transmission electron microscopy (STEM) and thermogravimetric analysis under air reveals that the CNT-supported catalysts exhibit high loading and good dispersion of the metallic nanoparticles with small average particle sizes. The present preparation procedure therefore allows obtaining high densities of small metallic nanoparticles at the surface of MWCNT.

  14. Central Au on Au collisions

    Energy Technology Data Exchange (ETDEWEB)

    Alard, J.P.; Amouroux, V. [Labo de Phys. Corp., IN2P3-CRNS, Univ. Blaise Pascal, Clermont-Fd. (France); Basrak, Z. [Rudjer Boskovic Institute, Zagreb (Croatia)] [and others; FOPI-Collaboration

    1995-02-06

    In nucleus-nucleus collisions the initial relative kinetic energy of target and projectile is available for internal excitation of the interacting system; it is however still not well established to what extent local equilibrium and thermalisation occur. Local equilibrium is of interest to derive, within the formalism of transport equations and of the equation of state, (EOS), general properties of compressed and excited nuclear matter. Such approach describes in relatively simple terms the complex many body interactions occuring within extended baryonic and hadronic (or quark) matter. For a basic microscopic understanding it is highly desirable to investigate the elementary in-medium interactions in relation to the free elementary processes. Excitation function measurements of central collisions between the heaviest available nuclei (like Au on Au), supply the best ground for such studies: the highest degree of thermalisation and compression is expected for such reactions. The consideration presented here of energy thermalisation and of an expanding system clusterizing at freeze-out in a situation close to the liquid gas phase transition can be of interest to astrophysics as well as to the quark gluon plasma deconfinement studied in nucleus-nucleus collisions at the higher energy regime of CERN and Brookhaven. (orig.).

  15. Crystallization of Zr2PdxCu1-x and Zr2NixCu1-x Metallic Glass

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Min [Iowa State Univ., Ames, IA (United States)

    2008-01-01

    One interesting aspect of rretallic glasses is the numerous instances of the deviation of the phase selection from the amorphous state to thermodynamically stable phases during the crystallization process. Their devitrification pathways allow us to study the relationship between the original amorphous structure and their crystalline counter parts. Among the various factors of phase selections, size and electronic effects have been most extensively studied. Elucidating the phase selection process of a glassy alloy will be helpful to fill in the puzzle of the changes from disordered to ordered structures. In this thesis, Two model Zr2PdxCu1-x and Zr2NixCu1-x (x = 0, 0.25, 0.5, 0.75 and 1) glassy systems were investigated since: (1) All of the samples can be made into a homogenous metallic glass; (2) The atomic radii differ from Pd to Cu is by 11%, while Ni has nearly the identical atomic size compare to Cu. Moreover, Pd and Ni differ by only one valence electron from Cu. Thus, these systems are ideal to test the idea of the effects of electronic structure and size factors; (3) The small number of components in these pseudo binary systems readily lend themselves to theoretical modeling. Using high temperature X-ray diffraction (HTXRD) and thermal analysis, topological, size, electronic, bond and chemical distribution factors on crystallization selections in Zr2PdxCu1-x and Zr2NixCu1-x metallic glass have been explored. All Zr2PdxCu1-x compositions share the same Cu11b phase with different pathways of meta-stable, icosahedral quasicrystalline phase (i-phase), and C16 phase formations. The quasicrystal phase formation is topologically related to the increasing icosahedral short range order (SRO) with Pd content in Zr2PdxCu1-x system. Meta-stable C16 phase is competitive with

  16. Electrochemical CO2 and CO reduction on metal-functionalized porphyrin-like graphene

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Vanin, Marco; Karamad, Mohammedreza

    2013-01-01

    Porphyrin-like metal-functionalized graphene structures have been investigated as possible catalysts for CO2 and CO reduction to methane or methanol. The late transition metals (Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os) and some p (B, Al, Ga) and s (Mg) metals comprised the center of the po......Porphyrin-like metal-functionalized graphene structures have been investigated as possible catalysts for CO2 and CO reduction to methane or methanol. The late transition metals (Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os) and some p (B, Al, Ga) and s (Mg) metals comprised the center...... instead of CO2. Volcano plots were constructed on the basis of scaling relations of reaction intermediates, and from these plots the reaction steps with the highest overpotentials were deduced. The Rh-porphyrin-like functionalized graphene was identified as the most active catalyst for producing methanol...... from CO, featuring an overpotential of 0.22 V. Additionally, we have also examined the hydrogen evolution and oxidation reaction, and in their case, too, Rh-porphyrin turned out to be the best catalyst with an overpotential of 0.15 V. © 2013 American Chemical Society....

  17. Investigating unexpected magnetism of mesoporous silica-supported Pd and PdO nanoparticles

    KAUST Repository

    Song, Hyon Min

    2015-01-13

    The synthesis and magnetic behavior of matrix-supported Pd and PdO nanoparticles (NPs) are described. Mesoporous silica with hexagonal columnal packing is selected as a template, and the impregnation method with thermal annealing is used to obtain supported Pd and PdO NPs. The heating rate and the annealing conditions determine the particle size and the phase of the NPs, with a fast heating rate of 30 °C/min producing the largest supported Pd NPs. Unusual magnetic behaviors are observed. (1) Contrary to the general belief that smaller Pd NPs or cluster size particles have higher magnetization, matrix-supported Pd NPs in this study maintain the highest magnetization with room temperature ferromagnetism when the size is the largest. (2) Twin boundaries along with stacking faults are more pronounced in these large Pd NPs and are believed to be the reason for this high magnetization. Similarly, supported PdO NPs were prepared under air conditions with different heating rates. Their phase is tetragonal (P42/mmc) with cell parameters of a = 3.050 Å and c = 5.344 Å, which are slightly larger than in the bulk phase (a = 3.03 Å, c = 5.33 Å). Faster heating rate of 30 °C/min also produces larger particles and larger magnetic hysteresis loop, although magnetization is smaller and few twin boundaries are observed compared to the supported metallic Pd NPs.

  18. Ultrafast carrier dynamics unravel role of surface ligands and metal domain size on the photocatalytic hydrogen evolution efficiency of Au-tipped CdS nanorods: an ultrafast transient absorption spectroscopy study

    Science.gov (United States)

    Ben-Shahar, Yuval; Kriegel, Ilka; Scotognella, Francesco; Waiskopf, Nir; Dal Conte, Stefano; Moretti, Luca; Cerullo, Giulio; Rabani, Eran; Banin, Uri

    2017-02-01

    Semiconductor-metal hybrid nanostructures are interesting materials for photocatalysis. Their tunable properties offer a highly controllable platform to design light-induced charge separation, a key to their function in photocatalytic water splitting. Hydrogen evolution quantum yields are influenced by factors as size, shape, material and morphology of the system, additionally the surface coating or the metal domain size play a dominant role. In this paper we present a study on a well-defined model system of Au-tipped CdS nanorods. We use transient absorption spectroscopy to get insights into the charge carrier dynamics after photoexcitation of the bandgap of CdS nanorods. The study of charge transfer processes combined with the hydrogen evolution efficiency unravels the effects of surface coating and the gold tip size on the photocatalytic efficiency. Differences in efficiency with various surface ligands are primarily ascribed to the effects of surface passivation. Surface trapping of charge carriers is competing with effective charge separation, a prerequisite for photocatalysis, leading to the observed lower hydrogen production quantum yields. Interestingly, non-monotonic hydrogen evolution efficiency with size of the gold tip is observed, resulting in an optimal metal domain size for the most efficient photocatalysis. These results are explained by the sizedependent interplay of the metal domain charging and the relative band-alignments. Taken together our findings are of major importance for the potential application of hybrid nanoparticles as photocatalysts.

  19. Potential Energy Surfaces for Reactions of X Metal Atoms (X = Cu, Zn, Cd, Ga, Al, Au, or Hg with YH4 Molecules (Y = C, Si, or Ge and Transition Probabilities at Avoided Crossings in Some Cases

    Directory of Open Access Journals (Sweden)

    Octavio Novaro

    2012-01-01

    Full Text Available We review ab initio studies based on quantum mechanics on the most important mechanisms of reaction leading to the C–H, Si–H, and Ge–H bond breaking of methane, silane, and germane, respectively, by a metal atom in the lowest states in Cs symmetry: X(2nd excited state, 1st excited state and ground state + YH4→ H3XYH → H + XYH3 and XH + YH3. with X = Au, Zn, Cd, Hg, Al, and G, and Y = C, Si, and Ge. Important issues considered here are (a the role that the occupation of the d-, s-, or p-shells of the metal atom plays in the interactions with a methane or silane or germane molecule, (b the role of either singlet or doublet excited states of metals on the reaction barriers, and (c the role of transition probabilities for different families of reacting metals with these gases, using the H–X–Y angle as a reaction coordinate. The breaking of the Y–H bond of YH4 is useful in the production of amorphous hydrogenated films, necessary in several fields of industry.

  20. Screening of catalytic oxygen reduction reaction activity of metal-doped graphene by density functional theory

    International Nuclear Information System (INIS)

    Chen, Xin; Chen, Shuangjing; Wang, Jinyu

    2016-01-01

    Highlights: • The screened M-G structures are very thermodynamically stable, and the stability is even higher than that of the corresponding bulk metal surfaces. • The binding energies of ORR intermediates suggest that they are not linear dependence, which are different form the cases found on some metal-based catalysts. • The Au-, Co-, and Ag-G structures could be used as the ORR catalysts. - Abstract: Graphene doping is a promising direction for developing effective oxygen reduction reaction (ORR) catalysts. In this paper, we computationally investigated the ORR performance of 10 kinds of metal-doped graphene (M-G) catalysts, namely, Al-, Si-, Mn-, Fe-, Co-, Ni-, Pd-, Ag-, Pt-, and Au-G. The results shown that the binding energies of the metal atoms incorporated into the graphene vacancy are higher than their bulk cohesive energies, indicating the formed M-G catalysts are even more stable than the corresponding bulk metal surfaces, and thus avoid the metals dissolution in the reaction environment. We demonstrated that the linear relation among the binding energies of the ORR intermediates that found on metal-based materials does not hold for the M-G catalysts, therefore a single binding energy of intermediate alone is not sufficient to evaluate the ORR activity of an arbitrary catalyst. By analysis of the detailed ORR processes, we predicted that the Au-, Co-, and Ag-G materials can be used as the ORR catalysts.

  1. Structural, electronic and magnetic properties of Au-based monolayer derivatives in honeycomb structure

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, Pooja, E-mail: pupooja16@gmail.com; Sharma, Munish; Ahluwalia, P. K. [Physics Department, Himachal Pradesh University, Shimla, Himachal Pradesh, India 171005 (India); Kumar, Ashok [Centre for Physical Sciences, School of Basic and Applied Sciences, Central University of Punjab, Bathinda, India, 151001 (India)

    2016-05-23

    We present electronic properties of atomic layer of Au, Au{sub 2}-N, Au{sub 2}-O and Au{sub 2}-F in graphene-like structure within the framework of density functional theory (DFT). The lattice constant of derived monolayers are found to be higher than the pristine Au monolayer. Au monolayer is metallic in nature with quantum ballistic conductance calculated as 4G{sub 0}. Similarly, Au{sub 2}-N and Au{sub 2}-F monolayers show 4G{sub 0} and 2G{sub 0} quantum conductance respectively while semiconducting nature with calculated band gap of 0.28 eV has been observed for Au{sub 2}-O monolayer. Most interestingly, half metalicity has been predicted for Au{sub 2}-N and Au{sub 2}-F monolayers. Our findings may have importance for the application of these monolayers in nanoelectronic and spintronics.

  2. Mesoporous metal catalysts formed by ultrasound

    Energy Technology Data Exchange (ETDEWEB)

    Schaeferhans, Jana; Pazos Perez, Nicolas; Andreeva, Daria [Physikalische Chemie II, Universitaet Bayreuth (Germany)

    2010-07-01

    We study the ultrasound-driven formation of mesoporous metal sponges. The collapse of acoustic cavitations leads to very high temperatures and pressures on very short scales. Therefore, structures may be formed and quenched far from equilibrium. Mechanism of metal modification by ultrasound is complex and involves a variety of aspects. We propose that modification of metal particles and formation of mesoporous inner structures can be achieved due to thermal etching of metals by ultrasound stimulated high speed jets of liquid. Simultaneously, oxidation of metal surfaces by free radicals produced in water during cavitation stabilizes developed metal structures. Duration and intensity of the ultrasonication treatment is able to control the structure and morphology of metal sponges. We expect that this approach to the formation of nanoscale composite sponges is universal and opens perspective for a whole new class of catalytic materials that can be prepared in a one-step process. The developed method makes it possible to control the sponge morphology and can be used for formation of modern types of catalysts. For example, the sonication technique allows to combine the fabrication of mesoporous support and distribution of metal (Cu, Pd, Au, Pt etc.) nanoparticles in its pores into a single step.

  3. Evidence of icosahedral short-range order in Zr70Cu30 and Zr70Cu29Pd1 metallic glasses

    DEFF Research Database (Denmark)

    Saksl, K.; Franz, H.; Jovari, P.

    2003-01-01

    Change in local atomic environment during crystallization of Zr-based glassy alloys was studied by extended x-ray absorption fine structure (EXAFS) spectroscopy. The formation of icosahedral quasicrystalline phase followed by crystallization of tetragonal CuZr2 has been observed in the Zr70Cu29Pd1...... glassy alloy during annealing up to 850 K. On the other hand, the binary Zr70Cu30 alloy shows a single glassy to crystalline CuZr2 phase transformation. The local atomic environment of as-quenched Zr70Cu30 alloy is matched to an icosahedral local atomic configuration, which is similar to that of the as......-quenched Zr70Cu29Pd1 alloy and the alloy annealed at 593 K containing icosahedral phase. Considering that the supercooled liquid region appears prior to crystallization in the Zr70Cu30 glassy alloy, the observed results support the theory claiming a strong correlation between the existence of local...

  4. Stable synthetic bacteriochlorins for photodynamic therapy: role of dicyano peripheral groups, central metal substitution (2H, Zn, Pd), and Cremophor EL delivery.

    Science.gov (United States)

    Huang, Ying-Ying; Balasubramanian, Thiagarajan; Yang, Eunkyung; Luo, Dianzhong; Diers, James R; Bocian, David F; Lindsey, Jonathan S; Holten, Dewey; Hamblin, Michael R

    2012-12-01

    A series of four stable synthetic bacteriochlorins was tested in vitro in HeLa cells for their potential in photodynamic therapy (PDT). The parent bacteriochlorin (BC), dicyano derivative (NC)(2)BC and corresponding zinc chelate (NC)(2)BC-Zn and palladium chelate (NC)(2)BC-Pd were studied. Direct dilution of a solution of bacteriochlorin in an organic solvent (N,N-dimethylacetamide) into serum-containing medium was compared with the dilution of bacteriochlorin in Cremophor EL (CrEL; polyoxyethylene glycerol triricinoleate) micelles into the same medium. CrEL generally reduced aggregation (as indicated by absorption and fluorescence) and increased activity up to tenfold (depending on bacteriochlorin), although it decreased cellular uptake. The order of PDT activity against HeLa human cancer cells after 24 h incubation and illumination with 10 J cm(-2) of near-infrared (NIR) light is (NC)(2)BC-Pd (LD(50)=25 nM) > (NC)(2)BC > (NC)(2)BC-Zn ≈ BC. Subcellular localization was determined to be in the endoplasmic reticulum, mitochondria and lysosomes, depending on the bacteriochlorin. (NC)(2)BC-Pd showed PDT-mediated damage to mitochondria and lysosomes, and the greatest production of hydroxyl radicals as determined using a hydroxyphenylfluorescein probe. The incorporation of cyano substituents provides an excellent motif for the enhancement of the photoactivity and photostability of bacteriochlorins as PDT photosensitizers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Transport characteristics in Au/pentacene/Au diodes

    Science.gov (United States)

    Hayashi, Toshiaki; Naka, Akiyoshi; Hiroki, Masanobu; Yokota, Tomoyuki; Someya, Takao; Fujiwara, Akira

    2018-03-01

    We have used scanning and transmission electron microscopes (SEM and TEM) to study the structure of a pentacene thin film grown on a Au layer with and shown that it consists of randomly oriented amorphous pentacene clusters. We have also investigated the transport properties of amorphous pentacene in a metal-semiconductor-metal (MSM) diode structure and shown that the current is logarithmically proportional to the square root of the applied voltage, which indicates that transport occurs as the result of hopping between localized sites randomly distributed in space and energy.

  6. Design of Pd-Based Bimetallic Catalysts for ORR: A DFT Calculation Study

    Directory of Open Access Journals (Sweden)

    Lihui Ou

    2015-01-01

    Full Text Available Developing Pd-lean catalysts for oxygen reduction reaction (ORR is the key for large-scale application of proton exchange membrane fuel cells (PEMFCs. In the present paper, we have proposed a multiple-descriptor strategy for designing efficient and durable ORR Pd-based alloy catalysts. We demonstrated that an ideal Pd-based bimetallic alloy catalyst for ORR should possess simultaneously negative alloy formation energy, negative surface segregation energy of Pd, and a lower oxygen binding ability than pure Pt. By performing detailed DFT calculations on the thermodynamics, surface chemistry and electronic properties of Pd-M alloys, Pd-V, Pd-Fe, Pd-Zn, Pd-Nb, and Pd-Ta, are identified theoretically to have stable Pd segregated surface and improved ORR activity. Factors affecting these properties are analyzed. The alloy formation energy of Pd with transition metals M can be mainly determined by their electron interaction. This may be the origin of the negative alloy formation energy for Pd-M alloys. The surface segregation energy of Pd is primarily determined by the surface energy and the atomic radius of M. The metals M which have smaller atomic radius and higher surface energy would tend to favor the surface segregation of Pd in corresponding Pd-M alloys.

  7. Covellite CuS as a matrix for "invisible" gold: X-ray spectroscopic study of the chemical state of Cu and Au in synthetic minerals

    Science.gov (United States)

    Tagirov, Boris R.; Trigub, Alexander L.; Kvashnina, Kristina O.; Shiryaev, Andrey A.; Chareev, Dmitriy A.; Nickolsky, Maximilian S.; Abramova, Vera D.; Kovalchuk, Elena V.

    2016-10-01

    Geological processes leading to formation of sulfide ores often result in precipitation of gold-bearing sulfides which can contain high concentrations of this metal in ;invisible; (or ;refractory;) state. Covellite (CuS) is ubiquitous mineral in many types of the ore deposits, and numerous studies of the natural ores show that covellite can contain high concentrations of Au. At the same time, Au-bearing covellite withstands cooling in contrast to other minerals of the Cu-Fe-S system (chalcocite, bornite, chalcopyrite), where Au exsolves at low temperatures. This makes covellite a convenient model system for investigation of the chemical state (local environment and valence) of the ;invisible; Au in copper-sulfide ores (copper-porphyry, epithermal, volcanogenic massive sulfide, SEDEX deposits). Therefore, it is necessary to determine the location of Au in the covellite matrix as it will have important implications for the methods employed by mineral processing industry to extract Au from sulfide ores. Here we investigate the chemical state of Cu and Au in synthetic covellite containing up to 0.3 wt.% of Au in the ;invisible; state. The covellite crystals were synthesized by hydrothermal and salt flux methods. Formation of the chemically bound Au is indicated by strong dependence of the concentration of Au in covellite on the sulfur fugacity in the experimental system (d(log C(Au))/d(log f(S2)) ∼ 0.65). The Au concentration of covellite grows with increasing temperature from 400 to 450 °C, whereas further temperature increase to 500 °C has only minor effect. The synthesized minerals were studied using X-ray absorption fine structure spectroscopy (XAFS) in high energy resolution fluorescence detection (HERFD) mode. Ab initio simulations of Cu K edge XANES spectra show that the Cu oxidation state in two structural positions in covellite (tetrahedral and triangular coordination with S atoms) is identical: the total loss of electronic charge for the 3d shell is ∼0

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

    Science.gov (United States)

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

    2013-09-01

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

  9. Improved ethanol electrooxidation performance by shortening Pd-Ni active site distance in Pd-Ni-P nanocatalysts

    Science.gov (United States)

    Chen, Lin; Lu, Lilin; Zhu, Hengli; Chen, Yueguang; Huang, Yu; Li, Yadong; Wang, Leyu

    2017-01-01

    Incorporating oxophilic metals into noble metal-based catalysts represents an emerging strategy to improve the catalytic performance of electrocatalysts in fuel cells. However, effects of the distance between the noble metal and oxophilic metal active sites on the catalytic performance have rarely been investigated. Herein, we report on ultrasmall (~5 nm) Pd-Ni-P ternary nanoparticles for ethanol electrooxidation. The activity is improved up to 4.95 A per mgPd, which is 6.88 times higher than commercial Pd/C (0.72 A per mgPd), by shortening the distance between Pd and Ni active sites, achieved through shape transformation from Pd/Ni-P heterodimers into Pd-Ni-P nanoparticles and tuning the Ni/Pd atomic ratio to 1:1. Density functional theory calculations reveal that the improved activity and stability stems from the promoted production of free OH radicals (on Ni active sites) which facilitate the oxidative removal of carbonaceous poison and combination with CH3CO radicals on adjacent Pd active sites.

  10. Nonlinear elastic properties of bulk metallic glasses Zr52.5Ti5Cu17.9Ni14.6Al10 and Pd40Cu30Ni10P20

    International Nuclear Information System (INIS)

    Kobelev, N.P.; Kolyvanov, E.L.; Khonik, V.A.

    2005-01-01

    The influence of uniaxial compression on the propagation of ultrasonic vibrations in Zr 52.5 Ti 5 Cu 17.9 Ni 14.6 Al 10 and Pd 40 Cu 30 Ni 10 P 20 bulk metallic glasses produced by melt quenching at a rate of 100 K/s is investigated. Elastic deformation was realized by compression of the samples along their long axis up to strains of about 1 GPa. Deriving of major ratios used during the calculation of the third-order elastic moduli of the glasses is described in brief, the results of the calculations being provided. A qualitative agreement between the calculated results and available data on the influence of the uniform pressure on the sound wave propagation rate was obtained [ru

  11. In-Plane Angular Effect of Magnetoresistance of Quasi-One-Dimensional Organic Metals, (DMET) 2AuBr 2 and (TMTSF) 2ClO 4

    Science.gov (United States)

    Yoshino, Harukazu; Saito, Kazuya; Nishikawa, Hiroyuki; Kikuchi, Koichi; Kobayashi, Keiji; Ikemoto, Isao

    1997-08-01

    Comparative study is presented for the in-plane angular effect of magnetoresistance of quasi-one-dimensional organic conductors, (DMET)2AuBr2 and (TMTSF)2ClO4. The magnetoresistance for the magnetic and electrical fields parallel and perpendicular to the most conducting plane, respectively, was measured at 4.2 K and up to 7.0 T. (DMET)2AuBr2 shows an anomalous hump in the field-orientation dependence of the magnetoresistance for the magnetic field nearly parallel to the most conducting axis and this is very similar to what previously reported for (DMET)2I3. Weak anomaly was detected for the magnetoresistance of (TMTSF)2ClO4 in the Relaxed state, while no anomaly was observed in the SDW phase in the Quenched state. By comparing the numerical angular derivatives of the magnetoresistance, it is shown that the anomaly in the in-plane angular effect continuously develops from zero magnetic field and is closely related to the quasi-one-dimensional Fermi surface. A simple method is proposed to estimate the anisotropy of the transfer integral from the width of the hump anomaly.

  12. Ion beam mixing in Ag-Pd alloys

    International Nuclear Information System (INIS)

    Klatt, J.L.; Averback, R.S.; Peak, D.

    1989-01-01

    Ion beam mixing during 750 keV Kr + irradiation at 80 K was measured on a series of Ag-Pd alloys using Au marker atoms. The mixing in pure Ag was the greatest and it decreased monotonically with increasing Pd content, being a factor of 10 higher in pure Ag than in pure Pd. This large difference in mixing cannot be explained by the difference in cohesion energy between Ag and Pd in the thermodynamic model of ion beam mixing proposed by Johnson et al. [W. L. Johnson, Y. T. Cheng, M. Van Rossum, and M-A. Nicolet, Nucl. Instrum. Methods B 7/8, 657 (1985)]. An alternative model based on local melting in the cascade is shown to account for the ion beam mixing results in Ag and Pd

  13. Synthesis of Alkanethiolate-Capped Metal Nanoparticles Using Alkyl Thiosulfate Ligand Precursors: A Method to Generate Promising Reagents for Selective Catalysis

    Directory of Open Access Journals (Sweden)

    Khin Aye San

    2018-05-01

    Full Text Available Evaluation of metal nanoparticle catalysts functionalized with well-defined thiolate ligands can be potentially important because such systems can provide a spatial control in the reactivity and selectivity of catalysts. A synthetic method utilizing Bunte salts (sodium S-alkylthiosulfates allows the formation of metal nanoparticles (Au, Ag, Pd, Pt, and Ir capped with alkanethiolate ligands. The catalysis studies on Pd nanoparticles show a strong correlation between the surface ligand structure/composition and the catalytic activity and selectivity for the hydrogenation/isomerization of alkenes, dienes, trienes, and allylic alcohols. The high selectivity of Pd nanoparticles is driven by the controlled electronic properties of the Pd surface limiting the formation of Pd–alkene adducts (or intermediates necessary for (additional hydrogenation. The synthesis of water soluble Pd nanoparticles using ω-carboxylate-S-alkanethiosulfate salts is successfully achieved and these Pd nanoparticles are examined for the hydrogenation of various unsaturated compounds in both homogeneous and heterogeneous environments. Alkanethiolate-capped Pt nanoparticles are also successfully synthesized and further investigated for the hydrogenation of various alkynes to understand their geometric and electronic surface properties. The high catalytic activity of activated terminal alkynes, but the significantly low activity of internal alkynes and unactivated terminal alkynes, are observed for Pt nanoparticles.

  14. Method of making sulfur-resistant composite metal membranes

    Science.gov (United States)

    Way, J Douglas [Boulder, CO; Lusk, Mark [Golden, CO; Thoen, Paul [Littleton, CO

    2012-01-24

    The invention provides thin, hydrogen-permeable, sulfur-resistant membranes formed from palladium or palladium-alloy coatings on porous, ceramic or metal supports. Also disclosed are methods of making these membranes via sequential electroless plating techniques, wherein the method of making the membrane includes decomposing any organic ligands present on the substrate, reducing the palladium crystallites on the substrate to reduced palladium crystallites, depositing a film of palladium metal on the substrate and then depositing a second, gold film on the palladium film. These two metal films are then annealed at a temperature between about 200.degree. C. and about 1200.degree. C. to form a sulfur-resistant, composite PdAu alloy membrane.

  15. Core-Shell Structuring of Pure Metallic Aerogels towards Highly Efficient Platinum Utilization for the Oxygen Reduction Reaction.

    Science.gov (United States)

    Cai, Bin; Hübner, René; Sasaki, Kotaro; Zhang, Yuanzhe; Su, Dong; Ziegler, Christoph; Vukmirovic, Miomir B; Rellinghaus, Bernd; Adzic, Radoslav R; Eychmüller, Alexander

    2018-03-05

    The development of core-shell structures remains a fundamental challenge for pure metallic aerogels. Here we report the synthesis of Pd x Au-Pt core-shell aerogels composed of an ultrathin Pt shell and a composition-tunable Pd x Au alloy core. The universality of this strategy ensures the extension of core compositions to Pd transition-metal alloys. The core-shell aerogels exhibited largely improved Pt utilization efficiencies for the oxygen reduction reaction and their activities show a volcano-type relationship as a function of the lattice parameter of the core substrate. The maximum mass and specific activities are 5.25 A mg Pt -1 and 2.53 mA cm -2 , which are 18.7 and 4.1 times higher than those of Pt/C, respectively, demonstrating the superiority of the core-shell metallic aerogels. The proposed core-based activity descriptor provides a new possible strategy for the design of future core-shell electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. CO oxidation on PdO surfaces

    DEFF Research Database (Denmark)

    Hirvi, Janne T.; Kinnunen, Toni-Jani J.; Suvanto, Mika

    2010-01-01

    Density functional calculations were performed in order to investigate CO oxidation on two of the most stable bulk PdO surfaces. The most stable PdO(100) surface, with oxygen excess, is inert against CO adsorption, whereas strong adsorption on the stoichiometric PdO(101) surface leads to favorable...... oxidation via the Langmuir–Hinshelwood mechanism. The reaction with a surface oxygen atom has an activation energy of 0.66 eV, which is comparable to the lowest activation energies observed on metallic surfaces. However, the reaction rate may be limited by the coverage of molecular oxygen. Actually...... adsorption, following the Eley–Rideal mechanism and taking advantage of the reaction tunnel provided by the adjacent palladium atom, has an activation energy of only 0.24 eV. The reaction mechanism and activation energy for the palladium activated CO oxidation on the most stable PdO(100)–O surface...

  17. Adsorption and migration of single metal atoms on the calcite (10.4) surface

    International Nuclear Information System (INIS)

    Pinto, H; Haapasilta, V; Lokhandwala, M; Foster, Adam S; Öberg, S

    2017-01-01

    Transition metal atoms are one of the key ingredients in the formation of functional 2D metal organic coordination networks. Additionally, the co-deposition of metal atoms can play an important role in anchoring the molecular structures to the surface at room temperature. To gain control of such processes requires the understanding of adsorption and diffusion properties of the different transition metals on the target surface. Here, we used density functional theory to investigate the adsorption of 3 d (Ti, Cr, Fe, Ni, Cu), 4 d (Zr, Nb, Mo, Pd, Ag) and 5 d (Hf, W, Ir, Pt, Au) transition metal adatoms on the insulating calcite (10.4) surface. We identified the most stable adsorption sites and calculated binding energies and corresponding ground state structures. We find that the preferential adsorption sites are the Ca–Ca bridge sites. Apart from the Cr, Mo, Cu, Ag and Au all the studied metals bind strongly to the calcite surface. The calculated migration barriers for the representative Ag and Fe atoms indicates that the metal adatoms are mobile on the calcite surface at room temperature. Bader analysis suggests that there is no significant charge transfer between the metal adatoms and the calcite surface. (paper)

  18. Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt{sub 3}M (where M = 3d transition metals) alloy catalyst from first-principles

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Chang-Eun [Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Global E3 Institute and Department of Materials Science and Engineering, Yonsei University, 120-749 Seoul (Korea, Republic of); Lim, Dong-Hee [Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Environmental Engineering, Chungbuk National University, 1 Chungdae-ro, Seowon-Gu, Cheongju, Chungbuk 362-763 (Korea, Republic of); Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo [Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Hong, Seong-Ahn [Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Advanced Materials Chemistry, Korea University, Sejong-city 339-700 (Korea, Republic of); Soon, Aloysius, E-mail: aloysius.soon@yonsei.ac.kr, E-mail: hchahm@kist.re.kr [Global E3 Institute and Department of Materials Science and Engineering, Yonsei University, 120-749 Seoul (Korea, Republic of); Ham, Hyung Chul, E-mail: aloysius.soon@yonsei.ac.kr, E-mail: hchahm@kist.re.kr [Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), 39-1 Hawolgok, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Clean Energy and Chemical Engineering, University of Science and Technology (UST), 217 Gajungro, Yuseong-gu, Daejeon 305-333 (Korea, Republic of)

    2015-01-21

    The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt{sub 3}M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt{sub 3}M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt{sub 3}M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt{sub 3}M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

  19. Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles.

    Science.gov (United States)

    Kim, Chang-Eun; Lim, Dong-Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo; Hong, Seong-Ahn; Soon, Aloysius; Ham, Hyung Chul

    2015-01-21

    The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

  20. Comparing Ullmann Coupling on Noble Metal Surfaces: On-Surface Polymerization of 1,3,6,8-Tetrabromopyrene on Cu(111) and Au(111)

    DEFF Research Database (Denmark)

    Pham, Tuan Anh; Song, Fei; Nguyen, Manh-Thuong

    2016-01-01

    to a dissociation of the C−Br bonds and the formation of disordered metal-coordinated molecular networks. Further annealing at 573 K resulted in the formation of covalently linked disordered networks. Importantly, we found that the chosen substrate not only plays an important role as catalyst for the Ullmann...

  1. Ion-stimulated Gas Desorption Yields of Electropolished, Chemically Etched, and Coated (Au, Ag, Pd, TiZrV) Stainless Steel Vacuum Chambers and St707 Getter Strips Irradiated with 4.2 MeV/u lead ions

    CERN Document Server

    Mahner, E; Küchler, D; Malabaila, M; Taborelli, M

    2005-01-01

    The ion-induced desorption experiment, installed in the CERN Heavy Ion Accelerator LINAC 3, has been used to measure molecular desorption yields for 4.2 MeV/u lead ions impacting under grazing incidence on different accelerator-type vacuum chambers. Desorption yields for H2, CH4, CO, and CO2, which are of fundamental interest for future accelerator applications, are reported for different stainless steel surface treatments. In order to study the effect of the surface oxide layer on the gas desorption, gold-, silver-, palladium-, and getter-coated 316 LN stainless steel chambers and similarly prepared samples were tested for desorption at LINAC 3 and analysed for chemical composition by X-ray Photoemission Spectroscopy (XPS). The large effective desorption yield of 2 x 104 molecules/Pb53+ ion, previously measured for uncoated, vacuum fired stainless steel, was reduced after noble-metal coating by up to 2 orders of magnitude. In addition, pressure rise measurements, the effectiveness of beam scrubbing with le...

  2. Leaching of gold, silver and accompanying metals from circuit boards (PCBs waste

    Directory of Open Access Journals (Sweden)

    Jana Ficeriová

    2011-12-01

    Full Text Available Au-Ag noble metal wastes represent a wide range of waste types and forms, with various accompanying metallic elements.The presented leaching strategy for Au-Ag contained in circuit boards (PCBs aims at gaining gold and silver in the metallic form.Application of the proposed ammonium thiosulphate leaching process for the treatment of the above mentioned Au-Ag containing wastesrepresents a practical, economic and at the same time an ecological solution. The ammonium thiosulphate based leaching of gold and silverfrom PCBs waste, using crushing as a pretreatment, was investigated. It was possible to achieve 98 % gold and 93 % silver recovery within48 hours of ammonium thiosulphate leaching. This type of leaching is a better leaching procedure for recovery of gold and silver from PCBwaste than the classical toxic cyanide leaching. 84 % Cu, 82 % Fe, 77 % Al, 76 % Zn, 70 % Ni, 90 % Pd, 88 % Pb and 83 % Sn recovery ofthe accompanying metals was achieved, using sulphuric acid with hydrogen peroxide, sodium chloride and aqua regia. A four steps leachingprocess gave a very satisfactory yield and a more rapid kinetics for all observed metals solubilization than other technologies.

  3. The hydrogen interaction in an FCC FePd alloy with a vacancy

    Energy Technology Data Exchange (ETDEWEB)

    Ardenghi, S [Instituto de AstronomIa y Fisica del Espacio (IAFE), CC 67-Suc 28 (C1428ZAA) Ciudad Autonoma de Buenos Aires (Argentina); Gonzalez, E; Jasen, P; Juan, A [Departamento de Fisica, Universidad Nacional del Sur, Av. Alem 1253 BahIa Blanca (8000) (Argentina)], E-mail: cajuan@uns.edu.ar

    2009-04-15

    The absorption of hydrogen in the ordered face-centered cubic FePd alloy is investigated using a density functional calculation method. Changes in the electronic structure and bonding after introducing an Fe or Pd vacancy are analysed. H locates close to a tetrahedral site and the H-metal bond is achieved at the expense of the interfacial Fe-Pd bond.

  4. CO tolerance of PdPt/C and PdPtRu/C anodes for PEMFC

    International Nuclear Information System (INIS)

    Garcia, Amanda C.; Paganin, Valdecir A.; Ticianelli, Edson A.

    2008-01-01

    The performance of H 2 /O 2 proton exchange membrane fuel cells (PEMFCs) fed with CO-contaminated hydrogen was investigated for anodes with PdPt/C and PdPtRu/C electrocatalysts. The physicochemical properties of the catalysts were characterized by energy dispersive X-ray (EDX) analyses, X-ray diffraction (XRD) and 'in situ' X-ray absorption near edge structure (XANES). Experiments were conducted in electrochemical half and single cells by cyclic voltammetry (CV) and I-V polarization measurements, while DEMS was employed to verify the formation of CO 2 at the PEMFC anode outlet. A quite high performance was achieved for the PEMFC fed with H 2 + 100 ppm CO with the PdPt/C and PdPtRu/C anodes containing 0.4 mg metal cm -2 , with the cell presenting potential losses below 200 mV at 1 A cm -2 , with respect to the system fed with pure H 2 . For the PdPt/C catalysts no CO 2 formation was seen at the PEMFC anode outlet, indicating that the CO tolerance is improved due to the existence of more free surface sites for H 2 electrooxidation, probably due to a lower Pd-CO interaction compared to pure Pd or Pt. For PdPtRu/C the CO tolerance may also have a contribution from the bifunctional mechanism, as shown by the presence of CO 2 in the PEMFC anode outlet

  5. Measurement of benzenethiol adsorption to nanostructured Pt, Pd, and PtPd films using Raman spectroelectrochemistry.

    Science.gov (United States)

    Pomfret, Michael B; Pietron, Jeremy J; Owrutsky, Jeffrey C

    2010-05-04

    Raman spectroscopy and electrochemical methods were used to study the behavior of the model adsorbate benzenethiol (BT) on nanostructured Pt, Pd, and PtPd electrodes as a function of applied potential. Benzenethiol adsorbs out of ethanolic solutions as the corresponding thiolate, and voltammetric stripping data reveal that BT is oxidatively removed from all of the nanostructured metals upon repeated oxidative and reductive cycling. Oxidative stripping potentials for BT increase in the order Pt oxidizing potentials via cleavage of the Pt-S bond. In contrast, on nanoscale Pd and PtPd, BT is irreversibly lost due to cleavage of BT C-S bonds at oxidizing potentials, which leaves adsorbed sulfur oxides on Pd and PtPd films and effects the desulfurization of BT. While Pd and PtPd films are less sulfur-resistant than Pt films, palladium oxides, which form at higher potentials than Pt oxides, oxidatively desulfurize BT. In situ spectroelectrochemical Raman spectroscopy provides real-time, chemically specific information that complements the cyclic voltammetric data. The combination of these techniques affords a powerful and convenient method for guiding the development of sulfur-tolerant PEMFC catalysts.

  6. Influence of Au Nanoparticle Shape on Au@Cu2O Heterostructures

    Directory of Open Access Journals (Sweden)

    Jie Zhu

    2015-01-01

    Full Text Available Synthesis of metal-semiconductor heterostructures may allow the combination of function of the corresponding components and/or the enhanced performance resulting from the interactions between all the components. In this paper, Au@Cu2O core-shell heterostructures are prepared by a seed-growth method, using different-shaped Au nanocrystals as the seeds such as nanorods, octahedra, decahedra, dots, and nanocubes. The results revealed that the final structure of Au@Cu2O was greatly influenced by the shape of the seeds used. Exposure of Cu2O{111} and Cu2O{001} favored when the overgrowth happened on Au{111} and Au{001} surface, respectively. The size of the product can also be tuned by the amount of the seeds. The results reported here provide a thinking clue to modulate the shape and size of core-shell nanocrystals, which is useful in developing new materials with desired performance.

  7. Deposition-precipitation with Urea to prepare Au/Mg(OH)2 catalysts: Influence of the preparation conditions on metal size and load

    International Nuclear Information System (INIS)

    Milone, Candida; Trapani, Mariachiara; Zanella, Rodolfo; Piperopolulos, Elpida; Galvagno, Signorino

    2010-01-01

    Deposition-precipitation with Urea method to prepare Au/Mg(OH) 2 was investigated. The preparation was carried out at 80 o C using an aqueous solution of HAuCl 4 and Urea in presence of MgO as support precursor. The pH of the solution was 9.5-10 owing to the rapid hydration of MgO to Mg(OH) 2 . The influence of the preparation conditions (Urea concentration, preparation procedure, addition of magnesium citrate) on the gold load and particle size distribution was evaluated. The structural characterization of preparations was carried out by means of X-ray diffractometry and transmission electron microscopy. Among the parameters investigated, the preparation procedure, that is the control of the interaction between gold species and the support, is the main step for the deposition of the highest amount of gold (> 80% of the theoretical amount) having small size and a narrow distribution (d = 4.1 nm, σ = ±1.1 nm). The synthesized catalysts were tested in the CO oxidation reaction.

  8. A DFT study of volatile organic compounds adsorption on transition metal deposited graphene

    International Nuclear Information System (INIS)

    Kunaseth, Manaschai; Poldorn, Preeyaporn; Junkeaw, Anchalee; Meeprasert, Jittima; Rungnim, Chompoonut; Namuangruk, Supawadee; Kungwan, Nawee; Inntam, Chan; Jungsuttiwong, Siriporn

    2017-01-01

    Highlights: • VOCs removal via modified carbon-based adsorbent using density functional theory. • The single-vacancy defective graphene (SDG) with metal-deposited significantly increase the adsorption efficiency. • TM-doped SDG is a suitable adsorbent material for VOC removal. • Electron in hybridized sp"2-orbitals of heteroatoms has an effect on mode of adsorption. - Abstract: Recently, elevated global emission of volatile organic compounds (VOCs) was associated to the acceleration and increasing severity of climate change worldwide. In this work, we investigated the performance of VOCs removal via modified carbon-based adsorbent using density functional theory. Here, four transition metals (TMs) including Pd, Pt, Ag, and Au were deposited onto single-vacancy defective graphene (SDG) surface to increase the adsorption efficiency. Five prototypical VOCs including benzene, furan, pyrrole, pyridine, and thiophene were used to study the adsorption capability of metal-deposited graphene adsorbent. Calculation results revealed that Pd, Pt, Au, and Ag atoms and nanoclusters bind strongly onto the SDG surface. In this study, benzene, furan and pyrrole bind in the π-interaction mode using delocalized π-electron in aromatic ring, while pyridine and thiophene favor X- interaction mode, donating lone pair electron from heteroatom. In terms of adsorption, pyridine VOC adsorption strengths to the TM-cluster doped SDG surfaces are Pt_4 (−2.11 eV) > Pd_4 (−2.05 eV) > Ag_4 (−1.53 eV) > Au_4 (−1.87 eV). Our findings indicate that TM-doped SDG is a suitable adsorbent material for VOC removal. In addition, partial density of states analysis suggests that benzene, furan, and pyrrole interactions with TM cluster are based on p-orbitals of carbon atoms, while pyridine and thiophene interactions are facilitated by hybridized sp"2-orbitals of heteroatoms. This work provides a key insight into the fundamentals of VOCs adsorption on carbon-based adsorbent.

  9. LA-ICP-MS Study of Trace Elements in the Chanuskij Metal

    Science.gov (United States)

    Petaev, Michail I.

    2005-01-01

    This progress report covers work done during the second year of the 3-year proposal. During this year we resolved many issues relevant to the analytical technique developed by us for measuring trace elements in meteoritic metals. This technique was used to measure concentrations of Fe, Ni, Co, Cr, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, Sb, W, Re, Os, Ir, Pt, and Au in eight large (120 - 160 microns) metal grains from both "igneous" and "metamorphic" lithologies of the Chanuskij silicate inclusions. The first application of OUT technique to metal grains from thin sections showed some limitations. Small thickness of metal grains in the thin section limited the signal to 3-4 time-slices instead of 10- 1 1 ones in polished sections of iron meteorites studied before.

  10. Influence of Au Nanoparticle Shape on Au@Cu2O Heterostructures

    OpenAIRE

    Zhu, Jie; Lu, Na; Chen, Wei; Kong, Lina; Yang, Yun; Ma, Dekun; Huang, Shaoming

    2015-01-01

    Synthesis of metal-semiconductor heterostructures may allow the combination of function of the corresponding components and/or the enhanced performance resulting from the interactions between all the components. In this paper, Au@Cu2O core-shell heterostructures are prepared by a seed-growth method, using different-shaped Au nanocrystals as the seeds such as nanorods, octahedra, decahedra, dots, and nanocubes. The results revealed that the final structure of Au@Cu2O was greatly influenced by ...

  11. Screening the best catalyst with group 9, 10 and 11 metals monolayer loading on NbC(001) from first-principles study

    Science.gov (United States)

    Kan, Dongxiao; Zhang, Xilin; Zhang, Yanxing; Yang, Zongxian

    2018-02-01

    The supported catalysts have received great attentions due to their high catalytic activity, low cost and good stability. Here we report the stability, wetting ability, corrosion resistance and catalytic activity of the supported catalysts with group 9, 10 and 11 metals (M = Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au) monolayers (ML) deposited on NbC(001), denoted as MML/NbC(001). The PdML/NbC(001) and PtML/NbC(001) are testified as the most stable and active ones with the former even better on the whole. The catalytic activities toward oxygen reduction reactions (ORR) are clarified by the dissociation and the change in Gibbs free energies for the elementary reaction steps of O2 on PdML/NbC(001).

  12. XPS/STM study of model bimetallic Pd–Au/HOPG catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Bukhtiyarov, Andrey V., E-mail: avb@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva Ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Prosvirin, Igor P., E-mail: prosvirin@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva Ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Bukhtiyarov, Valerii I., E-mail: vib@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva Ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation)

    2016-03-30

    Graphical abstract: - Highlights: • The model Pd–Au/HOPG catalysts preparation has been studied by XPS and STM. • Model “core–shell” type Pd–Au/HOPG catalysts with different Pd/Au ratios were prepared. • Heating of the “core–shell” Pd–Au/HOPG samples up to 400 °C leads to alloy formation. • Contribution of parameters controlling the properties of Pd–Au alloyed particles has been discussed. - Abstract: 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.

  13. Hybrid NiCoOx adjacent to Pd nanoparticles as a synergistic electrocatalyst for ethanol oxidation

    Science.gov (United States)

    Wang, Wei; Yang, Yan; Liu, Yanqin; Zhang, Zhe; Dong, Wenkui; Lei, Ziqiang

    2015-01-01

    To improve the electrocatalytic activity of Pd for ethanol oxidation, hybrid NiCoOx adjacent to Pd catalyst (Pd-NiCoOx/C) is successfully synthesized. Physical characterization shows NiCoOx is closely adjacent to Pd nanoparticles in Pd-NiCoOx/C catalyst, which leads to Strong Metal-Support Interactions (SMSI) between the NiCoOx and Pd nanoparticles, in favor of the electrocatalytic properties. The Pd-NiCoOx/C catalyst is estimated to own larger electrochemically active surface area than Pd/C and Pd-NiO/C catalysts. Moreover, compared to Pd/C catalyst, the onset potential of Pd-NiCoOx/C catalyst is negative 40 mV for ethanol oxidation. Noticeably, the current density of Pd-NiCoOx/C catalyst is 2.05 and 1.43 times higher contrasted to Pd/C and Pd-NiO/C catalysts accordingly. Importantly, the Pd-NiCoOx/C catalyst exhibits better stability during ethanol oxidation, which is a promising electrocatalyst for application in direct alkaline alcohol fuel cells.

  14. Alternating voltage-induced electrochemical synthesis of colloidal Au nanoicosahedra

    Energy Technology Data Exchange (ETDEWEB)

    McCann, Kevin; Cloud, Jacqueline E.; Yang, Yongan, E-mail: yonyang@mines.edu [Colorado School of Mines, Department of Chemistry and Geochemistry (United States)

    2013-11-15

    A simple method of alternating voltage-induced electrochemical synthesis has been developed to synthesize highly dispersed colloidal Au nanoicosahedra of 14 ± 3 nm in size. This simple and effective method uses a common transformer to apply a zero-offset alternating voltage to a pair of identical Au electrodes that are immersed in an electrolyte solution containing ligands. The obtained Au nanoicosahedra in this work are among the smallest Au icosahedra synthesized in aqueous solutions. A series of experimental conditions have been studied, such as voltage, the electrolyte identity and concentration, stabilizer identity and concentration, and reaction temperature. The mechanistic study indicates that Au nanoicosahedra are produced on electrode surfaces through an intermediate state of AuO{sub x}. The kinetic rate constant of these Au icosahedra in catalyzing the reduction of 4-nitrophenol with sodium borohydride is found much larger than the literature values of similar Au nanocrystals. In addition, the synthesis of Au–Pd-alloyed NCs has also been attempted.Graphical Abstract.

  15. Determination of work function of graphene under a metal electrode and its role in contact resistance.

    Science.gov (United States)

    Song, Seung Min; Park, Jong Kyung; Sul, One Jae; Cho, Byung Jin

    2012-08-08

    Although the work function of graphene under a given metal electrode is critical information for the realization of high-performance graphene-based electronic devices, relatively little relevant research has been carried out to date. In this work, the work function values of graphene under various metals are accurately measured for the first time through a detailed analysis of the capacitance-voltage (C-V) characteristics of a metal-graphene-oxide-semiconductor (MGOS) capacitor structure. In contrast to the high work function of exposed graphene of 4.89-5.16 eV, the work function of graphene under a metal electrode varies depending on the metal species. With a Cr/Au or Ni contact, the work function of graphene is pinned to that of the contacted metal, whereas with a Pd or Au contact the work function assumes a value of ∼4.62 eV regardless of the work function of the contact metal. A study of the gate voltage dependence on the contact resistance shows that the latter case provides lower contact resistance.

  16. Direct measurement of time dependent diffusion for Ag and Au under ambient conditions

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Pil Sun; Jo, Han Yeol; Kim, Tae Kyeong [Hankuk University of Foreign Studies, Yongin (Korea, Republic of)

    2014-12-15

    Time-dependent diffusion for Ag and Au metal atoms was measured using the scanning tunneling microscope break-junction technique in ambient conditions. We observed that Ag contacts do not form long single-atomic chains compared to Au contacts during the elongation of each metal electrode, and Ag atoms diffuse more quickly than Au atoms after metal contact rupture. This is consistent with previous results of molecular dynamic simulations. Further, we found a correlation between diffusion length and the evolution time on an atomic scale to reveal the time-dependent diffusion for Ag and Au metal atoms.

  17. More active and sulfur resistant bimetallic Pd-Ni catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Betti, Carolina; Carrara, Nicolás; Badano, Juan; Lederhos, Cecilia; Vera, Carlos; Quiroga, Mónica, E-mail: mquiroga@fiq.unl.edu.ar [Instituto de Investigaciones en Catálisis y Petroquímica, INCAPE (FIQ-UNL, CONICET), Santa Fe (Argentina)

    2018-02-15

    The influence of the kind of metal precursor and the sequence of impregnation on the properties of Pd-Ni catalysts was evaluated during the test reaction of selective hydrogenation of styrene to ethylbenzene by means of physicochemical characterization. The focus was put on the final hydrogenating activity and the resistance to deactivation by sulfide compounds (thiophene). The used techniques of characterization were ICP, XPS, XDR, TPR, CO chemisorption and TEM. XPS results indicated the presence of different Pd species: Pd{sup δ-}, Pd{sup 0} and Pd{sup δ+}. In the case of the Ni containing catalysts, Ni{sup 0} and NiO species were also detected. These palladium and nickel species would be responsible of the variation of activity and sulfur resistance of the catalysts. NiClPd catalysts had a higher resistance to deactivation by sulfur poisoning. This was associated to a higher concentration of Pd{sup η+}Cl{sub x}O{sub y} species that would prevent the adsorption of thiophene by both steric and electronic effects. It could also be due to the lower concentration of Pd{sup 0} and Ni{sup 0} on these catalysts, as compared to those shown by the PdNiCl catalysts. Both the Pd{sup 0} and Ni{sup 0} species are more prone to poisoning because of their higher electronic availability. (author)

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

    International Nuclear Information System (INIS)

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

    2014-01-01

    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

  19. Glycerol electro-oxidation in alkaline medium using Pd/C and PdSn/C electrocatalysts prepared by electron beam irradiation

    International Nuclear Information System (INIS)

    Geraldes, Adriana Napoleao; Silva, Dionisio Fortunato da; Pino, Eddy Segura; Spinace, Estevan Vitorio; Oliveira Neto, Almir; Linardi, Marcelo; Santos, Mauro Coelhos dos

    2013-01-01

    Carbon-supported metal nanoparticles were prepared for fuel cell applications by radiation-induced reduction of metal ions precursors. Pd/C and PdSn/C electrocatalysts (Pd:Sn atomic ratio 90:10), prepared by using electron beam irradiation, were tested for glycerol electro-oxidation in single alkaline direct glycerol fuel cell (ADGFC). EDX analysis showed that the Pd:Sn atomic ratio is very similar to the nominal one. X-ray diffractograms of PdSn/C electrocatalyst showed the presence of Pd (fcc) phase. Cyclic voltammetry (CV) indicated that Pd/C and PdSn/C electrocatalysts have good activity for glycerol electro-oxidation, at room temperature. Experiments with single ADGFC were carried out from 60 to 90 deg C, using Pd/C and PdSn/C electrocatalysts and glycerol 2.0 mol.L -1 , as fuel. The best performance was obtained at 85 deg C, for both electrocatalysts. The Pd/C and PdSn/C electrocatalysts showed similar performance (34 mW cm -2 ), at 85 deg C. (author)

  20. Charge transport through O-deficient Au-MgO-Au junctions

    KAUST Repository

    Fadlallah, M. M.; Eckern, Ulrich; Rungger, Ivan; Schuster, Cosima; Schwingenschlö gl, Udo

    2009-01-01

    Metal-oxide heterostructures have been attracting considerable attention in recent years due to various technological applications. We present results of electronic structure and transport calculations for the Au-MgO-Au (metal-insulator-metal) heterostructure based on density-functional theory and the nonequilibrium Green’s functions method. The dependence of the conductance of the heterostructure on the thickness of the MgO interlayer and the interface spacing is studied. In addition, we address the effects of O vacancies. We observe deviations from an exponentially suppressed conductance with growing interlayer thickness caused by Au-O chemical bonds. Electronic states tracing back to O vacancies can increase the conductance. Furthermore, this effect can be enhanced by enlarging the interface spacing as the vacancy induced Mg states are shifted toward the Fermi energy.

  1. Charge transport through O-deficient Au-MgO-Au junctions

    KAUST Repository

    Fadlallah, M. M.

    2009-12-29

    Metal-oxide heterostructures have been attracting considerable attention in recent years due to various technological applications. We present results of electronic structure and transport calculations for the Au-MgO-Au (metal-insulator-metal) heterostructure based on density-functional theory and the nonequilibrium Green’s functions method. The dependence of the conductance of the heterostructure on the thickness of the MgO interlayer and the interface spacing is studied. In addition, we address the effects of O vacancies. We observe deviations from an exponentially suppressed conductance with growing interlayer thickness caused by Au-O chemical bonds. Electronic states tracing back to O vacancies can increase the conductance. Furthermore, this effect can be enhanced by enlarging the interface spacing as the vacancy induced Mg states are shifted toward the Fermi energy.

  2. High stability and high activity Pd/ITO-CNTs electrocatalyst for direct formic acid fuel cell

    International Nuclear Information System (INIS)

    Qu, Wei-Li; Gu, Da-Ming; Wang, Zhen-Bo; Zhang, Jing-Jia

    2014-01-01

    Graphical abstract: The addition of ITO in Pd/CNTs catalyst significantly improves the activity and stability of catalyst for formic acid electrooxidation due to excellent stability and high electrical conductivity of ITO, and metal-support interaction between Pd nanoparticles and ITO. - Highlights: • Pd catalyst with ITO and CNTs as a mixture support for DFAFC was first prepared by microwave-assisted polyol process. • The activity and stability of Pd/ITO-CNTs catalyst is significantly higher than those of Pd/CNTs. • When ITO content is 50% of ITO/CNTs support mass, Pd/ITO-CNTs exhibits the best performance. - Abstract: Indium tin oxide (ITO) and carbon nanotube hybrid has been explored as a support for Pd catalyst. Pd/ITO-CNTs catalysts with different ITO contents were prepared by the microwave-assisted polyol process. The as-prepared Pd/ITO-CNTs catalysts were characterized by X-ray diffraction (XRD), energy dispersive analysis of X-ray (EDAX), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), and electrochemical measurements in this work. The TEM results show that Pd particle size distribution in the Pd/ITO-CNTs catalyst is more uniform than that in Pd/CNTs, indicating that the ITO can promote the dispersion of Pd nanoparticles. It is found that there is metal-support interaction between Pd nanoparticles and ITO in the Pd/ITO-CNTs catalyst through XPS test. The results of electrochemical tests prove that the Pd/ITO-CNTs catalysts exhibit higher electro-catalytic activity and stability than Pd/CNTs toward formic acid electrooxidation. When the ITO content is 50% of ITO-CNTs support mass, the Pd/ITO-CNTs catalyst has the best catalytic performance for formic acid electrooxidation. The peak current density of formic acid electrooxidation on the Pd/ITO-CNTs50% electrode is 1.53 times as high as that on Pd/CNTs, 2.31 times higher than that on Pd/ITO. The results of aging

  3. Ultra-relativistic Au+Au and d+Au collisions:

    Science.gov (United States)

    Back, B. B.; Baker, M. D.; Ballintijn, M.; Barton, D. S.; Betts, R. R.; Bickley, A. A.; Bindel, R.; Budzanowski, A.; Busza, W.; Carroll, A.; Chai, Z.; Decowski, M. P.; García, E.; Gburek, T.; George, N.; Gulbrandsen, K.; Gushue, S.; Halliwell, C.; Hamblen, J.; Hauer, M.; Heintzelman, G. A.; Henderson, C.; Hofman, D. J.; Hollis, R. S.; Hołyński, R.; Holzman, B.; Iordanova, A.; Johnson, E.; Kane, J. L.; Katzy, J.; Khan, N.; Kucewicz, W.; Kulinich, P.; Kuo, C. M.; Lin, W. T.; Manly, S.; McLeod, D.; Mignerey, A. C.; Nouicer, R.; Olszewski, A.; Pak, R.; Park, I. C.; Pernegger, H.; Reed, C.; Remsberg, L. P.; Reuter, M.; Roland, C.; Roland, G.; Rosenberg, L.; Sagerer, J.; Sarin, P.; Sawicki, P.; Seals, H.; Sedykh, I.; Skulski, W.; Smith, C. E.; Stankiewicz, M. A.; Steinberg, P.; Stephans, G. S. F.; Sukhanov, A.; Tang, J.-L.; Tonjes, M. B.; Trzupek, A.; Vale, C.; van Nieuwenhuizen, G. J.; Vaurynovich, S. S.; Verdier, R.; Veres, G. I.; Wenger, E.; Wolfs, F. L. H.; Wosiek, B.; Woźniak, K.; Wuosmaa, A. H.; Wysłouch, B.

    In this talk I will review PHOBOS data on charged particle multiplicities, obtained in Au+Au and d+Au collisions at RHIC. The general features of the Au+Au pseudorapidity distributions results will be discussed and compared to those of /line{p}p collisions. The total charged particle multiplicity, scaled by the number of participant pairs, is observed to be about 40% higher in Au+Au collisions than in /line{p}p and d+Au systems, but, surprisingly at the same level of e+e- collisions. Limiting fragmentation scaling is seen to be obeyed in Au+Au collisions.

  4. Mechanisms for the reactions of group 10 transition metal complexes with metal-group 14 element bonds, Bbt(Br)E═M(PCy3)2 (E = C, Si, Ge, Sn, Pb; M = Pd and Pt).

    Science.gov (United States)

    Liao, Wei-Hung; Ho, Pei-Yun; Su, Ming-Der

    2013-02-04

    The electronic structures of the Bbt(Br)E═M(PCy(3))(2) (E = C, Si, Ge, Sn, Pb and M = Pt, Pd) complexes and their potential energy surfaces for the formation and water addition reactions were studied using density functional theory (B3LYP/LANL2DZ). The theoretical evidence suggests that the bonding character of the E═M double bond between the six valence-electron Bbt(Br)E: species and the 14 valence-electron (PCy(3))(2)M complexes has a predominantly high s-character. That is, on the basis of the NBO, this theoretical study indicates that the σ-donation from the E element to the M atom prevails. Also, theoretical computations suggest that the relative reactivity decreases in the order: Bbt(Br)C═M(PCy(3))(2) > Bbt(Br)Si═M(PCy(3))(2) > Bbt(Br)Ge═M(PCy(3))(2) > Bbt(Br)Sn═M(PCy(3))(2) > Bbt(Br)Pb═M(PCy(3))(2), irrespective of whether M = Pt or M = Pd is chosen. Namely, the greater the atomic weight of the group 14 atom (E), the larger is the atomic radius of E and the more stable is its Bbt(Br)E═M(PCy(3))(2) doubly bonded species toward chemical reactions. The computational results show good agreement with the available experimental observations. The theoretical results obtained in this work allow a number of predictions to be made.

  5. Bifunctional chelates of Rh-105 and Au-199 as potential radiotherapeutic agents

    International Nuclear Information System (INIS)

    Troutner, D.E.; Schlemper, E.O.

    1990-01-01

    Since last year we have: continued the synthesis of pentadentate bifunctional chelating agents based on diethylene triamine; studied the chelation Rh-105, Au-198 (as model for Au-199) and Tc-99m with these agents as well as chelation of Pd-109, Cu-67, In-111, and Co-57 with some of them; synthesized a new class of potential bifunctional chelating agents based on phenylene diamine; investigated the behavior of Au-198 as a model for Au-199; begun synthesis of bifunctional chelating agents based on terpyridly and similar ligands; and continued attempts to produce tetradentate bifunctional chelates based on diaminopropane. Each of these will be addressed in this report

  6. Novel WSi/Au T-shaped gate GaAs metal-semiconductor field-effect-transistor fabrication process for super low-noise microwave monolithic integrated circuit amplifiers

    International Nuclear Information System (INIS)

    Takano, H.; Hosogi, K.; Kato, T.

    1995-01-01

    A fully ion-implanted self-aligned T-shaped gate Ga As metal-semiconductor field-effect transistor (MESFET) with high frequency and extremely low-noise performance has been successfully fabricated for super low-noise microwave monolithic integrated circuit (MMIC) amplifiers. A subhalf-micrometer gate structure composed of WSi/Ti/Mo/Au is employed to reduce gate resistance effectively. This multilayer gate structure is formed by newly developed dummy SiON self-alignment technology and a photoresist planarization process. At an operating frequency of 12 GHz, a minimum noise figure of 0.87 dB with an associated gain of 10.62 dB has been obtained. Based on the novel FET process, a low-noise single-stage MMIC amplifier with an excellent low-noise figure of 1.2 dB with an associated gain of 8 dB in the 14 GHz band has been realized. This is the lowest noise figure ever reported at this frequency for low-noise MMICs based on ion-implanted self-aligned gate MESFET technology. 14 refs., 9 figs

  7. Distance of the image plane from metal surfaces

    International Nuclear Information System (INIS)

    Smith, N.V.; Chen, C.T.; Weinert, M.

    1989-01-01

    The data base of surface-state energies on the metals Cu, Ag, Au, Ni, Pd, and Pt is assembled and, with the aid of a simple model, is used to estimate the distance of the image plane and its trends from surface to surface and metal to metal. The model combines a nearly-free-electron representation of the crystal with a Jones-Jennings-Jepsen ansatz for the saturated image barrier. The projected bulk-band gaps are taken from published determinations. Constraints are placed on the surface barrier parameters by appeal to the results of self-consistent first-principles slab calculations. The general experimental trend observed is for the image-plane distance z 0 to decrease in the sequence (111) to (001) to (110), in the same sense but not as rapidly as z J , the distance of the effective jellium edge. This trend is rationalized using a simple model of the tail of the surface charge density. Typical values for z 0 -z J fall in the range -0.2 to +0.5 a.u., with the larger values occurring for the 3d metals Cu and Ni

  8. Shaping metal nanocrystals through epitaxial seeded growth

    Energy Technology Data Exchange (ETDEWEB)

    Habas, Susan E.; Lee, Hyunjoo; Radmilovic, Velimir; Somorjai,Gabor A.; Yang, Peidong

    2008-02-17

    Morphological control of nanocrystals has becomeincreasingly important, as many of their physical and chemical propertiesare highly shape-dependent. Nanocrystal shape control for both single andmultiple material systems, however, remains fairly empirical andchallenging. New methods need to be explored for the rational syntheticdesign of heterostructures with controlled morphology. Overgrowth of adifferent material on well-faceted seeds, for example, allows for the useof the defined seed morphology to control nucleation and growth of thesecondary structure. Here, we have used highly faceted cubic Pt seeds todirect the epitaxial overgrowth of a secondary metal. We demonstrate thisconcept with lattice matched Pd to produce conformal shape-controlledcore-shell particles, and then extend it to lattice mismatched Au to giveanisotropic growth. Seeding with faceted nanocrystals may havesignificant potential towards the development of shape-controlledheterostructures with defined interfaces.

  9. Liquid phase catalytic hydrodebromination of tetrabromobisphenol A on supported Pd catalysts

    International Nuclear Information System (INIS)

    Wu, Ke; Zheng, Mengjia; Han, Yuxiang; Xu, Zhaoyi; Zheng, Shourong

    2016-01-01

    Highlights: • Pd catalysts supported on TiO_2, CeO_2, Al_2O_3 and SiO_2 were prepared. • Deposition-precipitation method resulted in positively charged smaller Pd particle. • Complete debromination of tetrabromobisphenol A could be achieved on Pd/TiO_2. • Pd/TiO_2 prepared by the deposition-precipitation method was more active. - Abstract: Tetrabromobisphenol A (TBBPA) is a widely used brominated flame retardant and reductive debromination is an effective method for the abatement of TBBPA pollution. In this study, Pd catalysts supported on TiO_2, CeO_2, Al_2O_3 and SiO_2 were prepared by the impregnation (the resulting catalyst denoted as im-Pd/support), deposition-precipitation (the resulting catalyst denoted as dp-Pd/support), and photo-deposition (the resulting catalyst denoted as pd-Pd/support) methods. The catalysts were characterized by N_2 adsorption-desorption isotherm, X-ray diffraction, transmission electron microscopy, measurement of zeta potential, CO chemisorption, and X-ray photoelectron spectroscopy. The results showed that at an identical Pd loading amount (2.0 wt.%) Pd particle size in dp-Pd/TiO_2 was much smaller than those in im-Pd/TiO_2 and pd-Pd/TiO_2. Pd particle size of the dp-Pd/TiO_2 catalyst increased with Pd loading amount. Additionally, Pd particles in the dp-Pd/TiO_2 catalysts were positively charged due to the strong metal-support interaction, whereas the cationization effect was gradually attenuated with the increase of Pd loading amount. For the liquid phase catalytic hydrodebromination (HDB) of TBBPA, tri-bromobisphenol A (tri-BBPA), di-bromobisphenol A (di-BBPA), and mono-bromobisphenol A (mono-BBPA) were identified as the intermediate products, indicative of a stepwise debromination process. The catalytic HDB of TBBPA followed the Langmuir-Hinshelwood model, reflecting an adsorption enhanced catalysis mechanism. At an identical Pd loading amount, the Pd catalyst supported on TiO_2 exhibited a much higher catalytic activity

  10. Liquid phase catalytic hydrodebromination of tetrabromobisphenol A on supported Pd catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Ke [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China); Zheng, Mengjia [Kuang Yaming Honors School, Nanjing University, Nanjing 210023 (China); Han, Yuxiang [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China); Xu, Zhaoyi, E-mail: zhaoyixu@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China); Zheng, Shourong [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China)

    2016-07-15

    Highlights: • Pd catalysts supported on TiO{sub 2}, CeO{sub 2}, Al{sub 2}O{sub 3} and SiO{sub 2} were prepared. • Deposition-precipitation method resulted in positively charged smaller Pd particle. • Complete debromination of tetrabromobisphenol A could be achieved on Pd/TiO{sub 2}. • Pd/TiO{sub 2} prepared by the deposition-precipitation method was more active. - Abstract: Tetrabromobisphenol A (TBBPA) is a widely used brominated flame retardant and reductive debromination is an effective method for the abatement of TBBPA pollution. In this study, Pd catalysts supported on TiO{sub 2}, CeO{sub 2}, Al{sub 2}O{sub 3} and SiO{sub 2} were prepared by the impregnation (the resulting catalyst denoted as im-Pd/support), deposition-precipitation (the resulting catalyst denoted as dp-Pd/support), and photo-deposition (the resulting catalyst denoted as pd-Pd/support) methods. The catalysts were characterized by N{sub 2} adsorption-desorption isotherm, X-ray diffraction, transmission electron microscopy, measurement of zeta potential, CO chemisorption, and X-ray photoelectron spectroscopy. The results showed that at an identical Pd loading amount (2.0 wt.%) Pd particle size in dp-Pd/TiO{sub 2} was much smaller than those in im-Pd/TiO{sub 2} and pd-Pd/TiO{sub 2}. Pd particle size of the dp-Pd/TiO{sub 2} catalyst increased with Pd loading amount. Additionally, Pd particles in the dp-Pd/TiO{sub 2} catalysts were positively charged due to the strong metal-support interaction, whereas the cationization effect was gradually attenuated with the increase of Pd loading amount. For the liquid phase catalytic hydrodebromination (HDB) of TBBPA, tri-bromobisphenol A (tri-BBPA), di-bromobisphenol A (di-BBPA), and mono-bromobisphenol A (mono-BBPA) were identified as the intermediate products, indicative of a stepwise debromination process. The catalytic HDB of TBBPA followed the Langmuir-Hinshelwood model, reflecting an adsorption enhanced catalysis mechanism. At an identical Pd

  11. In vitro corrosion and biocompatibility screening of sputtered Ti{sub 40}Cu{sub 36}Pd{sub 14}Zr{sub 10} thin film metallic glasses on steels

    Energy Technology Data Exchange (ETDEWEB)

    Subramanian, B., E-mail: subramanianb3@gmail.com

    2015-02-01

    The growth of multi-component thin film metallic glasses (TFMGs) of Ti{sub 40}Cu{sub 36}Pd{sub 14}Zr{sub 10} (at.%) alloys fabricated using magnetron sputtering on bioimplantable 316L stainless steel substrates has been investigated. The vapor–solid quenching during sputtering enables the amorphous phases to be formed. The amorphous films consist of a single glassy phase, as evidenced by a broad hump and no detectable crystalline peaks as observed from XRD and selective area electron diffraction (SAED) patterns. The average surface roughness (Ra) of the coated film as observed from AFM was 0.3 nm. Nanohardness of about 7.7 GPa and Young's modulus of 110 GPa were measured from nanoindentation analysis. The potentiodynamic polarization and impedance measurements showed that coated stainless steel substrates have higher corrosion resistance compared to uncoated SS substrate in simulated body fluid (SBF) solution. The cytotoxicity studies using L929 fibroblast cells showed that these coatings were non-cytotoxic in nature. The interactions between the coated surface and bacteria were investigated by agar diffusion method, solution suspension and wet interfacial contact methods. - Highlights: • Ti-based TFMG coated specimen showed superior corrosion resistance. • Ti-based TFMG coated SS 316L specimen was non-cytotoxic in nature. • Antimicrobial activity of Ti-based TFMG was noticed.

  12. Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd- Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

    Directory of Open Access Journals (Sweden)

    Mphilisi M. Mahlambi

    2012-01-01

    Full Text Available Metal-ion- (Ag, Co, Ni and Pd doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL self-assembly technique using a poly(styrene sulfonate sodium salt (PSS and poly(allylamine hydrochloride (PAH polyelectrolyte system. Solid diffuse reflectance (SDR studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM, the thin films had a porous morphology and the atomic force microscope (AFM studies showed “rough” surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation. The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5 reusability cycles.

  13. Structural optimization of Au–Pd bimetallic nanoparticles with improved particle swarm optimization method

    International Nuclear Information System (INIS)

    Shao Gui-Fang; Zhu Meng; Shangguan Ya-Li; Li Wen-Ran; Zhang Can; Wang Wei-Wei; Li Ling

    2017-01-01

    Due to the dependence of the chemical and physical properties of the bimetallic nanoparticles (NPs) on their structures, a fundamental understanding of their structural characteristics is crucial for their syntheses and wide applications. In this article, a systematical atomic-level investigation of Au–Pd bimetallic NPs is conducted by using the improved particle swarm optimization (IPSO) with quantum correction Sutton–Chen potentials (Q-SC) at different Au/Pd ratios and different sizes. In the IPSO, the simulated annealing is introduced into the classical particle swarm optimization (PSO) to improve the effectiveness and reliability. In addition, the influences of initial structure, particle size and composition on structural stability and structural features are also studied. The simulation results reveal that the initial structures have little effects on the stable structures, but influence the converging rate greatly, and the convergence rate of the mixing initial structure is clearly faster than those of the core-shell and phase structures. We find that the Au–Pd NPs prefer the structures with Au-rich in the outer layers while Pd-rich in the inner ones. Especially, when the Au/Pd ratio is 6:4, the structure of the nanoparticle (NP) presents a standardized Pd core Au shell structure. (paper)

  14. Formation and Diffusion of Metal Impurities in Perovskite Solar Cell Material CH3NH3PbI3: Implications on Solar Cell Degradation and Choice of Electrode.

    Science.gov (United States)

    Ming, Wenmei; Yang, Dongwen; Li, Tianshu; Zhang, Lijun; Du, Mao-Hua

    2018-02-01

    Solar cells based on methylammonium lead triiodide (MAPbI 3 ) have shown remarkable progress in recent years and have demonstrated efficiencies greater than 20%. However, the long-term stability of MAPbI 3 -based solar cells has yet to be achieved. Besides the well-known chemical and thermal instabilities, significant native ion migration in lead halide perovskites leads to current-voltage hysteresis and photoinduced phase segregation. Recently, it is further revealed that, despite having excellent chemical stability, the Au electrode can cause serious solar cell degradation due to Au diffusion into MAPbI 3 . In addition to Au, many other metals have been used as electrodes in MAPbI 3 solar cells. However, how the external metal impurities introduced by electrodes affect the long-term stability of MAPbI 3 solar cells has rarely been studied. A comprehensive study of formation energetics and diffusion dynamics of a number of noble and transition metal impurities (Au, Ag, Cu, Cr, Mo, W, Co, Ni, Pd) in MAPbI 3 based on first-principles calculations is reported herein. The results uncover important general trends of impurity formation and diffusion in MAPbI 3 and provide useful guidance for identifying the optimal metal electrodes that do not introduce electrically active impurity defects in MAPbI 3 while having low resistivities and suitable work functions for carrier extraction.

  15. Recommended values of clean metal surface work functions

    International Nuclear Information System (INIS)

    Derry, Gregory N.; Kern, Megan E.; Worth, Eli H.

    2015-01-01

    A critical review of the experimental literature for measurements of the work functions of clean metal surfaces of single-crystals is presented. The tables presented include all results found for low-index crystal faces except cases that were known to be contaminated surfaces. These results are used to construct a recommended value of the work function for each surface examined, along with an uncertainty estimate for that value. The uncertainties are based in part on the error distribution for all measured work functions in the literature, which is included here. The metals included in this review are silver (Ag), aluminum (Al), gold (Au), copper (Cu), iron (Fe), iridium (Ir), molybdenum (Mo), niobium (Nb), nickel (Ni), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), tantalum (Ta), and tungsten (W)

  16. Recommended values of clean metal surface work functions

    Energy Technology Data Exchange (ETDEWEB)

    Derry, Gregory N., E-mail: gderry@loyola.edu; Kern, Megan E.; Worth, Eli H. [Department of Physics, Loyola University Maryland, 4501 N. Charles St., Baltimore, Maryland 21210 (United States)

    2015-11-15

    A critical review of the experimental literature for measurements of the work functions of clean metal surfaces of single-crystals is presented. The tables presented include all results found for low-index crystal faces except cases that were known to be contaminated surfaces. These results are used to construct a recommended value of the work function for each surface examined, along with an uncertainty estimate for that value. The uncertainties are based in part on the error distribution for all measured work functions in the literature, which is included here. The metals included in this review are silver (Ag), aluminum (Al), gold (Au), copper (Cu), iron (Fe), iridium (Ir), molybdenum (Mo), niobium (Nb), nickel (Ni), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), tantalum (Ta), and tungsten (W)

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

    Energy Technology Data Exchange (ETDEWEB)

    Boomi, Pandi [Department of Industrial Chemistry, School of Chemical Sciences, Alagappa University, Karaikudi 630 003, Tamil Nadu (India); Prabu, Halliah Gurumallesh, E-mail: hgprabu2010@gmail.com [Department of Industrial Chemistry, School of Chemical Sciences, Alagappa University, Karaikudi 630 003, Tamil Nadu (India); Manisankar, Paramasivam [Department of Industrial Chemistry, School of Chemical Sciences, Alagappa University, Karaikudi 630 003, Tamil Nadu (India); Ravikumar, Sundaram [Department of Oceanography and Coastal Area Studies, School of Marine Sciences, Alagappa University, Thondi Campus 623 409, Tamil Nadu (India)

    2014-05-01

    Graphical abstract: - Highlights: • New method of synthesizing PANI-Ag-Au nanocomposite. • Surface Plasmon resonance and formation of composite at nano level were analyzed. • HR-TEM study revealed uniform distribution of nanoparticles. • PANI-Ag-Au nanocomposite exhibited good antibacterial activity. - Abstract: 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.

  18. Ultra-low Pt decorated PdFe Alloy Nanoparticles for Formic Acid Electro-oxidation

    International Nuclear Information System (INIS)

    Zhou, Yawei; Du, Chunyu; Han, Guokang; Gao, Yunzhi; Yin, Geping

    2016-01-01

    Highlights: • A cost-efficient way is used to prepare transition-noble metal alloy nanoparticles. • The Pd 50 Fe 50 /C catalyst shows excellent activity for formic acid oxidation (FAO). • Much activity enhancement of FAO is acquired by ultra-low Pt decorated Pd 50 Fe 50 . • A synergistic mechanism between Pt clusters and PdFe is proposed during the FAO. - Abstract: Palladium (Pd), has demonstrated promising electro-catalytic activity for formic acid oxidation, but suffers from extremely low abundance. Recently alloying with a transition metal has been considered as an effective approach to reducing the loading of Pd and enhancing the activity of Pd-based catalysts simultaneously. Herein, carbon supported PdFe nanoparticles (NPs) are synthesized at room temperature by using sodium borohydride as reducing agent and potassium ferrocyanide as Fe precursor. The Pd 50 Fe 50 alloy sample annealed at 900 °C for 1 h shows the best catalytic activity among Pd x Fe 1-x (x = 0.2, 0.4, 0.5, 0.6, and 0.8) towards formic acid oxidation. To further improve both catalytic activity and stability, the ultra-low Pt (0.09 wt %) decorated Pd 50 Fe 50 NPs (PtPd/PdFe) are prepared via the galvanic replacement reaction. Compared with Pd 50 Fe 50 /C, the PtPd/PdFe/C Exhibits 1.52 times higher catalytic activity and lower onset potential (−0.12 V). The significant enhancements of formic acid oxidation can be attributed to the accelerated dehydrogenation reaction of formic acid by Pt atomic clusters. Moreover, the PtPd/PdFe/C also demonstrates better tolerance to poisons during formic acid oxidation.

  19. Adsorption of precious metals in water by dendrimer modified magnetic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Yen, Chia-Hsin [Institute of Environmental Engineering, National Chiao Tung University, 300 Hsinchu, Taiwan (China); Lien, Hsing-Lung, E-mail: lien.sam@nuk.edu.tw [Department of Civil and Environmental Engineering, National University of Kaohsiung, 811 Kaohsiung, Taiwan (China); Chung, Jung-Shing [Department of Civil and Environmental Engineering, National University of Kaohsiung, 811 Kaohsiung, Taiwan (China); Yeh, Hund-Der [Institute of Environmental Engineering, National Chiao Tung University, 300 Hsinchu, Taiwan (China)

    2017-01-15

    Highlights: • A reusable magnetic nano-adsorbent is prepared for precious metal adsorption. • The nano-adsorbent (MNP-G3) is synthesized by magnetic nanoparticles and dendrimer. • Higher valent ions show higher adsorption capacity by MNP-G3 suggesting complexation involved. • The pseudo second-order model best describe the adsorption kinetics. • MNP-G3 modified by EDTA significantly improve its adsorption ability for Ag(I). - Abstract: Magnetic nanoparticles modified by third-generation dendrimers (MNP-G3) and MNP-G3 further modified by ethylenediaminetetraacetic acid (EDTA) (MNP-G3-EDTA) were conducted to investigate their ability for recovery of precious metals (Pd(IV), Au(III), Pd(II) and Ag(I)) in water. Experiments were carried out using batch reactors for the studies of adsorption kinetics, adsorption isotherms, competitive adsorption and regeneration. The pseudo second-order model is the best-fit model among others suggesting that the adsorption of precious metals by MNP-G3 in water is a chemisorption process. Three adsorption isotherms namely Langmuir, Freundlich and Dubinin-Radushkevich isotherm were examined and the results showed the similarities and consistency of both linear and nonlinear analyses. Pd(IV) and Au(III) with higher valence exhibited relatively better adsorption efficiency than Pd(II) and Ag(I) with lower valence suggesting that the adsorption of precious metals by MNP-G3 is a function of valence. In the presence of the competing ion Zn(II), the adsorption efficiency of MNP-G3 for all four precious metals was declined significantly. The use of MNP-G3-EDTA revealed an increase in the adsorption efficiency for all four precious metals. However, the low selectivity of MNP-G3 towards precious metals was not enhanced by the modification of EDTA onto the MNP-G3. The regeneration of metal-laden MNP-G3 can be readily performed by using 1.0% HCl solution as a desorbent solution.

  20. Mise au point

    African Journals Online (AJOL)

    31 mai 2013 ... traités au service de chirurgie maxillo-faciale et chirurgie plastique de l'hôpital ... qui est la fracture simple isolée du corps, on a inclut ce type de fracture ... sion latérale au niveau de la queue du sourcil. La voie vestibulaire ...

  1. Ge-Au eutectic bonding of Ge (100) single crystals

    International Nuclear Information System (INIS)

    Knowlton, W.B.; Beeman, J.W.; Emes, J.H.; Loretto, D.; Itoh, K.M.; Haller, E.E.

    1993-01-01

    The author present preliminary results on the eutectic bonding between two (100) Ge single crystal surfaces using thin films of Au ranging from 900 angstrom/surface to 300 angstrom/surface and Pd (10% the thickness of Au). Following bonding, plan view optical microscopy (OM) of the cleaved interface of samples with Au thicknesses ≤ 500 angstrom/surface show a eutectic morphology more conducive to phonon transmission through the bond interface. High resolution transmission electron microscopy (HRTEM) cross sectional interface studies of a 300 angstrom/surface Au sample show epitaxial growth of Ge. In sections of the bond, lattice continuity of the Ge is apparent through the interface. TEM studies also reveal heteroepitaxial growth of Au with a Au-Ge lattice mismatch of less than 2%. Eutectic bonds with 200 angstrom/surface Au have been attained with characterization pending. An optical polishing technique for Ge has been optimized to insure intimate contact between the Ge surfaces prior to bonding. Interferometry analysis of the optically polished Ge surface shows that surface height fluctuations lie within ±150 angstrom across an interval of lmm. Characterization of phonon transmission through the interface is discussed with respect to low temperature detection of ballistic phonons

  2. Au pair trajectories

    DEFF Research Database (Denmark)

    Dalgas, Karina Märcher

    2015-01-01

    pair-sending families in the Philippines, this dissertation examines the long-term trajectories of these young Filipinas. It shows how the au pairs’ local and transnational family relations develop over time and greatly influence their life trajectories. A focal point of the study is how au pairs...... that Filipina au pairs see their stay abroad as an avenue of personal development and social recognition, I examine how the au pairs re-position themselves within their families at home through migration, and how they navigate between the often conflicting expectations of participation in the sociality......Since 2000, thousands of young Filipino migrants have come to Denmark as au pairs. Officially, they are there to “broaden their cultural horizons” by living temporarily with a Danish host family, but they also conduct domestic labor in exchange for food and money, which allows them to send...

  3. A study on the reaction between SiC and Pd, (2)

    International Nuclear Information System (INIS)

    Namba, Takashi; Minato, Kazuo; Yamawaki, Michio; Fukuda, Kousaku.

    1989-01-01

    An out of pile experiment was performed on the corrosion of the SiC layer by fission product Pd in the Triso-coated fuel particles of high temperature gas-cooled reactor. In order to clarify the corrosion mechanism, influence of Pd activity on the corrosion was studied. Seven Au-Pd alloys with different Pd contents were prepared and simulated TRISO-coated particles were heated in the powder of the alloys at 1473 and 1573K. The Pd-SiC reaction zones were observed and analyzed by XMA. From the experimental results, the reaction rate was found to be dependent on Pd activity. The dependence of the reaction rate on temperature and time was also discussed. (author)

  4. Enhanced middle-infrared light transmission through Au/SiO(x)N(y)/Au aperture arrays.

    Science.gov (United States)

    Xiao, Gongli; Yao, Xiang; Ji, Xinming; Zhou, Jia; Bao, Zongming; Huang, Yiping

    2011-12-01

    The enhanced middle-infrared light transmission through Au/SiO(x)N(y)/Au aperture arrays by changing the refractive index and the thickness of a dielectric layer was studied experimentally. The results indicated that the transmission spectra was highly dependent on the refractive index and the thickness of SiO(x)N(y). We found that the transmission peaks redshifted regularly along with the refractive index from 1.6 to 1.8, owing to the role of surface plasmon polaritons (SPP) coupling in the Au/SiO(x)N(y)/Au cascaded metallic structure. Simultaneously, a higher transmission efficiency and narrower transmission peak was obtained in Au/SiO2.1N0.3/Au cascaded metallic structure with small refractive index (1.6) than in Au/SiO0.6N1/Au cascaded metallic structure with large refractive index (1.8). When the thickness of SiO(x)N(y) changes from 0.2 to 0.4 microm, the shape of transmission spectra exhibits a large change. It was found that a higher transmission efficiency and narrower transmission peak was obtained in Au/SiO(x)N(y)/Au cascaded metallic structure with a thin dielectric film (0.2 microm), with the increase of SiO(x)N(y) film's thickness, the transmission peak gradually widened and disappeared finally. This effect is useful in applications of biochemical sensing and tunable integrated plasmonic devices in the middle-infrared region.

  5. Plot Description (PD)

    Science.gov (United States)

    Robert E. Keane

    2006-01-01

    The Plot Description (PD) form is used to describe general characteristics of the FIREMON macroplot to provide ecological context for data analyses. The PD data characterize the topographical setting, geographic reference point, general plant composition and cover, ground cover, fuels, and soils information. This method provides the general ecological data that can be...

  6. Density functional calculations on 13-atom Pd12M (M = Sc—Ni) bimetallic clusters

    International Nuclear Information System (INIS)

    Tang Chun-Mei; Chen Sheng-Wei; Zhu Wei-Hua; Tao Cheng-Jun; Zhang Ai-Mei; Gong Jiang-Feng; Zou Hua; Liu Ming-Yi; Zhu Feng

    2012-01-01

    The geometric structures, electronic and magnetic properties of the 3d transition metal doped clusters Pd 12 M (M = Sc—Ni) are studied using the semi-core pseudopots density functional theory. The groundstate geometric structure of the Pd 12 M cluster is probably of pseudoicosahedron. The I h -Pd 12 M cluster has the most thermodynamic stability in five different symmetric isomers. The energy gap shows that Pd 12 M cluster is partly metallic. Both the absolutely predominant metal bond and very weak covalent bond might exist in the Pd 12 M cluster. The magnetic moment of Pd 12 M varies from 0 to 5 μ B , implying that it has a potential application in new nanomaterials with tunable magnetic properties

  7. Nitrite reduction mechanism on a Pd surface.

    Science.gov (United States)

    Shin, Hyeyoung; Jung, Sungyoon; Bae, Sungjun; Lee, Woojin; Kim, Hyungjun

    2014-11-04

    Nitrate (NO3-) is one of the most harmful contaminants in the groundwater, and it causes various health problems. Bimetallic catalysts, usually palladium (Pd) coupled with secondary metallic catalyst, are found to properly treat nitrate-containing wastewaters; however, the selectivity toward N2 production over ammonia (NH3) production still requires further improvement. Because the N2 selectivity is determined at the nitrite (NO2-) reduction step on the Pd surface, which occurs after NO3- is decomposed into NO2- on the secondary metallic catalyst, we here performed density functional theory (DFT) calculations and experiments to investigate the NO2- reduction pathway on the Pd surface activated by hydrogen. Based on extensive DFT calculations on the relative energetics among ∼100 possible intermediates, we found that NO2- is easily reduced to NO* on the Pd surface, followed by either sequential hydrogenation steps to yield NH3 or a decomposition step to N* and O* (an adsorbate on Pd is denoted using an asterisk). Based on the calculated high migration barrier of N*, we further discussed that the direct combination of two N* to yield N2 is kinetically less favorable than the combination of a highly mobile H* with N* to yield NH3. Instead, the reduction of NO2- in the vicinity of the N* can yield N2O* that can be preferentially transformed into N2 via diverse reaction pathways. Our DFT results suggest that enhancing the likelihood of N* encountering NO2- in the solution phase before combination with surface H* is important for maximizing the N2 selectivity. This is further supported by our experiments on NO2- reduction by Pd/TiO2, showing that both a decreased H2 flow rate and an increased NO2- concentration increased the N2 selectivity (78.6-93.6% and 57.8-90.9%, respectively).

  8. Development of a high temperature ceramic-to-metal seal for Air Force Weapons Laboratory Laser

    Science.gov (United States)

    Honnell, R. E.; Stoddard, S. D.

    1987-03-01

    Procedures were developed for fabricating vacuum tight metal-to-ceramic ring seals between Inconel 625 and MgO-3 wt % Y2O3 tubes metallized with a calcia-alumina-silica glass (CaO-29 wt % Al2O3-35 wt % SiO2) containing 50 vol % molybdenum filler. Palniro No. 1 (Au-25 wt % Pd-25 wt % Ni) was found to be the most reliable braze for joining Inconel to metallized MgO-3 wt % Y2O3 bodies. The reliabilities of the processing procedures and the material systems were demonstrated. A prototype electrical feedthrough was fabricated for 1173 K operation in air or vacuum.

  9. Amorphous Pd-assisted H 2 detection of ZnO nanorod gas sensor with enhanced sensitivity and stability

    KAUST Repository

    Kim, Hyeonghun

    2018-02-05

    For monitoring H2 concentrations in air, diverse resistive gas sensors have been demonstrated. In particular, Pd-decorated metal oxides have shown remarkable selectivity and sensing response for H2 detection. In this work, H2 sensing behavior of amorphous Pd layer covering ZnO nanorods (am-Pd/ZnO NRs) is investigated. This is the first report on the enhanced gas sensing performance attained by using an amorphous metal layer. The amorphous Pd layer is generated by reduction reaction with a strong reducing agent (NaBH4), and it covers the ZnO nanorods completely with a thickness of 2 ∼ 5 nm. For comparison, crystalline Pd nanoparticles-decorated ZnO nanorods (c-Pd/ZnO NRs) are produced using a milder reducing agent like hydrazine. Comparing the c-Pd/ZnO NRs sensor and other previously reported hydrogen sensors based on the crystalline Pd and metal oxides, the am-Pd/ZnO NRs sensor exhibits a remarkable sensing response (12,400% at 2% H2). The enhancement is attributed to complete cover of the amorphous Pd layer on the ZnO NRs, inducing larger interfaces between the Pd and ZnO. In addition, the amorphous Pd layer prevents surface contamination of the ZnO NRs. Therefore, the am-Pd/ZnO NRs sensor maintains initial sensing performance even after 5 months.

  10. Amorphous Pd-assisted H 2 detection of ZnO nanorod gas sensor with enhanced sensitivity and stability

    KAUST Repository

    Kim, Hyeonghun; Pak, Yusin; Jeong, Yeonggyo; Kim, Woochul; Kim, Jeongnam; Jung, Gun Young

    2018-01-01

    For monitoring H2 concentrations in air, diverse resistive gas sensors have been demonstrated. In particular, Pd-decorated metal oxides have shown remarkable selectivity and sensing response for H2 detection. In this work, H2 sensing behavior of amorphous Pd layer covering ZnO nanorods (am-Pd/ZnO NRs) is investigated. This is the first report on the enhanced gas sensing performance attained by using an amorphous metal layer. The amorphous Pd layer is generated by reduction reaction with a strong reducing agent (NaBH4), and it covers the ZnO nanorods completely with a thickness of 2 ∼ 5 nm. For comparison, crystalline Pd nanoparticles-decorated ZnO nanorods (c-Pd/ZnO NRs) are produced using a milder reducing agent like hydrazine. Comparing the c-Pd/ZnO NRs sensor and other previously reported hydrogen sensors based on the crystalline Pd and metal oxides, the am-Pd/ZnO NRs sensor exhibits a remarkable sensing response (12,400% at 2% H2). The enhancement is attributed to complete cover of the amorphous Pd layer on the ZnO NRs, inducing larger interfaces between the Pd and ZnO. In addition, the amorphous Pd layer prevents surface contamination of the ZnO NRs. Therefore, the am-Pd/ZnO NRs sensor maintains initial sensing performance even after 5 months.

  11. Modification of the sulphur resistance of platinum by addition of metals for aromatics hydrogenation; Modification de la thioresistance du platine par ajouts d'elements metalliques pour l'hydrogenation d'aromatiques

    Energy Technology Data Exchange (ETDEWEB)

    Guillon, E

    1999-09-15

    The aim of this study is based on the understanding of sulphur resistance of platinum catalytic systems. In this work, bimetallic systems (Pt-Ge, Pt-Au and Pt-Pd) supported on {gamma}-alumina have been studied. Preparation methods have been chosen to give the best control of the physicochemical properties of final system. Electronic and geometrical properties of the metallic phase were characterised by various techniques (TPR, infrared spectroscopy of adsorbed CO (IR(CO)), EXAFS, LEIS). Ortho-xylene hydrogenation in presence of 100 ppm of sulphur was used as model catalytic test in order to study the sulphur resistance of the catalysts. It has been shown that germanium and palladium act as electro-acceptors toward platinum. The ranking of catalytic activity in presence of sulphur is as followed: Pt-Pd > Pt-Au {approx_equal} Pt >> Pt-Ge {approx_equal} 0. The best sulphur resistance for Pt-Pd was obtained for the composition Pt{sub 20}Pd{sub 80} (Pd/Pt=4). An eggshell PdS structure with Pt (sulfur free) core is proposed. These works show that the sulphur resistance of platinum is not only linked with its electronic properties. They allow us to propose an original concept of sulphur resistant catalyst taking into account each catalytic parameters such as chemical bonding of S and aromatic compounds on the metallic site, physico-chemical characteristics of the bimetallic aggregates (particle size, structure, surface composition) and electronic modification of surface atoms in bimetallic catalysts. (author)

  12. Modification of the sulphur resistance of platinum by addition of metals for aromatics hydrogenation; Modification de la thioresistance du platine par ajouts d'elements metalliques pour l'hydrogenation d'aromatiques

    Energy Technology Data Exchange (ETDEWEB)

    Guillon, E.

    1999-09-15

    The aim of this study is based on the understanding of sulphur resistance of platinum catalytic systems. In this work, bimetallic systems (Pt-Ge, Pt-Au and Pt-Pd) supported on {gamma}-alumina have been studied. Preparation methods have been chosen to give the best control of the physicochemical properties of final system. Electronic and geometrical properties of the metallic phase were characterised by various techniques (TPR, infrared spectroscopy of adsorbed CO (IR(CO)), EXAFS, LEIS). Ortho-xylene hydrogenation in presence of 100 ppm of sulphur was used as model catalytic test in order to study the sulphur resistance of the catalysts. It has been shown that germanium and palladium act as electro-acceptors toward platinum. The ranking of catalytic activity in presence of sulphur is as followed: Pt-Pd > Pt-Au {approx_equal} Pt >> Pt-Ge {approx_equal} 0. The best sulphur resistance for Pt-Pd was obtained for the composition Pt{sub 20}Pd{sub 80} (Pd/Pt=4). An eggshell PdS structure with Pt (sulfur free) core is proposed. These works show that the sulphur resistance of platinum is not only linked with its electronic properties. They allow us to propose an original concept of sulphur resistant catalyst taking into account each catalytic parameters such as chemical bonding of S and aromatic compounds on the metallic site, physico-chemical characteristics of the bimetallic aggregates (particle size, structure, surface composition) and electronic modification of surface atoms in bimetallic catalysts. (author)

  13. k-asymmetric spin splitting at the interface between transition metal ferromagnets and heavy metals

    KAUST Repository

    Grytsiuk, Sergii

    2016-05-23

    We systematically investigate the spin-orbit coupling-induced band splitting originating from inversion symmetry breaking at the interface between a Co monolayer and 4d (Tc, Ru, Rh, Pd, and Ag) or 5d (Re, Os, Ir, Pt, and Au) transition metals. In spite of the complex band structure of these systems, the odd-in-k spin splitting of the bands displays striking similarities with the much simpler Rashba spin-orbit coupling picture. We establish a clear connection between the overall strength of the odd-in-k spin splitting of the bands and the charge transfer between the d orbitals at the interface. Furthermore, we show that the spin splitting of the Fermi surface scales with the induced orbital moment, weighted by the spin-orbit coupling.

  14. k-asymmetric spin splitting at the interface between transition metal ferromagnets and heavy metals

    KAUST Repository

    Grytsyuk, Sergiy; Belabbes, Abderrezak; Haney, Paul M.; Lee, Hyun-Woo; Lee, Kyung-Jin; Stiles, M. D.; Schwingenschlö gl, Udo; Manchon, Aurelien

    2016-01-01

    We systematically investigate the spin-orbit coupling-induced band splitting originating from inversion symmetry breaking at the interface between a Co monolayer and 4d (Tc, Ru, Rh, Pd, and Ag) or 5d (Re, Os, Ir, Pt, and Au) transition metals. In spite of the complex band structure of these systems, the odd-in-k spin splitting of the bands displays striking similarities with the much simpler Rashba spin-orbit coupling picture. We establish a clear connection between the overall strength of the odd-in-k spin splitting of the bands and the charge transfer between the d orbitals at the interface. Furthermore, we show that the spin splitting of the Fermi surface scales with the induced orbital moment, weighted by the spin-orbit coupling.

  15. Ion beam induced effects on the ferromagnetism in Pd nanoparticles

    International Nuclear Information System (INIS)

    Kulriya, P. K.; Mehta, B. R.; Agarwal, D. C.; Agarwal, Kanika; Kumar, Praveen; Shivaprasad, S. M.; Avasthi, D. K.

    2012-01-01

    Present study demonstrates the role of metal-insulator interface and ion irradiation induced defects on the ferromagnetic properties of the non-magnetic materials. Magnetic properties of the Pd nanoparticles(NPs) embedded in the a-silica matrix synthesized using atom beam sputtering technique, were determined using SQUID magnetometry measurements which showed that ferromagnetic response of Pd increased by 3.5 times on swift heavy ion(SHI) irradiation. The ferromagnetic behavior of the as-deposited Pd NPs is due to strain induced by the surrounding matrix and modification in the electronic structure at the Pd-silica interface as revealed by insitu XRD and XPS investigations, respectively. The defects created by the SHI bombardment are responsible for enhancement of the magnetization in the Pd NPs.

  16. Fabrication of vertically aligned Pd nanowire array in AAO template by electrodeposition using neutral electrolyte

    Directory of Open Access Journals (Sweden)

    Yüzer Hayrettin

    2010-01-01

    Full Text Available Abstract A vertically aligned Pd nanowire array was successfully fabricated on an Au/Ti substrate using an anodic aluminum oxide (AAO template by a direct voltage electrodeposition method at room temperature using diluted neutral electrolyte. The fabrication of Pd nanowires was controlled by analyzing the current–time transient during electrodeposition using potentiostat. The AAO template and the Pd nanowires were characterized by scanning electron microscopy (SEM, energy-dispersive X-ray (EDX methods and X-Ray diffraction (XRD. It was observed that the Pd nanowire array was standing freely on an Au-coated Ti substrate after removing the AAO template in a relatively large area of about 5 cm2, approximately 50 nm in diameter and 2.5 μm in length with a high aspect ratio. The nucleation rate and the number of atoms in the critical nucleus were determined from the analysis of current transients. Pd nuclei density was calculated as 3.55 × 108 cm−2. Usage of diluted neutral electrolyte enables slower growing of Pd nanowires owing to increase in the electrodeposition potential and thus obtained Pd nanowires have higher crystallinity with lower dislocations. In fact, this high crystallinity of Pd nanowires provides them positive effect for sensor performances especially.

  17. A three-dimensional hierarchical nanoporous PdCu alloy for enhanced electrocatalysis and biosensing

    International Nuclear Information System (INIS)

    Liu Aihua; Geng Haoran; Xu Caixia; Qiu Huajun

    2011-01-01

    Highlights: → Nanotubular mesoporous PdCu (NM-PdCu) alloy is facilely fabricated via one-step metal replacement reaction between nanoporous Cu and H 2 PdCl 4 . → The NM-PdCu exhibits remarkably improved structure stability and electrocatalytic activity towards formic acid and hydrogen peroxide oxidation compared with NP-Pd. → When coupled with GOx, the GOx/NM-PdCu electrode can be used for sensitive detection of glucose over a wide concentration range. - Abstract: Nanoporous copper (NPC) obtained by dealloying CuAl alloy is used as both three-dimensional template and reducing agent for the fabrication of nanoporous PdCu alloy with hollow ligaments by a simple galvanic replacement reaction with H 2 PdCl 4 aqueous solution. Electron microscopy and X-ray diffraction characterizations demonstrate that after the replacement reaction, the ligaments become hollow tubular structure and the ligament shell is also comprised of small pores and nanoparticles with a typical size of ∼4 nm (third order porosity). The as-prepared nanotubular mesoporous PdCu alloy (NM-PdCu) structure exhibits remarkably improved electrocatalytic activity towards the oxidation of formic acid and H 2 O 2 compared with nanoporous Pd (NP-Pd), and can be used for sensitive electrochemical sensing applications. After coupled with glucose oxidase (GOx), the enzyme modified NM-PdCu electrode can sensitively detect glucose over a wide linear range (0.5-20 mM).

  18. Colorimetric determination of the fluoride ion - application to uranium metal and to uranous fluoride; Dosage colorimetrique de l'ion fluor - application a l'uranium metal et au fluorure uraneux

    Energy Technology Data Exchange (ETDEWEB)

    Hering, H; Hure, J; Legrand, S [Commissariat a l' Energie Atomique (France)

    1949-12-01

    In the determination described for fluoride in U metal, the U is brought into H{sub 2}SO{sub 4} solution by anodic oxidation, the fluo-silicic acid is distilled by entrainment in water vapor, and the F ion is determined in the distillate by using the fact that it complexes Zr and thus prevents the formation of the Zr-alizarin S lake. For F ion in UF{sub 4}, the compound is dissolved in a Na{sub 2}CO{sub 3}-H{sub 2}O{sub 2} mixture, and F is determined in the solution by the colorimetric method described. (author)

  19. Colorimetric determination of the fluoride ion - application to uranium metal and to uranous fluoride; Dosage colorimetrique de l'ion fluor - application a l'uranium metal et au fluorure uraneux

    Energy Technology Data Exchange (ETDEWEB)

    Hering, H.; Hure, J.; Legrand, S. [Commissariat a l' Energie Atomique (France)

    1949-12-01

    In the determination described for fluoride in U metal, the U is brought into H{sub 2}SO{sub 4} solution by anodic oxidation, the fluo-silicic acid is distilled by entrainment in water vapor, and the F ion is determined in the distillate by using the fact that it complexes Zr and thus prevents the formation of the Zr-alizarin S lake. For F ion in UF{sub 4}, the compound is dissolved in a Na{sub 2}CO{sub 3}-H{sub 2}O{sub 2} mixture, and F is determined in the solution by the colorimetric method described. (author)

  20. Photothermal radiometry applied to characterization and control of thermal contact resistance of crimped metals; Radiometrie photothermique appliquee a la caracterisation et au controle de la resistance thermique de contact de metaux sertis

    Energy Technology Data Exchange (ETDEWEB)

    Van Schel, Etienne

    1989-11-15

    Modulated photothermal radiometry is used to study the thermal contact between two metals. At first, two models using a bidimensional axisymmetric geometry are proposed to describe the interface: the first one deals with thermal contact resistance, the second one with an equivalent layer. A thorough calculation of the photothermal signal taking into account the nature of the sample and the detection is here presented. Theoretical simulations show the influence of several parameters (frequency. dimensions of the excitation and the detection) on the sensitivity of the method applied to the detection of the thermal resistance. The comparison, with a three layer-model justifies the use of thermal resistance in periodical regime, for air layers between metals. Then, we present an experimental device that is used to validate the model. The results, obtained on duralumin-copper samples, show the sensitivity of the method and lead us to propose values of thermal contact resistance for different crimpings. At last an industrial testing equipment is described. The results, obtained on laboratory samples, are confirmed. Heat exchanger pipes, including voluntary defects are tested. Thanks to this device, we are able to make an in situ crimping control that can also be applied to other types of contacts. [French] La radiometrie photothermique est utilisee pour etudier le contact thermique entre deux metaux. Tout d'abord, deux modeles utilisant une geometrie bidimensionnelle axisymetrique sont proposes pour decrire l'interface: le premier utilise une resistance thermique de contact, le second un milieu equivalent Un calcul complet du signal photothermique, prenant en compte la nature de l'echantillon et de la detection, est presente. Des simulations theoriques montrent l'influence de quelques parametres (frequence, dimensions de l'excitation et de la detection) sur la sensibilite de la methode a la detection de la resistance thermique. La comparaison, avec un modele a trois

  1. Chemical and electrical characteristics of annealed Ni/Au and Ni/Ir/Au contacts on AlGaN

    Energy Technology Data Exchange (ETDEWEB)

    Ngoepe, P.N.M., E-mail: phuti.ngoepe@up.ac.za [Department of Physics, University of Pretoria, Private Bag X20, Hatfield 0028 (South Africa); Meyer, W.E.; Auret, F.D.; Omotoso, E.; Diale, M. [Department of Physics, University of Pretoria, Private Bag X20, Hatfield 0028 (South Africa); Swart, H.C.; Duvenhage, M.M.; Coetsee, E. [Department of Physics, University of the Free State, P.O. Box 339, Bloemfontein 9300 (South Africa)

    2016-01-01

    The evolution of Ni/Au and Ni/Ir/Au metal contacts deposited on AlGaN was investigated at different annealing temperatures. The samples were studied with electrical and chemical composition techniques. I–V characteristics of the Schottky diodes were optimum after 500 and 600 °C annealing for Ni/Au and Ni/Ir/Au based diodes, respectively. The depth profiles of the contacts were measured by x-ray photoelectron spectroscopy and time of flight secondary ion mass spectroscopy. These chemical composition techniques were used to examine the evolution of the metal contacts in order to verify the influence the metals have on the electrical properties of the diodes. The insertion of Ir as a diffusion barrier between Ni and Au effected the electrical properties, improving the stability of the contacts at high temperatures. Gold diffused into the AlGaN film, degrading the electrical properties of the Ni/Au diode. At 500 °C, the insertion of Ir, however, prevented the in-diffusion of Au into the AlGaN substrate.

  2. A simple approach for facile synthesis of Ag, anisotropic Au and bimetallic (Ag/Au) nanoparticles using cruciferous vegetable extracts

    International Nuclear Information System (INIS)

    Jacob, Jasmine; Mukherjee, Tulsi; Kapoor, Sudhir

    2012-01-01

    We present a simple and straightforward approach for the synthesis and stabilization of relatively monodisperse Ag, Au and bimetallic (Ag/Au) nanoparticles by using cruciferous vegetable (green/red) extracts by simply adjusting the pH environment in the aqueous medium. The vegetable extracts act both as reducing and capping agents. The monometallic and bimetallic nanoparticles of Ag and Au so obtained were characterized by UV–visible spectroscopy, X-ray diffraction (XRD), dynamic light scattering (DLS) and transmission electron microscopy (TEM). It is shown that red cabbage extract can be used for the preparation of anisotropic Au nanoparticles. The formation of Au anisotropic nanoparticles was found to depend on a number of environmental factors, such as the pH of the reaction medium, reaction time, and initial reactant concentrations. Additionally, it is shown that these extract-stabilized Au and Ag nanoparticles can be used as a seed for preparation of bimetallic Au/Ag nanoparticles. For bimetallic alloy nanoparticles the absorption peak was observed between the two maxima of the corresponding metallic particles. The surface plasmon absorption maxima for bimetallic nanoparticles changed linearly with increasing Au mole ratio content in various alloy compositions. It has been shown that the formation of hollow Au spheres depends on the experimental conditions. - Graphical abstract: TEM image of gold nanoparticles at pH 3.27 formed by red cabbage extract. Highlights: ► First report on the reactivity of the extracts toward metal ions using a spectrophotometric technique. ► Red cabbage extract has better reducing properties than green cabbage extract. ► Red cabbage extract can reduce metal ions at any pH. ► Reduction of metal ions can have important consequences in the study of soil chemistry.

  3. A simple approach for facile synthesis of Ag, anisotropic Au and bimetallic (Ag/Au) nanoparticles using cruciferous vegetable extracts

    Energy Technology Data Exchange (ETDEWEB)

    Jacob, Jasmine; Mukherjee, Tulsi; Kapoor, Sudhir, E-mail: sudhirk@barc.gov.in

    2012-10-01

    We present a simple and straightforward approach for the synthesis and stabilization of relatively monodisperse Ag, Au and bimetallic (Ag/Au) nanoparticles by using cruciferous vegetable (green/red) extracts by simply adjusting the pH environment in the aqueous medium. The vegetable extracts act both as reducing and capping agents. The monometallic and bimetallic nanoparticles of Ag and Au so obtained were characterized by UV-visible spectroscopy, X-ray diffraction (XRD), dynamic light scattering (DLS) and transmission electron microscopy (TEM). It is shown that red cabbage extract can be used for the preparation of anisotropic Au nanoparticles. The formation of Au anisotropic nanoparticles was found to depend on a number of environmental factors, such as the pH of the reaction medium, reaction time, and initial reactant concentrations. Additionally, it is shown that these extract-stabilized Au and Ag nanoparticles can be used as a seed for preparation of bimetallic Au/Ag nanoparticles. For bimetallic alloy nanoparticles the absorption peak was observed between the two maxima of the corresponding metallic particles. The surface plasmon absorption maxima for bimetallic nanoparticles changed linearly with increasing Au mole ratio content in various alloy compositions. It has been shown that the formation of hollow Au spheres depends on the experimental conditions. - Graphical abstract: TEM image of gold nanoparticles at pH 3.27 formed by red cabbage extract. Highlights: Black-Right-Pointing-Pointer First report on the reactivity of the extracts toward metal ions using a spectrophotometric technique. Black-Right-Pointing-Pointer Red cabbage extract has better reducing properties than green cabbage extract. Black-Right-Pointing-Pointer Red cabbage extract can reduce metal ions at any pH. Black-Right-Pointing-Pointer Reduction of metal ions can have important consequences in the study of soil chemistry.

  4. Au Based Nanocomposites Towards Plasmonic Applications

    Science.gov (United States)

    Panniello, A.; Curri, M. L.; Placido, T.; Reboud, V.; Kehagias, N.; Sotomayor Torres, C. M.; Mecerreyes, D.; Agostiano, A.; Striccoli, M.

    2010-06-01

    Incorporation of nano-sized metals in polymers can transfer their unique features to the host matrix, providing nanocomposite materials with improved optical, electric, magnetic and mechanical properties. In this work, colloidal Au nanorods have been incorporated into PMMA based random co-polymer, properly functionalized with amino groups and the optical and morphological properties of the resulting nanocomposite have been investigated by spectroscopic and AFM measurements. Au nanorods have demonstrated to preserve the plasmon absorption and to retain morphological features upon the incorporation, thus making the final metal modified polymer composite exploitable for the fabrication of plasmonic devices. The prepared nanocomposites have been then patterned by Nano Imprint Lithography technique in order to demonstrate the viability of the materials towards optical applications.

  5. DFT study on stability and H2 adsorption activity of bimetallic Au79−nPdn (n = 1–55) clusters

    International Nuclear Information System (INIS)

    Liu, Xuejing; Tian, Dongxu; Meng, Changgong

    2013-01-01

    Highlights: ► Stability of Pd substitution type is face > mid-edge > corner > edge. ► H 2 adsorption activity is in contrast with the stability of Pd substitution type. ► Non-activated dissociation of H 2 occurs in Au 36 Pd 43−3 with high thermal stability. ► ε d agrees with that Pd at edge and corner are more active than face and mid-edge. - Abstract: The stability and H 2 adsorption activity of bimetallic Au 79−n Pd n (n = 1–55) clusters were studied by density functional theory with GGA-PW91 functional. The stability order for four Pd substitution types is face > mid-edge > corner > edge, and the stability is improved with increasing Pd content. In contrast with the stability order, H 2 adsorption activity is corner ≈ edge > mid-edge > face. The Au 36 Pd 43 (3) with Au:Pd ≈ 1:1 ratio and twenty-four Pd substitutions at (1 1 1) facets and nineteen Pd substitutions at subshell sites shows high stability and H 2 non-activated dissociation activity. The partial density of d-states and d band center revealed that the electronic properties are closely associated with the geometric characteristic and adsorption activity. Correlating the d band center ε d and the adsorption energies, the ε d order agrees with the adsorption activity that the Pd substitution at edge and corner sites are more active than at face and mid-edge sites

  6. Neutron scattering study of Ce3Au3Sb4

    International Nuclear Information System (INIS)

    Kasaya, Mitsuo; Katoh, Kenichi; Kohgi, Masahumi; Osakabe, Toyotaka

    1993-01-01

    Rare-earth compounds with an Y 3 Au 3 Sb 4 -type crystal structure are semiconductors or semi-metals. Among them, Ce 3 Au 3 Sb 4 is a semiconductor with an activation energy of about 640 K and shows no magnetic order down to 1.5 K. The magnetic part of the specific heat for Ce 3 Au 3 Sb 4 obtained by subtracting the value for La 3 Au 3 Sb 4 from the total specific heat of Ce 3 Au 3 Sb 4 shows a broad peak at around 10 K, the origin of which is well explained by the crystalline-field splitting determined by neutron scattering. (author)

  7. Quantum interference effects in nanostructured Au

    CERN Document Server

    Pratumpong, P; Evans, S D; Johnson, S; Howson, M A

    2002-01-01

    We present results on the magnetoresistance and temperature dependence of the resistivity for nanostructured Au produced by chemical means. The magnetoresistance was typical of highly disordered metals exhibiting quantum interference effects. We fitted the data and were able to determine the spin-orbit scattering relaxation time to be 10 sup - sup 1 sup 2 s and we found the inelastic scattering time at 10 K to be 10 sup - sup 1 sup 1 s. The inelastic scattering rate varied as T sup 3 between 4 and 20 K, which is typical for electron-phonon scattering in disordered metals.

  8. Trace- and rare-earth element geochemistry and Pb-Pb dating of black shales and intercalated Ni-Mo-PGE-Au sulfide ores in Lower Cambrian strata, Yangtze Platform, South China

    Science.gov (United States)

    Jiang, Shao-Yong; Chen, Yong-Quan; Ling, Hong-Fei; Yang, Jing-Hong; Feng, Hong-Zhen; Ni, Pei

    2006-08-01

    The Lower Cambrian black shale sequence of the Niutitang Formation in the Yangtze Platform, South China, hosts an extreme metal-enriched sulfide ore bed that shows >10,000 times enrichment in Mo, Ni, Se, Re, Os, As, Hg, and Sb and >1,000 times enrichment in Ag, Au, Pt, and Pd, when compared to average upper continental crust. We report in this paper trace- and rare-earth-element concentrations and Pb-Pb isotope dating for the Ni-Mo-PGE-Au sulfide ores and their host black shales. Both the sulfide ores and their host black shales show similar trace-element distribution patterns with pronounced depletion in Th, Nb, Hf, Zr, and Ti, and extreme enrichment in U, Ni, Mo, and V compared to average upper crust. The high-field-strength elements, such as Zr, Hf, Nb, Ta, Sc, Th, rare-earth elements, Rb, and Ga, show significant inter-element correlations and may have been derived mainly from terrigenous sources. The redox sensitive elements, such as V, Ni, Mo, U, and Mn; base metals, such as Cu, Zn, and Pb; and Sr and Ba may have been derived from mixing of seawater and venting hydrothermal sources. The chondrite-normalized REE patterns, positive Eu and Y anomalies, and high Y/Ho ratios for the Ni-Mo-PGE-Au sulfide ores are also suggestive for their submarine hydrothermal-exhalative origin. A stepwise acid-leaching Pb-Pb isotope analytical technique has been employed for the Niutitang black shales and the Ni-Mo-PGE-Au sulfide ores, and two Pb-Pb isochron ages have been obtained for the black shales (531±24 Ma) and for the Ni-Mo-PGE-Au sulfide ores (521±54 Ma), respectively, which are identical and overlap within uncertainty, and are in good agreement with previously obtained ages for presumed age-equivalent strata.

  9. Diastereoselective Au-Catalyzed Allene Cycloisomerizations to Highly Substituted Cyclopentenes.

    Science.gov (United States)

    Reeves, Ryan D; Phelps, Alicia M; Raimbach, William A T; Schomaker, Jennifer M

    2017-07-07

    Site- and regiocontrolled Au-catalyzed allene carbocyclizations furnish highly substituted cyclopentenes in >1:1 dr. Significant substitution on the substrate is tolerated, with potential to install five contiguous stereocenters after alkene functionalization. Major challenges include identifying a Au/Cu catalyst that controls both the relative rates of allene epimerization/cyclization and the facial selectivity in addition of a metal enolate to the allene. Experiments to achieve stereodivergent cyclizations and transform key cyclopentenes into useful synthetic building blocks are described.

  10. Typomorphic Characteristics of Molybdenite from the Bystrinsky Cu-Au Porphyry-Skarn Deposit, Eastern Transbaikal Region, Russia

    Science.gov (United States)

    Kovalenker, V. A.; Trubkin, N. V.; Abramova, V. D.; Plotinskaya, O. Yu.; Kiseleva, G. D.; Borisovskii, S. E.; Yazykova, Yu. I.

    2018-01-01

    The paper presents pioneering data on the composition, texture, and crystal structure of molybdenite from various types of molybdenum mineralization at the Bystrinsky Cu-Au-Fe porphyry-skarn deposit in the eastern Transbaikal region, Russia. The data were obtained using electron microprobe analysis (EMPA), laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), and high-resolution transmission electron microscopy (HRTEM). Molybdenite found at the deposit in skarn, sulfide-poor quartz veins, and quartz-feldspar alteration markedly differs in the concentrations of trace elements determined by their species in the mineral, as well as in its structural features. Molybdenite-2H from skarn associated with phyllosilicates occurs as ultrafine crystals with uniform shape and texture; no dislocations or inclusions were found but amorphous silica was. The molybdenite composition is highly contrasting in the content and distribution of both structure-related (Re, W, and Se) and other (Mn, Co, Ni, Cu, Zn, As, Ag, Cd, Sb, Te, Ag, Pd, Au, Hg, Pb, and Bi) metals. In the sulfide-poor quartz veins, highly structurally heterogeneous (2H + 3R) molybdenite microcrystals with abundant defects (dislocations and volumetrically distributed inclusions) are associated with illite, goethite, and barite. Some single crystals are unique three-phase (2H + 3R polytypes + amorphous MoS2). The mineral has a low concentration of all trace elements, which are uniformly distributed. However, individual domains with uniquely high Pd, Te, Ni, Hg, and W concentrations caused by mineral inclusions are found in some grains. Molybdenite from quartz-feldspar alteration is characterized by low concentrations of all trace elements except for Re and Se, which enrich some domains of the grains. Our data indicate that the compositional and structural heterogeneity of molybdenite from the Bystrinsky deposit are its crucial features, which obviously correlate with the types of Mo mineralization.

  11. Electric-field effects on magnetic anisotropy in Pd/Fe/Pd(0 0 1) surface

    International Nuclear Information System (INIS)

    Haraguchi, Shinya; Tsujikawa, Masahito; Gotou, Junpei; Oda, Tatsuki

    2011-01-01

    Electric-field (EF) effects have been studied on magnetic anisotropy in the metallic surfaces Pt/Fe/Pt(0 0 1) and Pd/Fe/Pd(0 0 1) by means of the first-principles electronic structure calculation which employs the generalized gradient approximation. The variation of anisotropy energy with respect to the EF is found to be opposite to each other. The modulus rate of the variation is larger by a few factors in the Pt substrate than in the Pd one. These results agree qualitatively well with the available experimental data. The electronic structures are presented and the origins in EF effects are discussed along a line of the second perturbative fashion.

  12. On the electron density localization in elemental cubic ceramic and FCC transition metals by means of a localized electrons detector.

    Science.gov (United States)

    Aray, Yosslen; Paredes, Ricardo; Álvarez, Luis Javier; Martiz, Alejandro

    2017-06-14

    The electron density localization in insulator and semiconductor elemental cubic materials with diamond structure, carbon, silicon, germanium, and tin, and good metallic conductors with face centered cubic structure such as α-Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au, was studied using a localized electrons detector defined in the local moment representation. Our results clearly show an opposite pattern of the electron density localization for the cubic ceramic and transition metal materials. It was found that, for the elemental ceramic materials, the zone of low electron localization is very small and is mainly localized on the atomic basin edges. On the contrary, for the transition metals, there are low-valued localized electrons detector isocontours defining a zone of highly delocalized electrons that extends throughout the material. We have found that the best conductors are those in which the electron density at this low-value zone is the lowest.

  13. Efficient Pd@MIL-101(Cr) hetero-catalysts for 2-butyne-1,4-diol hydrogenation exhibiting high selectivity

    KAUST Repository

    Yin, Dongdong; Li, Chuang; Ren, Hangxing; Shekhah, Osama; Liu, Jinxuan; Liang, Changhai

    2017-01-01

    Pd@MIL-101(Cr) hetero-catalysts have been successfully prepared using the metal-organic chemical vapour deposition (MOCVD) approach, by choosing [Pd(η-CH)(η-CH)] as a volatile precursor, and the hydrothermally stable metal-organic framework, MIL-101

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

    Directory of Open Access Journals (Sweden)

    Reynaldo Martínez Guerrero

    2014-01-01

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

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

    International Nuclear Information System (INIS)

    Sharma, Geeta K.

    2011-01-01

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

  16. Weak aurophilic interactions in a series of Au(III) double salts.

    Science.gov (United States)

    Chernyshev, Alexander N; Chernysheva, Maria V; Hirva, Pipsa; Kukushkin, Vadim Yu; Haukka, Matti

    2015-08-28

    In this work, several new examples of rare Au(III)Au(III) aurophilic contacts are reported. A series of gold(iii) double salts and complexes, viz. [AuX2(L)][AuX4] (L = 2,2'-bipyridyl, X = Cl , Br ; L = 2,2'-bipyrimidine, X = Cl , Br ; L = 2,2'-dipyridylamine, X = Cl , Br ), [AuX3(biq)] (biq = 2,2'-biquinoline, X = Cl , Br ), [LH][AuX4] (L = 2,2'-bipyridyl, X = Cl ; L = 2,2'-bipyrimidine, X = Cl ; L = 2,2'-dipyridylamine, X = Cl , Br ; L = 2,2'-biquinoline, X = Cl , Br ), [AuBr2(bpy)]2[AuBr4][AuBr2] , [AuCl2(bpm)][AuCl2] , (bpmH)2[AuBr4][AuBr2] , and (dpaH)[AuBr2] (, , and were reported earlier) was synthesized by coordination of a particular ligand to the Au(III) center and subsequent reduction of the formed product with acetone. Inspection of the X-ray structural data for , , and indicates that the Au(III) metal centers approach each other closer than the sum of their van der Waals radii, thus forming the aurophilic contacts, which were confirmed by topological charge density analysis according to the Quantum Theory of Atoms in Molecules (QTAIM). In , , and , such contacts are located only between the metal centers of the ion pair, whereas in , the aurophilic interactions form the cation-anion-anion array, and in , the aurophilicity exists between the gold atoms of the cations. It was also demonstrated that the interatomic distance alone is not a reliable measure of the aurophilic interactions, at least at the weakest limit of the interaction strength, and it needs to be complemented with structural analysis of the whole molecule and computational results.

  17. Measurements of the thermal neutron cross-section and resonance integral for the 108Pd(n,γ)109Pd reaction

    Science.gov (United States)

    Hien, Nguyen Thi; Kim, Guinyun; Kim, Kwangsoo; Do, Nguyen Van; Khue, Pham Duc; Thanh, Kim Tien; Shin, Sung-Gyun; Cho, Moo-Hyun

    2018-06-01

    The thermal neutron capture cross-section (σ0) and resonance integral (I0) of the 108Pd(n,γ)109Pd reaction have been measured relative to that of the monitor reaction 197Au(n,γ)198Au. The measurements were carried out using the neutron activation with the cadmium ratio method. Both the samples and monitors were irradiated with and without cadmium cover of 0.5 mm thickness. The induced activities of the reaction products were measured with a well calibrated HPGe γ-ray detector. In order to improve the accuracy of the results, the necessary correcti