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Sample records for pt ni pd

  1. Magnetic hyperfine interaction studies of isolated Ni impurities in Pd and Pd-Pt alloys

    Science.gov (United States)

    Müller, W.; Bertschat, H. H.; Haas, H.; Spellmeyer, B.; Zeitz, W.-D.

    1989-10-01

    The magnetic hyperfine fields at isolated Ni impurities in Pd and Pd-Pt alloys were studied with the perturbed-angular-distribution (PAD) method by measuring the temperature, magnetic field, and concentration dependence of the nuclear-spin Larmor precession of isomeric states in 63Ni. The recoil-implanted Ni nuclei, as products of heavy-ion nuclear reactions, are present in extreme dilution (Pd-Pt alloys a considerable positive shift remains even at 30 at. % Pt content. The variation of the shift with Pt concentration and temperature reflects the variation of the Pd-Pt alloy susceptibility. The different contributions to the hyperfine field could be differentiated by comparing the Knight shift for Ni in Pd with its susceptibility contribution obtained from extrapolated susceptibility measurements in dilute Pd-Ni alloys. The negative core-polarization field of the impurity spin moment is compensated for by a transferred hyperfine field correlated with the host polarization in the neighborhood of the impurity. The remaining positive hyperfine field is due to a weak orbital moment of 0.3μB at the impurity site. The values obtained for the different contributions are compared with results of the Korringa-Kohn-Rostoker-coherent-potential-approximation calculations for concentrated Pd-Ni alloys extrapolated to the dilute limit.

  2. 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...

  3. The role of Pt and Pd in enhancing the conversion of sorbitol to hydrogen over supported Ni-Pt and Ni-Pd catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tanksale, A.; Lu, G.Q. [Queensland Univ., Brisbane (Australia); Beltramini, J.N. [Queensland Univ., Brisbane (Australia). ARC Centre of Excellence for Functional Nanomaterials

    2009-07-01

    This study investigated the enhanced activity of bimetallic nickel-platinum (Ni-Pt) and nickel-palladium (Ni-Pd) catalysts for the production of hydrogen from reformed biomass-based products. The catalysts were prepared on an aluminum oxide (Al203) nanofibre. Mesoporous zirconia and composite silica-zirconia-ceria were used to determine the role of noble metals and supports. Desorption, oxidation, and temperature programmed reduction studies were conducted to investigate metal-metal and metal-support interactions. The study showed that Pt and Pd additions increased the reducibility of Ni catalysts. The bimetallic catalysts exhibited rates of hydrogen production 6 times higher than rates observed in pure metal catalysts. Sorbitol conversion increased from 35 per cent for the Ni catalyst to 62 per cent for the Ni-Pt catalyst. It was concluded that the alloying effect of the Ni-Pt and Ni-Pd systems lowered the carbon monoxide (CO) adsorption heat, and facilitated removal of the adsorbed CO by the water gas shift reaction.

  4. Highly efficient anode catalyst with a Ni@PdPt core–shell nanostructure for methanol electrooxidation in alkaline media

    Institute of Scientific and Technical Information of China (English)

    Pei-shu Yu; Chun-tao Liu; Bo Feng; Jia-feng Wan; Li Li; Chun-yu Du

    2015-01-01

    To enhance the electrocatalytic activity of anode catalysts used in alkaline-media direct methanol fuel cells (DMFCs), a Ni@PdPt electrocatalyst was successfully prepared using a three-phase-transfer method. The Ni@PdPt electrocatalyst was characterized by X-ray dif-fraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and high-resolution TEM (HRTEM) techniques. The experimental results indicate that the average particle size of the core–shell-structured Ni@PdPt electrocatalyst is approxi-mately 5.6 nm. The Ni@PdPt electrocatalyst exhibits a catalytic activity 3.36 times greater than that of PdPt alloys for methanol oxidation in alkaline media. The developed Ni@PdPt electrocatalyst offers a promising alternative as a highly electrocatalytically active anode catalyst for alkaline DMFCs.

  5. Comparison of the thermal stabilities of NiSi films in Ni/Si, Ni/Pd/Si and Ni/Pt/Si systems

    CERN Document Server

    Wang, R N

    2003-01-01

    The effects of different interlayer materials (Pd and Pt) deposited between Ni films and Si substrates on the NiSi thermal stability are discussed. Ni sub 0 sub . sub 9 sub 4 sub 3 Pd sub 0 sub . sub 0 sub 5 sub 7 Si and Ni sub 0 sub . sub 9 sub 4 sub 5 Pt sub 0 sub . sub 0 sub 5 sub 5 Si solid solutions were formed when the samples were annealed at high temperatures and the lattice parameters of Ni sub 0 sub . sub 9 sub 4 sub 3 Pd sub 0 sub . sub 0 sub 5 sub 7 Si were calculated according to Vegard's law. The NiSi thermal stability was enhanced by interposing a Pd or Pt interlayer, and the sample with the Pt interlayer had the highest NiSi thermal stability among all the samples studied. This is attributed to the reduction of the interface energy between NiSi and Si substrates and the decrease of the driving force for the nucleation of NiSi sub 2 , induced by formation of the NiSi(200) preferred orientation and the solid solution respectively.

  6. Effective-medium calculations for hydrogen in Ni, Pd, and Pt

    DEFF Research Database (Denmark)

    Christensen, Ole Bøssing; Stoltze, Per; Jacobsen, Karsten Wedel;

    1990-01-01

    The effective-medium theory is applied to a study of the energetics of the hydrides of Ni, Pd, and Pt, stressing the properties of PdHθ for 0≤θ≤1. The calculated heat of solution and the heat of hydride formation for the three systems agree very well with experiment. We determine the favored...... structure for PdHθ by calculating the total energy and lattice expansion of different configurations. Vibrational frequencies and diffusion barriers of H in Pd are also treated. A simple and transparent physical picture of the hydrogen-metal interaction is developed. From the calculated energetics we make...

  7. Role of Van der Waals Forces in Graphene Adsorption over Pd, Pt, and Ni

    Science.gov (United States)

    Quiroga, Matias A. O.; Cabeza, Gabriela F.

    2013-06-01

    We report ab initio computations with the Vienna Ab initio Simulation Package (VASP) aimed at elucidating the adsorption mechanism of graphene-like structures on (111) Pd, Pt, and Ni surfaces. To study the adsorption properties, we simulate an already-formed graphene layer. We present a comparative discussion of the graphene interactions with the three metals, focusing on the very particular adsorption of graphene over Pd.

  8. Role of Van der Waals forces in graphene adsorption over Pd, Pt, and Ni

    Energy Technology Data Exchange (ETDEWEB)

    Quiroga, Matias A.O.; Cabeza, Gabriela F. [Instituto de Física del Sur, CONICET, Bahia Blanca, Buenos Aires (Argentina)

    2013-07-01

    We report ab initio computations with the Vienna Ab initio Simulation Package (VASP) aimed at elucidating the adsorption mechanism of graphene-like structures on (111) Pd, Pt, and Ni surfaces. To study the adsorption properties, we simulate an already-formed graphene layer. We present a comparative discussion of the graphene interactions with the three metals, focusing on the very particular adsorption of graphene over Pd. (author)

  9. The electrochemical atomic layer deposition of Pt and Pd nanoparticles on Ni foam for the electro oxidation of alcohols

    CSIR Research Space (South Africa)

    Modibedi, RM

    2013-01-01

    Full Text Available of the electrocatalytic activity of the prepared catalysts. TABLE I. Electrochemical Activity of Pt and Pd Towards the Oxidation of Methanol. Catalyst Onset potential (V vs Ag/AgCl) If/Ib Pt/Carbon paper 0.41 4.30 Pt/Ni foam 0.38 2.16 Pd/Carbon paper* Pd.../Ni foam* -0.456 -0.429 2.86 1.30 *: methanol oxidation performed in alkaline medium TABLE II. Electrochemical Activity of Pd Towards the Oxidation of Ethanol in alkaline electrolyte. Catalyst Onset potential (V vs Ag/AgCl) If/Ib Pd...

  10. Electronic and magnetic properties of X-doped (X=Ni, Pd, Pt) WS{sub 2} monolayer

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Xu, E-mail: zhaoxu@htu.cn [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, Henan 453007 (China); Xia, Congxin [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, Henan 453007 (China); Dai, Xianqi [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, Henan 453007 (China); Department of Physics, Zhengzhou Normal University, Zhengzhou, Henan 450044 (China); Wang, Tianxing; Chen, Peng; Tian, Liang [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, Henan 453007 (China)

    2016-09-15

    We investigate the electronic and magnetic properties of X-doped (X=Ni, Pd, Pt) WS{sub 2} monolayer using the first-principles methods based on density functional theory. The results show that WS{sub 2} monolayer doped by Ni, Pd and Pt is ferromagnetic. The impurity states near the Fermi level depend highly on the atomic size and electronegativity. For different X-doped WS{sub 2}, the formation energy is lower under S-rich conditions, which indicates that it is energy favorable and relatively easier to incorporate X atom into WS{sub 2} under S-rich experimental conditions. Moreover, Ni-doped system owns the lowest formation energy compared with other atoms under S-rich experimental condition. Our studies predict X-doped (X=Ni, Pd, Pt) WS{sub 2} monolayers to be candidates for thin dilute magnetic semiconductors. Ni-doped WS{sub 2} has relatively wide half-metallic gap. So Ni-doped WS{sub 2} is the most ideal for spin injection among Ni, Pd, and Pt, which is important for application in semiconductor spintronics. - Highlights: • WS{sub 2} monolayer doped by Ni, Pd and Pt is ferromagnetic. • The formation energy is lower under S-rich conditions. • Ni-doped system owns wide half-metallic gap and the lowest formation energy. • Ni-doped WS{sub 2} is the most ideal for spin injection among Ni, Pd, and Pt.

  11. Analysis of the applicability of Ni, Cu, Au, Pt, and Pd nanoclusters for data recording

    Science.gov (United States)

    Redel', L. V.; Gafner, S. L.; Gafner, Yu. Ya.; Zamulin, I. S.; Goloven'ko, Zh. V.

    2017-02-01

    The applicability of individual Ni, Cu, Au, Pt, and Pd nanoclusters as data bits in next generation memory devices constructed on the phase-change carrier principle is studied. To this end, based on the modified tight-binding potential (TB-SMA), structure formation from the melt of nanoparticles of these metals to 10 nm in diameter was simulated by the molecular dynamics method. The effect of various crystallization conditions on the formation of the internal structures of Ni, Cu, Au, Pt, and Pd nanoclusters is studied. The stability boundaries of various crystalline isomers are analyzed. The obtained systematic features are compared for nanoparticles of copper, nickel, gold, platinum, and palladium of identical sizes. It is concluded that platinum nanoclusters of diameter D > 8 nm are the best materials among studied metals for producing memory elements based on phase transitions.

  12. Effect of nanoparticle (Pd, Pd/Pt, Ni deposition on high temperature hydrogenation of Ti-V alloys in gaseous flow containing CO

    Directory of Open Access Journals (Sweden)

    S. Suwarno

    2017-02-01

    Full Text Available The hydrogenation properties of Ti-V hydrides coated with nanoparticles have been studied in gaseous mixtures of argon and hydrogen with and without additions of 1% CO. Nanoparticles of Pd, Ni, and co-deposited Pd/Pt with particle sizes of ~30–60 nm were formed by electroless deposition on the hydride surfaces. The alloy resistance to CO could be significantly improved by particle deposition. Large amounts of hydrogen were absorbed in a CO-containing gas when Ni and Pd/Pt deposition had been applied, while pure Pd deposition had no positive effect. Ni was found to have a stronger effect than those of Pd/Pt and Pd, possibly because of the size effect of Ni nanoparticles.

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

    Science.gov (United States)

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

    2016-07-01

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

  14. Epitaxial Growth of Multimetallic Pd@PtM (M = Ni, Rh, Ru) Core-Shell Nanoplates Realized by in Situ-Produced CO from Interfacial Catalytic Reactions.

    Science.gov (United States)

    Yan, Yucong; Shan, Hao; Li, Ge; Xiao, Fan; Jiang, Yingying; Yan, Youyi; Jin, Chuanhong; Zhang, Hui; Wu, Jianbo; Yang, Deren

    2016-12-14

    Pt-based multimetallic core-shell nanoplates have received great attention as advanced catalysts, but the synthesis is still challenging. Here we report the synthesis of multimetallic Pd@PtM (M = Ni, Rh, Ru) nanoplates including Pd@Pt nanoplates, in which Pt or Pt alloy shells with controlled thickness epitaxially grow on plate-like Pd seeds. The key to achieve high-quality Pt-based multimetallic nanoplates is in situ generation of CO through interfacial catalytic reactions associated with Pd nanoplates and benzyl alcohol. In addition, the accurate control in a trace amount of CO is also of great importance for conformal growth of multimetallic core-shell nanoplates. The Pd@PtNi nanoplates exhibit substantially improved activity and stability for methanol oxidation reaction (MOR) compared to the Pd@Pt nanoplates and commercial Pt catalysts due to the advantages arising from plate-like, core-shell, and alloy structures.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mosca, H.O., E-mail: hmosca@cnea.gov.ar [Gcia. Investigacion y Aplicaciones, CNEA, Av. Gral Paz 1499, B1650KNA San Martin (Argentina); GCMM, UTN, FRG Pacheco, Av. H. Yrigoyen 288, Gral. Pacheco (Argentina); Bozzolo, G. [Loyola University Maryland, 4501 N. Charles St., Baltimore, MD 21210 (United States); Grosso, M.F. del [Gcia. Investigacion y Aplicaciones, CNEA, Av. Gral Paz 1499, B1650KNA San Martin (Argentina); GCMM, UTN, FRG Pacheco, Av. H. Yrigoyen 288, Gral. Pacheco (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas, CONICET (Argentina)

    2012-08-15

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

  16. The Crystal Growth and Characterization of CeT2Si2 Ternary Intermetallics (T = Ni, Pd, Pt)

    NARCIS (Netherlands)

    Menovsky, A.A.; Snel, C.E.; Gortenmulder, T.J.; Palstra, T.T.M.

    1986-01-01

    Bulk single crystals of the ternary intermetallic compounds CeNi2Si2, CePd2Si2 and CePt2Si2 have been grown from the melt with a modified “tri-arc” Czochralski method. The as-grown crystals were characterized by X-ray, microprobe, and chemical analyses. The measured densities were compared with the

  17. The Crystal Growth and Characterization of CeT2Si2 Ternary Intermetallics (T = Ni, Pd, Pt)

    NARCIS (Netherlands)

    Menovsky, A.A.; Snel, C.E.; Gortenmulder, T.J.; Palstra, T.T.M.

    1986-01-01

    Bulk single crystals of the ternary intermetallic compounds CeNi2Si2, CePd2Si2 and CePt2Si2 have been grown from the melt with a modified “tri-arc” Czochralski method. The as-grown crystals were characterized by X-ray, microprobe, and chemical analyses. The measured densities were compared with the

  18. The Sticking Probability for Hydrogen on Ni, Pd, and Pt at a Hydrogen pressure of 1 bar

    DEFF Research Database (Denmark)

    Johansson, Martin; Lytken, Ole; Chorkendorff, Ib

    2007-01-01

    A technique for measurements of the sticking probability of hydrogen on metal surfaces at high (ambient) pressure is described. As an example, measurements for Ni, Pd and Pt at a hydrogen pressure of 1 bar and temperatures between 40 and 200 degrees C are presented. The sticking probabilities...

  19. Martensitic transformation in Heusler alloys Mn{sub 2}YIn (Y=Ni, Pd and Pt): Theoretical and experimental investigation

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Hongzhi, E-mail: luo_hongzhi@163.com [School of Material Science and Engineering, Hebei University of Technology, Tianjin 300130 (China); Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Liu, Bohua; Xin, Yuepeng; Jia, Pengzhong; Meng, Fanbin [School of Material Science and Engineering, Hebei University of Technology, Tianjin 300130 (China); Liu, Enke; Wang, Wenhong; Wu, Guangheng [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China)

    2015-12-01

    The martensitic transformation and electronic structure of Heusler alloys Mn{sub 2}YIn (Y=Ni, Pd, Pt) have been investigated by both first-principles calculation and experimental investigation. Theoretical calculation reveals that, the energy difference ΔE between the tetragonal martensitic phase and cubic austenitic phase increases with Y varying from Ni to Pt in Mn{sub 2}YIn. Thus a structural transition from cubic to tetragonal is most likely to happen in Heusler alloy Mn{sub 2}PtIn. A single Heusler phase can be obtained in both Mn{sub 2}PtIn and Mn{sub 2}PdIn. A martensitic transformation temperature of 615 K has been identified in Mn{sub 2}PtIn. And in Mn{sub 2}PdIn, the austenitic phase is stable and no martensitic transformation is observed till 5 K. This indicates there may exist a positive relation between ΔE and martensitic transformation temperature. Calculated results show that Mn{sub 2}YIn are all ferrimagnets in both austenitic and martensitic phases. The magnetic properties are mainly determined by the antiparallel aligned Mn spin moments. These findings can help to develop new FSMAs with novel properties. - Highlights: • Positive relation between ΔE and martensitic transformation temperature has been observed. • Heusler alloy Mn{sub 2}PdIn has been synthesized successfully and investigated. • Martensitic transformation in Heusler alloys can be predicted by first -principles calculations.

  20. Thermomechanical behavior of NiTiPdPt high temperature shape memory alloy springs

    Science.gov (United States)

    Nicholson, D. E.; Padula, S. A., II; Noebe, R. D.; Benafan, O.; Vaidyanathan, R.

    2014-12-01

    Transformation strains in high temperature shape memory alloys (HTSMAs) are generally smaller than for conventional NiTi alloys and can be purposefully limited in cases where stability and repeatability at elevated temperatures are desired. Yet such alloys can still be used in actuator applications that require large strokes when used in the form of springs. Thus there is a need to understand the thermomechanical behavior of shape memory alloy spring actuators, particularly those consisting of alternative alloys. In this work, a modular test setup was assembled with the objective of acquiring stroke, stress, temperature, and moment data in real time during joule heating and forced convective cooling of Ni19.5Ti50.5Pd25Pt5 HTSMA springs. The spring actuators were subjected to both monotonic axial loading and thermomechanical cycling. The role of rotational constraints (i.e., by restricting rotation or allowing for free rotation at the ends of the springs) on stroke performance was also assessed. Finally, recognizing that evolution in the material microstructure can result in changes in HTSMA spring geometry, the effect of material microstructural evolution on spring performance was examined. This was done by taking into consideration the changes in geometry that occurred during thermomechanical cycling. This work thus provides insight into designing with HTSMA springs and predicting their thermomechanical performance.

  1. DFT study of the formate formation on Ni(111) surface doped by transition metals [Ni(111)-M; M=Cu, Pd, Pt, Rh

    Science.gov (United States)

    Nugraha; Saputro, A. G.; Agusta, M. K.; Rusydi, F.; Maezono, R.; Dipojono, H. K.

    2016-08-01

    We report on a theoretical study of the formation of formate (HCOO) from the reaction of CO2 gas and a pre- adsorbed H atom (CO2 (g) + *H → *HCOO) on Ni(111) surface doped by transition-metals [Ni(111)-M; M= Cu, Pd, Pt, Rh] by means of density functional theory (DFT) calculations. This *HCOO formation reaction is one of the most important rate- limiting steps in the methanol synthesis process. We find that the presence of transition metal doping on the first-layer of Ni(111) surface could reduce the activation barrier of this reaction [up to ~38.4%, compared to clean Ni(111) surface].

  2. Theoretical investigation of CO adsorption on TM-doped (MgO){sub 12} (TM = Ni, Pd, Pt) nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Yang Mingxia [Division of Molecule and Materials Simulation, State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Zhang Yonghong [Dept. of Applied Physics, Tianjin Polytechnic University, Tianjin 300160 (China); Huang Shiping, E-mail: huangsp@mail.buct.edu.cn [Division of Molecule and Materials Simulation, State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Liu Hui [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Wang Peng; Tian Huiping [Research Institute of Petroleum Processing, SINOPEC, Beijing 100083 (China)

    2011-12-01

    CO adsorption on TM-doped magnesia nanotubes (TM = Ni, Pd and Pt) have been studied by using density functional theory. Our calculation results show that CO favors adsorption on TM-doped magnesia nanotubes in the form of C atom bonding with TM atom. Fukui indices analysis clearly exhibits that doping of impurity TM atom allows for a noticeably enhancement of nucleophilic reactivity ability of magnesia nanotube. The adsorption energies demonstrate that CO molecule is more strongly bound on the 3-fold TM atoms than the 4-fold TM atoms. This finding is well confirmed by TM-C bond length, charge transfer and C-O vibrational frequency. The high adsorption energy of 2.55 eV is found when CO adsorbs on 3-fold Pt in Pt-doped magnesia nanotubes, implying the kind of the doping TM atom has a significant influence on the chemical reactivity.

  3. Ni-, Pd-, or Pt-catalyzed ethylene dimerization: a mechanistic description of the catalytic cycle and the active species.

    Science.gov (United States)

    Roy, Dipankar; Sunoj, Raghavan B

    2010-03-07

    Two key mechanistic possibilities for group 10 transition metal [M(eta(3)-allyl)(PMe(3))](+) catalyzed (where M = Ni(II), Pd(II) and Pt(II)) ethylene dimerization are investigated using density functional theory methods. The nature of the potential active catalysts in these pathways is analyzed to gain improved insights into the mechanism of ethylene dimerization to butene. The catalytic cycle is identified as involving typical elementary steps in transition metal-catalyzed C-C bond formation reactions, such as oxidative insertion as well as beta-H elimination. The computed kinetic and thermodynamic features indicate that a commonly proposed metal hydride species (L(n)M-H) is less likely to act as the active species as compared to a metal-ethyl species (L(n)M-CH(2)CH(3)). Of the two key pathways considered, the active species is predicted to be a metal hydride in pathway-1, whereas a metal alkyl complex serves as the active catalyst in pathway-2. A metal-mediated hydride shift from a growing metal alkyl chain to the ethylene molecule, bound to the metal in an eta(2) fashion, is predicted to be the preferred route for the generation of the active species. Among the intermediates involved in the catalytic cycle, metal alkyls with a bound olefin are identified as thermodynamically stable for all three metal ions. In general, the Ni-catalyzed pathways are found to be energetically more favorable than those associated with Pd and Pt catalysts.

  4. Intercomparison of electron probe micro-analyses and particle induced X-ray emission analyses of Pt-Pd-Ni-S matrices

    Energy Technology Data Exchange (ETDEWEB)

    Merkle, R.K.W. E-mail: rkwm@scientia.up.ac.zarmerkle@postino.up.ac.za; Franklyn, C.B.; Przybylowicz, W.; Verryn, S.M.C

    2002-05-01

    Divergencies in the compositions of phases from the Pt-Pd-Ni-S system, derived from electron probe micro-analysis and micro-PIXE analysis of thick samples have been investigated. Discrepancies stem from the different penetration and excitation processes of the two techniques. A specially prepared set of targets, of varying element ratios of Pt, Pd, Ni and S, were studied in a round robin analysis using three independent experimental facilities and analytical procedures. The results allow identification of the different phases, but the observed deviations can only partly be explained by software deficiencies.

  5. NMR shielding and spin-rotation constants in XCO (X = Ni, Pd, Pt) molecules

    Science.gov (United States)

    Demissie, Taye B.; Jaszuński, Michał; Malkin, Elena; Komorovský, Stanislav; Ruud, Kenneth

    2015-07-01

    Ab initio nonrelativistic and four-component relativistic DFT (density functional theory) methods are combined to study the spin-rotation and absolute nuclear magnetic resonance (NMR) shielding constants of group 10 transition metal monocarbonyls. Good agreement is obtained between the calculated and available experimental data for the spin-rotation constants and shielding spans for PdCO and PtCO. These data allow us to determine accurate absolute chemical shielding constants for all the nuclei, as well as for the unknown spin-rotation constants. We compare the four-component shielding constants with those obtained from the spin-orbit zeroth-order regular approximation, together with an assessment of the performance of different basis sets. For the first time, relativistically optimised basis sets for the heavy atoms used in the four-component calculations are shown to give converged results for both magnetic properties studied. We dedicate this article to the memory of Professor Nicholas C. Handy.

  6. One-pot synthesis of Pd@PtNi core-shell nanoflowers supported on the multi-walled carbon nanotubes with boosting activity toward oxygen reduction in alkaline electrolyte

    Science.gov (United States)

    Liu, Sa; Wang, Yan; Liu, Liwen; Li, Mengli; Lv, Wenjie; Zhao, Xinsheng; Qin, Zhenglong; Zhu, Ping; Wang, Guoxiang; Long, Zhouyang; Huang, Fangmin

    2017-10-01

    Pt-based nanocrystals with controlled morphologies and structures are one of most promising electrocatalysts for oxygen reduction reaction (ORR). Herein, a facile one-pot wet-chemical method is developed to synthesize Pd@PtNi core-shell nanoflowers (CSNFs) supported on the multi-walled carbon nanotubes (MWNCTs). Brij 58 is demonstrated as a structure-directing agent to generate the nanoflower and ascorbic acid acts as a reductant to form a core-shell structure. By tuning the molar ratio of Pd and Pt, Pd@PtNi/MWCNTs CSNFs show obviously improved ORR activity and durability in alkaline electrolyte compared with PtNi/MWCNTs nanoflowers and commercial Pt/C. The results illustrate that the core-shell structure and porous feature of nanoflower are both beneficial to the enhancement of the catalytic properties.

  7. 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.

  8. Search for unconventional superconductors among the YTE2Si2 compounds (TE = Cr, Co, Ni, Rh, Pd, Pt).

    Science.gov (United States)

    Pikul, Adam P; Samsel-Czekala, Malgorzata; Chajewski, Grzegorz; Romanova, Tetiana; Hackemer, Alicja; Gorzelniak, Roman; Wiśniewski, Piotr; Kaczorowski, Dariusz

    2017-03-21

    Motivated by the recent discovery of exotic superconductivity in YFe2Ge2 we undertook reinvestigation of formation and physical properties of yttrium-based 1:2:2 silicides. Here we report on syntheses and crystal structures of the YTE2Si2 compounds with TE = Cr, Co, Ni, Rh, Pd, and Pt, and their low-temperature physical properties measurements, supplemented by results of fully relativistic FPLO band structure calculations. We confirm that most of the members of that family crystallize in a tetragonal ThCr2Si2-type structure (space group I4/mmm) and have three-dimensional Fermi surface, while only one of them (YPt2Si2) forms with a closely-related primitive CaBe2Ge2-type unit cell (space group P4/nmm) and possess quasi-two-dimensional Fermi surface sheets. Physical measurements indicated that BCS-like superconductivity is observed only in YPt2Si2 (Tc = 1.54 K) and YPd2Si2 (Tc = 0.43 K), while no superconducting phase transition was found in other systems at least down to 0.35 K. Thermal analysis showed no polymorphism in both superconducting phases. No clear relation between the superconductivity and the crystal structure (and dimensionality of the Fermi surface) was observed.

  9. Synthesis, crystal structure and physical properties of EuTGe{sub 3} (T = Co, Ni, Rh, Pd, Ir, Pt) single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Bednarchuk, Oleksandr; Gągor, Anna; Kaczorowski, Dariusz, E-mail: D.Kaczorowski@int.pan.wroc.pl

    2015-02-15

    Highlights: • Single crystals of EuTGe{sub 3} (T = Co, Ni, Rh, Pd, Ir, Pt) compounds were prepared. • The crystal structures were refined from single-crystal X-ray diffraction data. • The physical properties of oriented single crystals were determined. • For each compound, an antiferromagnetic ordering was found at low temperatures. - Abstract: Single crystals of six EuTGe{sub 3} compounds with T = Co, Ni, Rh, Pd, Ir and Pt were prepared by high-temperature solution growth method. Their crystal structures of the BaNiSn{sub 3}-type were refined from single-crystal X-ray diffraction data. The physical properties of oriented single-crystalline specimens were studied by means of magnetic susceptibility, heat capacity and electrical resistivity measurements. For each compound, an antiferromagnetic ordering was found to set in at low temperatures due to localized magnetic moments carried on divalent Eu ions. Despite the same crystal structure, the EuTGe{sub 3} compounds exhibit diverse magnetic structures with different directions of the ordered magnetic moments and a variety of dissimilar mutual arrangements of adjacent spins.

  10. Partition coefficients for Ni, Cu, Pd, Pt, Rh, and Ir between monosulfide solid solution and sulfide liquid and the formation of compositionally zoned Ni-Cu sulfide bodies by fractional crystallization of sulfide liquid

    DEFF Research Database (Denmark)

    Barnes, S.J.; Makovicky, E.; Makovicky, M.

    1996-01-01

    Many nickel–copper sulfide orebodies contain Cu- and Fe-rich portions. The Fe-rich ore is generally richer in Os, Ir, Ru, and Rh and poorer in Pt, Pd, and Au than the Cu-rich ore. In komatiite-hosted ores Ni tends to be concentrated in the Cu-rich ore, whereas in tholeiitic ores it tends to be co...

  11. Room temperature biogenic synthesis of multiple nanoparticles (Ag, Pd, Fe, Rh, Ni, Ru, Pt, Co, and Li) by Pseudomonas aeruginosa SM1

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, Sarvesh Kumar; Constanti, Magda, E-mail: magdalena.constanti@urv.cat [Universitat Rovira i Virgili, Departament d' Enginyeria Quimica (Spain)

    2012-03-15

    Room temperature biosynthesis of Ag, Pd, Fe, Rh, Ni, Ru, Pt, Co, and Li nanoparticles was achieved using Pseudomonas aeruginosa SM1 without the addition of growth media, electron donors, stabilizing agents, preparation of cell/cell-free extract or temperature, and pH adjustments. The resulting nanoparticles were characterized by Transmission electron microscopy and X-ray diffraction. It was observed that P. aeruginosa SM1 is capable of producing both intracellular (Co and Li) and extracellular (Ag, Pd, Fe, Rh, Ni, Ru, and Pt) nanoparticles in both crystalline and amorphous state. The FT-IR spectra clearly showed the presence of primary and secondary amines which may be responsible for the reduction and subsequent stabilization of the resulting extracellular nanoparticles which were obtained as a one-step process. This suggests toward an unknown 'selection mechanism' that reduces certain metal ions and allows others to enter the cell membrane. Finally, in this first of its kind study, single strain of bacteria was used to produce several different mono-metallic nanoparticles.

  12. Room temperature biogenic synthesis of multiple nanoparticles (Ag, Pd, Fe, Rh, Ni, Ru, Pt, Co, and Li) by Pseudomonas aeruginosa SM1

    Science.gov (United States)

    Srivastava, Sarvesh Kumar; Constanti, Magda

    2012-03-01

    Room temperature biosynthesis of Ag, Pd, Fe, Rh, Ni, Ru, Pt, Co, and Li nanoparticles was achieved using Pseudomonas aeruginosa SM1 without the addition of growth media, electron donors, stabilizing agents, preparation of cell/cell-free extract or temperature, and pH adjustments. The resulting nanoparticles were characterized by Transmission electron microscopy and X-ray diffraction. It was observed that P. aeruginosa SM1 is capable of producing both intracellular (Co and Li) and extracellular (Ag, Pd, Fe, Rh, Ni, Ru, and Pt) nanoparticles in both crystalline and amorphous state. The FT-IR spectra clearly showed the presence of primary and secondary amines which may be responsible for the reduction and subsequent stabilization of the resulting extracellular nanoparticles which were obtained as a one-step process. This suggests toward an unknown "selection mechanism" that reduces certain metal ions and allows others to enter the cell membrane. Finally, in this first of its kind study, single strain of bacteria was used to produce several different mono-metallic nanoparticles.

  13. 1H, 1H, 2H, 2H-Perfluoroalkyl-Functionalization of Ni(II), Pd(II) and Pt(II) Mono- and Diphosphine Complexes : minimizing the Electronic Consequences for the Metal Center

    NARCIS (Netherlands)

    Koten, G. van; Wolf, E. de; Mens, A.J.M.; Gijzeman, O.L.J.; Lenthe, J.H. van; Jenneskens, L.W.; Deelman, B.J.

    2003-01-01

    A series of fluorous derivatives of group 10 complexes MCl2(dppe) and [M(dppe)2](BF4)2 (M = Ni, Pd or Pt; dppe = 1,2-bis(diphenylphosphino)ethane) and cis-PtCl2(PPh3)2 was synthesized. The influence of para-(1H,1H,2H,2H-perfluoroalkyl)dimethylsilyl-functionalization of the phosphine phenyl groups of

  14. The Dewar-Chatt-Duncanson model reversed Bonding analysis of group-10 complexes [(PMe3)2M-EX3] (M = Ni, Pd, Pt;; E = B, Al, Ga, In, Tl;; X = H, F, Cl, Br, I)

    National Research Council Canada - National Science Library

    Haunschild, Robin; Hillebrecht, Pierre; Goedecke, Catharina; Uhlemann, Till; Frenking, Gernot

    2009-01-01

    ...-acceptor complexes [(PMe 3 ) 2 M-EX 3 ] with X = H, F, Cl, Br, I;; E = B, Al, Ga, In, Tl; and M = Ni, Pd, Pt. The nature of the metal-ligand bond was investigated with an energy decomposition analysis...

  15. Coexistence of magnetic order, heavy fermion and intermediate valence behaviour in Ce{sub 7}X{sub 3} (X=Ni, Ru, Pd, Pt, Ir and Rh)

    Energy Technology Data Exchange (ETDEWEB)

    Trovarelli, O. [Comision Nacional de Energia Atomica, San Carlos de Bariloche (Argentina). Centro Atomico Bariloche; Sereni, J.G. [Comision Nacional de Energia Atomica, San Carlos de Bariloche (Argentina). Centro Atomico Bariloche; Schmerber, G. [IPCMS-GEMM, 23 rue du Loess, 67037 Strasbourg (France); Kappler, J.P. [IPCMS-GEMM, 23 rue du Loess, 67037 Strasbourg (France)

    1995-02-01

    Low temperature specific heat, AC magnetic susceptibility and magnetization measurements were performed on the Ce{sub 7}X{sub 3} compounds (X=Ni, Ru, Rh, Pd, Ir and Pt). They exhibit coexistence of magnetic order (MO), heavy fermion (HF) and intermediate valence (IV) behaviour and the results are interpreted in terms of the three Ce sublattices (1Ce{sub I}, 3Ce{sub II} and 3Ce{sub III}) present in the Th{sub 7}Fe{sub 3}-type structure. From entropic considerations it is found that sublattice Ce{sub III} presents an IV behaviour in all these compounds and Ce{sub II} show MO or have a HF behaviour depending on the Ce-ligand electronic structure. The Ce{sub I} atoms (more than 6A distant from each other) exhibit MO only when the Ce{sub II} sublattice provides a high density of electronic states. ((orig.)).

  16. Characterization of Ni19.5Ti50.5Pd25Pt5 High-Temperature Shape Memory Alloy Springs and their Potential Application in Aeronautics

    Science.gov (United States)

    Stebner, Aaron; Padula, Santo A.; Noebe, Ronald D.

    2008-01-01

    Shape memory alloys (SMAs) have been used as actuators in many different industries since the discovery of the shape memory effect, but the use of SMAs as actuation devices in aeronautics has been limited due to the temperature constraints of commercially available materials. Consequently, work is being done at NASA's Glenn Research Center to develop new SMAs capable of being used in high temperature environments. One of the more promising high-temperature shape memory alloys (HTSMAs) is Ni19.5Ti50.5Pd25Pt5. Recent work has shown that this material is capable of being used in operating environments of up to 250 C. This material has been shown to have very useful actuation capabilities, demonstrating repeatable strain recoveries up to 2.5% in the presence of an externally applied load. Based on these findings, further work has been initiated to explore potential applications and alternative forms of this alloy, such as springs. Thus, characterization of Ni19.5Ti50.5Pd25Pt5 springs, including their mechanical response and how variations in this response correlate to changes in geometric parameters, are discussed. The effects of loading history, or training, on spring behavior were also investigated. A comparison of the springs with wire actuators is made and the benefits of using one actuator form as opposed to the other discussed. These findings are used to discuss design considerations for a surge-control mechanism that could be used in the centrifugal compressor of a T-700 helicopter engine.

  17. Characterization of Ni19.5Ti50.5Pd25Pt5 High-Temperature Shape Memory Alloy Springs and their Potential Application in Aeronautics

    Science.gov (United States)

    Stebner, Aaron; Padula, Santo A.; Noebe, Ronald D.

    2008-01-01

    Shape memory alloys (SMAs) have been used as actuators in many different industries since the discovery of the shape memory effect, but the use of SMAs as actuation devices in aeronautics has been limited due to the temperature constraints of commercially available materials. Consequently, work is being done at NASA's Glenn Research Center to develop new SMAs capable of being used in high temperature environments. One of the more promising high-temperature shape memory alloys (HTSMAs) is Ni19.5Ti50.5Pd25Pt5. Recent work has shown that this material is capable of being used in operating environments of up to 250 C. This material has been shown to have very useful actuation capabilities, demonstrating repeatable strain recoveries up to 2.5% in the presence of an externally applied load. Based on these findings, further work has been initiated to explore potential applications and alternative forms of this alloy, such as springs. Thus, characterization of Ni19.5Ti50.5Pd25Pt5 springs, including their mechanical response and how variations in this response correlate to changes in geometric parameters, are discussed. The effects of loading history, or training, on spring behavior were also investigated. A comparison of the springs with wire actuators is made and the benefits of using one actuator form as opposed to the other discussed. These findings are used to discuss design considerations for a surge-control mechanism that could be used in the centrifugal compressor of a T-700 helicopter engine.

  18. The adsorption of CO and NO on the MoS{sub 2} monolayer doped with Au, Pt, Pd, or Ni: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Dongwei, E-mail: dwmachina@126.com [School of Physics, Anyang Normal University, Anyang 455000 (China); Ju, Weiwei [College of Physics and Engineering, Henan University of Science and Technology, Luoyang 471023 (China); Li, Tingxian; Zhang, Xiwei [School of Physics, Anyang Normal University, Anyang 455000 (China); He, Chaozheng, E-mail: hecz2013@nynu.edu.cn [Physics and Electronic Engineering College, Nanyang Normal University, Nanyang 473061 (China); Ma, Benyuan [Physics and Electronic Engineering College, Nanyang Normal University, Nanyang 473061 (China); Lu, Zhansheng; Yang, Zongxian [College of Physics and Electronic Engineering, Henan Normal University, Xinxiang 453007 (China)

    2016-10-15

    Graphical abstract: The MoS{sub 2} monolayers doped with Au, Pt, Pd, or Ni show enhanced adsorption and sensitivity toward CO or NO molecule. - Highlights: • CO and NO adsorption on the doped MoS{sub 2} monolayers is theoretically studied. • CO and NO are chemisorbed on the doped MoS{sub 2} monolayers. • Charge transfer can be observed between the adsorbed molecule and the substrates. • Molecular adsorption can induce the change in electronic structures of the doped MoS{sub 2} monolayers. - Abstract: By performing the first-principles calculation, the adsorption of CO and NO molecules on the Au, Pt, Pd, or Ni doped MoS{sub 2} monolayer has been studied. The interaction between CO or NO with the doped MoS{sub 2} monolayer is strong and belongs to the chemisorption, as evidenced by the large adsorption energy and the short distance between the adsorbed molecules and the dopants. The charge transfer and the electronic property induced by the molecule adsorption are discussed. It is found that for both CO and NO adsorption, for all the cases charge transfer between the substrates and the adsorbed molecules has been observed. For NO, the adsorption obviously induces new impurity states in the band gap or the redistribution of the original impurity states. These can lead to the change of the transport properties of the doped MoS{sub 2} monolayer, by which the adsorbed CO or NO can be detected. The present work shows that introducing appropriate dopants may be a feasible method to improve the performance of MoS{sub 2}-based gas sensors.

  19. Fermi-liquid behavior of binary intermetallic compounds Y3 M (M  =  Co, Ni, Rh, Pd, Ir, Pt)

    Science.gov (United States)

    Strychalska-Nowak, Judyta; Wiendlocha, Bartłomiej; Hołowacz, Katarzyna; Reczek, Paula; Podgórski, Mateusz; Winiarski, Michał J.; Klimczuk, Tomasz

    2017-06-01

    A series of polycrystalline samples of Y3 M (M  =  Co, Ni, Rh, Pd, Ir, Pt), intermetallic binary compounds were synthesized by the arc-melting method. Powder x-ray diffraction (pXRD) confirmed the orthorhombic cementite-type crystal structure and allowed for the estimation of the lattice parameters. Physical properties were investigated by means of electrical resistivity and heat capacity measurements between 1.9 K and 300 K. All tested compounds show metallic-like behaviour with RRR values ranging from 1.3 to 8.3, and power-law ρ \\propto {{T}n} temperature dependence of resistivity was observed, with 1.6≤slant n≤slant 2.2 . No superconductivity was detected above 1.9 K. The Debye temperature, estimated from the low temperature heat capacity fit, ranged from 180 K (Y3Pt) to 222 K (Y3Co). The highest value of the Sommerfeld coefficient γ was found for Y3Pd (19.5 mJ mol-1 K-2). The pXRD pattern of Y3Rh indicated the presence of Y5Rh2, a previously unreported Pd5B2-type phase, whose unit cell parameters were refined using the LeBail method. Density functional theory calculations were performed and theoretical results revealed strong enhancement of the measured electronic specific heat, which was 30%-100% larger than computed. Quadratic temperature dependence of resistivity and enhanced electronic specific heat indicated a Fermi-liquid behavior of electrons in these materials.

  20. Separation Studies of Pd(II from Acidic Chloride Solutions of Pt(IV, Ni(II and Rh(III by Using 4-Aroyl-3-Phenyl-5-Isoxazolones

    Directory of Open Access Journals (Sweden)

    Koduru Janardhan Reddy

    2012-01-01

    Full Text Available This study examined the effect influence of various factors on the extraction of Pd(II to develop a new liquid-liquid extraction mechanism for the selective separation of palladium(II from its acidic chloride solutions using 4-aroyl-3-phenyl-5-isoxazolones (HA, such as 3-phenyl-4-(4-fluorobenzoyl-5- isoxazolone (HFBPI, 3-phenyl-4-benzoyl-5-isoxazolone (HPBI and 3-phenyl-4- (4-toluoyl-5-isoxazolone (HTPI. The extraction strength of Pd(II with HA were in the following order: HFBPI > HPBI > HTPI, which is opposite to that observed with their pKa values. HPBI was used to separate Pd(II from Pt(IV, Ni(II and Rh(III metal ions and calculated their separation factors (S.F. were followed in the order: Pd/Ni (40±0.4 > Pd/Pt (25±0.2 > Pd/Rh (15±0.3 > Rh/Ni (2.7±0.3 > Pt/Ni ≈ Rh/Pt (1.7±0.2. The loading and striping of Pd(II (1.12×10-4 mol L-1 were also examined using 1.0×10-3 mol L-1 HPBI in CHCl3 and 1.0 mol L-1 HCl, respectively. The results demonstrated that the maximum (97.5% extraction and desorption (89% of metal required at least 3.0 cycles. The developed method was applied successfully to the separation of palladium from synthetic water samples.

  1. Self-consistent linear-muffin-tin-orbitals coherent-potential technique for bulk and surface calculations: Cu-Ni, Ag-Pd, and Au-Pt random alloys

    DEFF Research Database (Denmark)

    Abrikosov, I. A.; Skriver, Hans Lomholt

    1993-01-01

    energies and work functions for three fcc-based alloys (Cu-Ni, Ag-Pd, and Au-Pt) over the complete concentration range. The calculated mixing enthalpies for the Ag-Pd and Au-Pt systems agrees with experimental values, and the calculated concentration dependence of the lattice parameters agrees...... with experiment for all three systems. We find that the calculated surface energies and work functions in the unsegregated case exhibit a small positive deviation from a linear concentration dependence. Finally, we performed a segregation analysis based on the calculated surface energies by means of a simple...

  2. ESTUDIO EXPERIMENTAL Y SUPRAMOLECULARES DE Ni, Pd Y Pt, AUTOENSAMBLADOS COMPUTACIONAL DE POLÍGONOS CON 4,4´-BIPIRIDINA.

    Directory of Open Access Journals (Sweden)

    Paulo C Torres

    2013-12-01

    Full Text Available Los polígonos y poliedros supramoleculares presentan diversas y  novedosas aplicaciones como nanoreactores, en química de inclusión, nanosensores moleculares, entre otras. En este trabajo se presenta la síntesis, caracterización y comparación de polígonos supramoleculares autoensamblados entre complejos de tipo [M(dppe(TOF2], con centros metálicos de un mismo grupo (M = Ni, Pd y Pt y la molécula orgánica 4,4'-bipiridina. Los análisis realizados por Uv-vis, FT-IR, Raman, 1H-, 31P-, 1H COSY- y 19F- RMN, demostraron que el complejo que contiene níquel formó únicamente un cuadrado, mientras que los complejos que contienen paladio y platino presentaron un equilibrio triángulo-cuadrado. Además se realizaron cálculos PM6 para los complejos supramoleculares, considerando sistemas catíonicos y neutros, tanto en fase gaseosa como en disolución. Los resultados muestran que para los tres metales, sin importar el medio, se ve favorecida energéticamente la formación de cuadrados en comparación con la formación de triángulos. Además, se observa que los centros de Ni favorecen más la formación de cuadrados, mientras que los centros de Pd la favorecen menos. Las tendencias teóricas se encuentran en concordancia con los resultados experimentales.

  3. Phase stabilities of pyrite-related MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te): A systematic DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Bachhuber, Frederik [University of Regensburg, Institute of Inorganic Chemistry, Universitätsstr. 31, 93040 Regensburg (Germany); School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland (New Zealand); Krach, Alexander; Furtner, Andrea [University of Regensburg, Institute of Inorganic Chemistry, Universitätsstr. 31, 93040 Regensburg (Germany); Söhnel, Tilo [School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland (New Zealand); Centre for Theoretical Chemistry and Physics, The New Zealand Institute for Advanced Study, Massey University Auckland, Auckland (New Zealand); Peter, Philipp; Rothballer, Jan [University of Regensburg, Institute of Inorganic Chemistry, Universitätsstr. 31, 93040 Regensburg (Germany); Weihrich, Richard, E-mail: richard.weihrich@chemie.uni-r.de [University of Regensburg, Institute of Inorganic Chemistry, Universitätsstr. 31, 93040 Regensburg (Germany)

    2015-03-15

    Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine their stabilities, competing binary MT{sub 2} and MCh{sub 2} boundary phases are taken into account as well as ternary M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs{sub 2} type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units that are isoelectronic and structurally related to pyrite (FeS{sub 2}). - Highlights: • Study of compositional stability of MTCh vs. M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} compounds. • Study of structural stability of known and novel MTCh compounds. • Prediction of novel stable and metastable structures and compounds isoelectronic to pyrite, FeS{sub 2}.

  4. Laser synthesis of bimetallic nanoalloys in the vapor and liquid phases and the magnetic properties of PdM and PtM nanoparticles (M = Fe, Co and Ni).

    Science.gov (United States)

    Abdelsayed, Victor; Glaspell, Garry; Nguyen, Minh; Howe, James M; El-Shall, M Samy

    2008-01-01

    In this work, we present several examples of the synthesis and characterization of bimetallic nanoparticle alloys using the Laser Vaporization Controlled Condensation (LVCC) method. In the first example, the vapor phase synthesis of Au-Ag, Au-Pd, and Au-Pt nanoparticle alloys are presented. The formation of nanoalloys is concluded from the observation of one plasmon absorption band at a wavelength that varies linearly with the gold mole fraction in the nanoalloy. Both XRD data and HRTEM-EDX data confirm the formation of nanoparticle alloys and not simply mixtures of the two metal nanoparticles. Irradiation of a mixture of Au/Ag nanoparticles dispersed in water with the 532 nm unfocused laser results in efficient alloying while the 1064 nm laser radiation results only in evaporation and size reduction of the unalloyed nanoparticles. Selective absorption of the femtosecond 780 nm radiation by large Au aggregates results in the formation of smaller aggregates with fractal structures, and no evidence for the Au-Ag alloy formation. The synthesis of palladium and platinum nanoparticles alloyed with transition metals such as iron and nickel using the LVCC method is also presented. The alloyed nanoparticles (FePd, FePt, NiPd, NiPt, and FeNi) are found to be superparamagnetic.

  5. Ni(II), Pd(II) and Pt(II) complexes of (1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol. Structural, spectroscopic, biological, cytotoxicity, antioxidant and DNA binding

    Science.gov (United States)

    Gaber, M.; El-Ghamry, H. A.; Fathalla, S. K.

    2015-03-01

    Metal complexes of the general formula [ML(H2O)Cl]nH2O; n = 1 for M = Ni and Pt and n = 2 for M = Pd, L = Schiff base (HL) derived from the condensation of 3-amino-1,2,4-triazole and 2-hydroxy-1-naphthaldehyde, were prepared. The synthesized ligand and its metal complexes were characterized on the basis of elemental analyses, spectral and magnetic studies as well as thermal analysis. The IR spectra revealed that the ligand is coordinated to the metal ions in bidentate manner via the N-atom of the azomethine group and the phenolic OH group. Square planar geometry was proposed for Pd(II) and Pt(II) complexes and tetrahedral for Ni(II) complex. The ligand and its metal complexes were screened against the sensitive organisms Escherichia coli as Gram-negative bacteria, Staphylococcus aureus as Gram-positive bacteria, Aspergillus flavus and Candida albicans as fungi. Moreover, the anticancer activity of the ligand and its metal complexes was evaluated in liver carcinoma (HEPG2) cell line. The results obtained indicated that the Schiff base ligand is more effective than its metal complexes towards the tested cell line. Ni(II), Pd(II) and Pt(II) complexes as well as the free Schiff base ligand were tested for their antioxidant activities. The DNA-binding properties of the studied complexes have been investigated by electronic absorption and viscosity measurements.

  6. The adsorption of CO and NO on the MoS2 monolayer doped with Au, Pt, Pd, or Ni: A first-principles study

    Science.gov (United States)

    Ma, Dongwei; Ju, Weiwei; Li, Tingxian; Zhang, Xiwei; He, Chaozheng; Ma, Benyuan; Lu, Zhansheng; Yang, Zongxian

    2016-10-01

    By performing the first-principles calculation, the adsorption of CO and NO molecules on the Au, Pt, Pd, or Ni doped MoS2 monolayer has been studied. The interaction between CO or NO with the doped MoS2 monolayer is strong and belongs to the chemisorption, as evidenced by the large adsorption energy and the short distance between the adsorbed molecules and the dopants. The charge transfer and the electronic property induced by the molecule adsorption are discussed. It is found that for both CO and NO adsorption, for all the cases charge transfer between the substrates and the adsorbed molecules has been observed. For NO, the adsorption obviously induces new impurity states in the band gap or the redistribution of the original impurity states. These can lead to the change of the transport properties of the doped MoS2 monolayer, by which the adsorbed CO or NO can be detected. The present work shows that introducing appropriate dopants may be a feasible method to improve the performance of MoS2-based gas sensors.

  7. Surface Segregation in Supported Pd-Pt Nanoclusters and Alloys

    NARCIS (Netherlands)

    van den Oetelaar, L.C.A.; Nooij, O.W.; Oerlemans, S.; Denier van der Gon, A.W.; Brongersma, H.H.; Lefferts, Leonardus; Roosenbrand, A.G.; van Veen, J.A.R.

    1998-01-01

    Surface segregation processes in Pd-Pt alloys and bimetallic Pd-Pt nanoclusters on alumina and carbon supports (technical catalysts) have been investigated by determining the metal surface composition of these systems by low-energy ion scattering (LEIS). Both Pd-rich (Pd80Pt20) and Pt-rich

  8. Effect of Pt coverage in Pt-deposited Pd nanostructure electrodes on electrochemical properties

    Energy Technology Data Exchange (ETDEWEB)

    Park, Ah-Reum; Lee, Young-Woo; Kwak, Da-Hee; Park, Kyung-Won [Soongsil University, Seoul (Korea, Republic of)

    2015-06-15

    We have fabricated Pt-deposited Pd electrodes via a two-gun sputtering deposition system by separately operating Pd and Pt target as a function of sputtering time of Pt target. For Pt-deposited Pd electrodes (Pd/Pt-X), Pd were first deposited on the substrates at 20 W for 5min, followed by depositing Pt on the Pd-only electrodes as a function of sputtering time (X=1, 3, 5, 7, and 10min) at 20W on the Pt target. As the sputtering time of Pt target increased, the portion of Pt on the Pd electrodes increased, representing an increased coverage of Pt on the Pd electrodes. The Pd/Pt-7 electrode having an optimized Pt coverage exhibits an excellent electrocatalytic activity for methanol oxidation reaction.

  9. Amorphous Pt@PdCu/CNT Catalyst for Methanol Electrooxidation ...

    African Journals Online (AJOL)

    A multi-walled carbon nanotube-supported, Pt decorated nano-sized ... alloy cores (denoted as Pt@PdCu/CNT) catalyst with lower Pt loading is synthesized via a ... The electrochemical activity of the Pt@PdCu/CNT catalyst is tested by cyclic ...

  10. Synthesis and composition evolution of bimetallic Pd Pt alloy nanoparticles

    Science.gov (United States)

    Ren, Guoqiang; Shi, Honglan; Xing, Yangchuan

    2007-09-01

    This paper reports a study on the synthesis of Pd-Pt alloy nanoparticles and composition evolution of the alloys. The synthesis involves Pd and Pt acetylacetonate as the metal precursors and trioctylphosphine (TOP) as the solvent. Thermal decomposition of the Pd-TOP complex resulted in Pd nanoparticles, while substitution of Pt in the Pt-TOP complex by Pd allowed formation of the Pd-Pt alloys. It was observed that the Pd-Pt nanoparticles formed at the very beginning in the synthesis process are Pd rich with various nanoparticle sizes ranging from 1.5 to 25 nm in diameter. These nanoparticles averaged out through a digestive ripening process and reached a final size of 3.5 nm in about 10 min. The alloy compositions evolved throughout the synthesis process and only reached the preset Pd to Pt ratio of the precursors in 120 min. It was found that Pt acetylacetonate alone in TOP cannot produce Pt nanoparticles, which was attributed to the formation of a Pt-TOP complex and a strong coordination of Pt to the phosphine. This observation led us to propose an atomic exchange process between the Pt-TOP complex and the Pd atoms at the nanoparticle surface. As a result, the alloy formation process is limited by a substitution and diffusion rate of the Pt atoms at the surface of the alloy nanoparticles.

  11. Magnesium and cadmium in covalently bonded networks. Synthesis and structure of AETMg and AETCd (AE = Ca, Sr; T = Pd, Ag, Pt, Au) with TiNiSi type structure and the solid solution Yb{sub 2-x}PtMg{sub x}

    Energy Technology Data Exchange (ETDEWEB)

    Kersting, Marcel; Johnscher, Michael; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2013-07-01

    The equiatomic intermetallic compounds AETMg and AETCd (AE = Ca, Sr; T = Pd, Ag, Pt, Au) and the whole solid solution Yb{sub 2-x}PtMg{sub x} were synthesized from the elements in sealed niobium tubes in a high-frequency or a muffle furnace. All samples were characterized on the basis of their powder X-ray diffraction patterns. The structures of SrAuCd, CaPdCd, CaPtCd, CaPdMg, SrPtMg, CaAg{sub 1.017}Mg{sub 0.983}, SrAg{sub 1.032}Mg{sub 0.968}, and Yb{sub 1.792}PtMg{sub 0.208} were refined on the basis of single-crystal X-ray diffractometer data. Some of the crystals showed small homogeneity ranges. All compounds crystallize with the orthorhombic TiNiSi type structure, space group Pnma. The crystal chemistry is briefly discussed and variations in chemical bonding as a result of the electronegativity of the transition metal are described. (orig.)

  12. Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphyhaline

    Science.gov (United States)

    Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

    2015-02-01

    Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, 1H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ).

  13. Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline.

    Science.gov (United States)

    Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

    2015-02-25

    Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, (1)H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ).

  14. Synthesis and Characterization of New Schiff Bases Derived from N (1-Substituted Isatin with Dithiooxamide and Their Co(II, Ni(II, Cu(II, Pd(II, and Pt(IV Complexes

    Directory of Open Access Journals (Sweden)

    Ahlam J. Abdul-Ghani

    2009-01-01

    Full Text Available Three new Schiff bases of N-substituted isatin LI, LII, and LIII = Schiff base of N-acetylisatin, N-benzylisatin, and N-benzoylisatin, respectively, and their metal complexes C1a,b=[Co2(LI2Cl3]Cl, C2=[Ni(LI2Cl2]0.4BuOH, C3=[CuLICl(H2O]Cl⋅0.5BuOH, C4=[Pd(LI2Cl]Cl, C5=[Pt(L12Cl2]Cl2⋅1.8EtOH.H2O, C6a=[CoLIICl]Cl⋅0.4H2O⋅0.3DMSO, C6b=[CoLIICl]Cl⋅0.3H2O⋅0.1BuOH,C7=[NiLIICl2], C8=[CuLII]Cl2⋅H2O00000, C9=[Pd(LII2]Cl2, C10=[Pt(LII2.5Cl]Cl3, C11a=[Co(LIII]C12⋅H2O, C11b=[Co(LIII]Cl2⋅0.2H2O, and C12=[Ni(LIII2]Cl2, C13=[Ni(LIII2]Cl2 were reported. The complexes were characterized by elemental analyses, metal and chloride content, spectroscopic methods, magnetic moments, conductivity measurements, and thermal studies. Some of these compounds were tested as antibacterial and antifungal agents against Staphylococcus aureus, Proteus vulgaris, Candida albicans, and Aspergillus niger.

  15. Intermetallic compounds of the heaviest elements and their homologs: The electronic structure and bonding of MM', where M =Ge, Sn, Pb, and element 114, and M'=Ni, Pd, Pt, Cu, Ag, Au, Sn, Pb, and element 114

    Science.gov (United States)

    Pershina, V.; Anton, J.; Fricke, B.

    2007-10-01

    Fully relativistic (four-component) density-functional theory calculations were performed for intermetallic dimers MM', where M =Ge, Sn, Pb, and element 114, and M'=group 10 elements (Ni, Pd, and Pt) and group 11 elements (Cu, Ag, and Au). PbM and 114M, where M are group 14 elements, were also considered. The results have shown that trends in spectroscopic properties—atomization energies De, vibrational frequencies ωe, and bond lengths Re, as a function of M', are similar for compounds of Ge, Sn, Pb, and element 114, except for De of PbNi and 114Ni. They were shown to be determined by trends in the energies and space distribution of the valence ns(M ') atomic orbitals (AOs). According to the results, element 114 should form the weakest bonding with Ni and Ag, while the strongest with Pt due to the largest involvement of the 5d(Pt) AOs. In turn, trends in the spectroscopic properties of MM' as a function of M were shown to be determined by the behavior of the np1/2(M ) AOs. Overall, De of the element 114 dimers are about 1eV smaller and Re are about 0.2a.u. larger than those of the corresponding Pb compounds. Such a decrease in bonding of the element 114 dimers is caused by the large SO splitting of the 7p orbitals and a decreasing contribution of the relativistically stabilized 7p1/2(114) AO. On the basis of the calculated De for the dimers, adsorption enthalpies of element 114 on the corresponding metal surfaces were estimated: They were shown to be about 100-150kJ/mol smaller than those of Pb.

  16. Reaction of bis(o-phosphinophenyl)silane with M(PPh3)4 (M = Ni, Pd, Pt): synthesis and structural analysis of η2-(Si-H) metal(0) and pentacoordinate silyl metal(II) hydride complexes of the Ni triad bearing a PSiP-pincer ligand.

    Science.gov (United States)

    Takaya, Jun; Iwasawa, Nobuharu

    2011-09-21

    Reactions of bis(o-(diphenylphosphino)phenyl)methylsilane with M(PPh(3))(4) (M = Ni, Pd, Pt) were investigated. When M = Ni or Pd, synthesis and isolation of η(2)-(Si-H) complexes of mononuclear Ni(0) and Pd(0) were achieved for the first time as frozen intermediates for oxidative addition of the Si-H bond. Structural analysis by X-ray and NMR spectroscopy disclosed that their η(2)-(Si-H) structures were maintained in both solid and solution states and coordination of the Si-H bond to the metal center was relatively weak. On the other hand, reaction with a platinum(0) complex afforded two kinds of pentacoordinate silyl platinum(II) hydride complexes having a PSiP-pincer ligand, which underwent unique thermal isomerization from a square-pyramidal cis-H-Pt-Si to a trigonal-bipyramidal trans-H-Pt-Si isomer. Mechanistic investigations revealed that this isomerization proceeded via an intramolecular rearrangement process probably through a turnstile rotation.

  17. Synthesis, characterization and anticancer studies of Ni(II), Pd(II) and Pt(II) complexes with Schiff base derived from N-methylhydrazinecarbothioamide and 2-hydroxy-5-methoxy-3-nitrobenzaldehyde

    Science.gov (United States)

    Arafath, Md. Azharul; Adam, Farook; Razali, Mohd. R.; Ahmed Hassan, Loiy E.; Ahamed, Mohamed B. Khadeer; Majid, Amin Malik S. A.

    2017-02-01

    A carbothioamide NSO tridentate Schiff base ligand (HL) and its square planar complexes Na[NiLOAc], Na[PdLOAc] and [PtLdmso] have been synthesized and characterized on the basis of melting point, elemental analysis, FT-IR, 1H NMR, 13C NMR, UV-Vis spectra. The structure of HL was elucidated with X-ray diffraction analysis. In the present study, the synthesized compounds were evaluated for their anticancer properties against three human cancer cell lines breast cancer (MCF-7), cervical (Hela), and colon (HCT-116). In addition, the cytotoxicity of the synthesized compounds was tested on a normal human cell line (human endothelial cell line EA.hy926). Among the tested compounds, the complex [NiLOAc] excelled in halting proliferation of the cervical and colon cancer cells with median inhibitory concentration (IC50) values of 28.33 and 34.4 μM, respectively. The complex, [PdLOAc] demonstrated selective cytotoxicity against breast cancer line MCF-7 with IC50 = 47.5 μM, while HL showed inhibitory effect against colon cancer cell line (HCT-116) with IC50 = 55.66 μM. The complex, [PtLdmso] showed mild activity against breast cancer (MCF-7) and cervical cancer (Hela) cells with IC50 = 64.44 and 68.3 μM, respectively, whereas, it displayed insignificant cytotoxicity against human endothelial cells (EA.hy926) with IC50 > 200 μM. Cancer cells treated with [NiLOAc] showed apoptotic features such as membrane blebbing and DNA condensation. Thus, the findings of the present study demonstrated that the series of metal complexes of HL could form the new lead for development of cancer chemotherapies to treat human cervical, breast and colon malignancies.

  18. Synthesis of Supported NiPt Bimetallic Nanoparticles, Methods for Controlling the Surface Coverage of Ni Nanoparticles With Pt, Methods Of Making NiPt Multilayer Core-Shell Structures and Application of the Supported Catalysts for CO2 Reforming

    KAUST Repository

    Li, Lidong

    2015-06-25

    Embodiments of the present disclosure provide for supported Ni/Pt bimetallic nanoparticles, compositions including supported NiPt nanoparticles, methods of making supported NiPt nanoparticles, methods of using supported NiPt nanoparticles, and the like.

  19. A comparative study of Pt and Pt-Pd core-shell nanocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Long, Nguyen Viet, E-mail: nguyenviet_long@yahoo.com [Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Posts and Telecommunications Institute of Technology, km 10 Nguyen Trai, Thanh Xuan, Ha Dong, Hanoi (Viet Nam); Laboratory for Nanotechnology, Vietnam National University, Ho Chi Minh, Linh Trung, Thu Duc, Ho Chi Minh (Viet Nam); Department of Molecular and Material Sciences, Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasugakouen, Kasuga, Fukuoka 816-8580 (Japan); Ohtaki, Michitaka [Department of Molecular and Material Sciences, Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasugakouen, Kasuga, Fukuoka 816-8580 (Japan); Hien, Tong Duy [Laboratory for Nanotechnology, Vietnam National University, Ho Chi Minh, Linh Trung, Thu Duc, Ho Chi Minh (Viet Nam); Randy, Jalem [Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Nogami, Masayuki, E-mail: nogami@nitech.ac.jp [Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan)

    2011-10-30

    Highlights: > The syntheses of Pt (4-8 nm) and Pt-Pd core-shell nanoparticles (15-25 nm) are showed. > Pt-Pd core-shell catalysts possess catalytic property much better than Pt catalysts. > Pt-Pd core-shell catalysts exhibit fast and highly stable catalytic activity. > Fascinatingly, size effect is not as really important as nanostructuring effect. > Fast, stable, sensitive hydrogen adsorption is very crucial for fuel cells. - Abstract: This comparative study characterizes two types of metallic and core-shell bimetallic nanoparticles prepared with our modified polyol method. These nanoparticles consist of Pt and Pt-Pd core-shell nanocatalysts exhibiting polyhedral morphologies. The controlled syntheses of Pt metallic nanoparticles in the 10-nm regime (4-8 nm) and Pt-Pd bimetallic core-shell nanoparticles in the 30-nm regime (15-25 nm) are presented. To realize our ultimate research goals for proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs), we thoroughly investigate the dependence of the electrocatalytic properties of the nanoparticles on the structure, size and morphology. Significant differences in the electrocatalysis are also explained in experimental evidences of both Pt and Pt-Pd nanocatalysts. We suggested that the core-shell controlled morphologies and nanostructures of the Pd nanoshell as the Pd atomic monolayers will not only play an important role in producing inexpensive, novel Pt- and Pd-based nanocatalysts but also in designing more efficient Pt- and Pd-based nanocatalysts for practical use in DMFC technology. Our comparative results show that Pt-Pd nanocatalysts with Pd nanoshells exhibited much better electrocatalytic activity and stabilization compared to Pt nanocatalysts. Interestingly, we found that the size effect is not as strong as the nanostructuring effect on the catalytic properties of the researched nanoparticles. A nanostructure effect of the core-shell bimetallic nanoparticles was identified.

  20. Pt(Ⅱ), Pd(Ⅱ) and Ni(Ⅱ) Complexes Binding to the N(7) Position of Guanine: Influence on the Guanine and Watson-crick GC Base Pair

    Institute of Scientific and Technical Information of China (English)

    章志强; 周立新; 和芹; 赵亚英

    2005-01-01

    Comprehensive ab initio calculations were performed on the coordination of Pt(II), Pd(II) and Ni(II) adducts to the N(7) of guanine and guanine-cytosine (GC) base pair at the DFT level. The fully optimized geometries of the metal complexes were obtained and the stabilization energies of the interaction between metal adducts and nucleobase were calculated with B3LYP method by using 6-31* basis set for the light atom. While the effective core potential (ECP) is used for metal cation. The results show that both cispalladium and cisnickel cause similar geometric changes of the base pair as cisplatin. For the coordination of metal adducts to guanine, platinum adduct possesses the highest stabilization energy; but the interaction between metal-guanine and cytosine for nickel is larger than that for platinum and palladium. It is worthy to note that hydrolysis effect can also cause significant changes in H-bonds.

  1. SÍNTESE, PROPRIEDADES E INVESTIGAÇÃO ESTRUTURAL DE 1,3-DIARILTRIAZENOS E COMPLEXOS COM Ni(II), Pd(II), Pt(II) e Hg(II)

    OpenAIRE

    Lorenzo do Canto Visentin

    2006-01-01

    O estudo de complexos de coordenação com metais de transição, envolvendo pré-ligantes triazenos desperta interesse há muitas décadas. A síntese de moléculas derivadas do triazeno 1-3-diariltriazeno e seus complexos com Ni(II), Pd(II), (Pt)(II) e Hg(II) são tema de estudo neste trabalho. Triazenos são moléculas com pares de elétrons livres. Estes elétrons podem ser doados aos metais de transição formando complexos de coordenação. As estruturas dos compostos 3-(4-bromofenil)-1-(4-nitrofenil)tri...

  2. Elastic properties of antiperovskite-type Ni-rich nitrides MNNi 3 (M=Zn, Cd, Mg, Al, Ga, In, Sn, Sb, Pd, Cu, Ag and Pt) as predicted from first-principles calculations

    Science.gov (United States)

    Bannikov, V. V.; Shein, I. R.; Ivanovskii, A. L.

    2010-11-01

    We have performed accurate ab initio total energy calculations using the full-potential linearized augmented plane wave (FP-LAPW) method with the generalized gradient approximation (GGA) for the exchange-correlation potential to systematically investigate elastic properties of 12 synthesized and hypothetical cubic antiperovskite-type Ni-rich nitrides MNNi 3, where M are Zn, Cd, Mg, Al, Ga, In, Sn, Sb, Pd, Cu, Ag and Pt. As a result, the optimized lattice parameters, independent elastic constants ( Cij), bulk-, shear- and tetragonal shear moduli, Cauchy’s pressure and some indexes of elastic anisotropy, as well as the numerical estimations of Young’s modulus, Poisson’s ratio and Pugh's indicator of brittle/ductile behavior for the corresponding polycrystalline MNNi 3 (in the Voigt-Reuss-Hill approximation) were obtained and analyzed in comparison with the available theoretical and experimental data.

  3. Elastic properties of antiperovskite-type Ni-rich nitrides MNNi{sub 3} (M=Zn, Cd, Mg, Al, Ga, In, Sn, Sb, Pd, Cu, Ag and Pt) as predicted from first-principles calculations

    Energy Technology Data Exchange (ETDEWEB)

    Bannikov, V.V.; Shein, I.R. [Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences, 620990 Ekaterinburg (Russian Federation); Ivanovskii, A.L., E-mail: ivanovskii@ihim.uran.r [Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences, 620990 Ekaterinburg (Russian Federation)

    2010-11-15

    We have performed accurate ab initio total energy calculations using the full-potential linearized augmented plane wave (FP-LAPW) method with the generalized gradient approximation (GGA) for the exchange-correlation potential to systematically investigate elastic properties of 12 synthesized and hypothetical cubic antiperovskite-type Ni-rich nitrides MNNi{sub 3}, where M are Zn, Cd, Mg, Al, Ga, In, Sn, Sb, Pd, Cu, Ag and Pt. As a result, the optimized lattice parameters, independent elastic constants (C{sub ij}), bulk-, shear- and tetragonal shear moduli, Cauchy's pressure and some indexes of elastic anisotropy, as well as the numerical estimations of Young's modulus, Poisson's ratio and Pugh's indicator of brittle/ductile behavior for the corresponding polycrystalline MNNi{sub 3} (in the Voigt-Reuss-Hill approximation) were obtained and analyzed in comparison with the available theoretical and experimental data.

  4. Theoretical study of the structure, bonding and electronic behaviour of sandwich complexes [M3(C7H7)2X3]- (M = Ni, Pd, Pt; X = F, Cl)

    Science.gov (United States)

    Zhou, Ke; Min, Suotian; Xue, Ganglin; Huang, Wendeng

    2014-08-01

    The correlations between the structural and electronic properties of the clusters [M3X3]3- and sandwich complexes [M3(C7H7)2X3]- (where M = Ni, Pd, Pt; X = F, Cl) were studied with density functional theory (B3PW91). All of the sandwich complexes are donating and back-donating metal-ligand bonding structures. The influence of the ligand, significant variations in the Msbnd C, Msbnd X, Msbnd M, Csbnd C bond lengths and binding energies were examined to obtain qualitative and quantitative pictures of the intramolecular C7R7+-M3X33- interactions. Our theoretical investigations show that the binding energies of the sandwich complexes gradually reduce from Ni to Pt, as well as from F to Cl. Meanwhile, the geometric and electronic structures and the relative stabilities have a strong relation to each other. S1). 7-B-(H-10) is a delocalised σ orbital, which has contributions from Pt (15% s orbital of each Pt, 8% d orbital of each Pt), and there is little contribution from Cl (Table S2). 7-C-(H-11) is a delocalised π orbital, which mainly involves contribution from Pt (25% dxz and dyz of each Pt) and Cl (8.5% pz of each Cl) (Table S3). 7-D-(H-14) is a delocalised σ orbital, which is mostly composed of d orbitals (14% for each Pt) and p orbitals (16% for each Cl) (Table S4). Pt s (10%) and d (10%) orbitals mainly participate in the formations of 7-E-(H-23), and there is a 13% p orbital contribution from each Cl (Table S5). For structure 13, the LUMO is mainly s orbitals of C, and there is some contribution from the s and d orbitals of Pt (Table S6), whereas the HOMO is mainly s orbitals of C (Table S7). 13-c-(H-14) is mainly the dxz and dyz orbitals of Pt (Table S8).NICS can be used to predict and understand some of the properties of a molecule, especially its stability due to aromatic stabilisation, which is based on the negative of the magnetic shielding computed at or above the geometrical centres of rings or clusters. Systems with negative NICS values are aromatic

  5. Theoretical Study of CO Adsorption on Ni(111), Pt(111) and Pt/Ni(111) Surfaces

    Science.gov (United States)

    Cabeza, G. F.; Castellani, N. J.; Légaré, P.

    CO adsorption on a pseudomorphic Pt overlayer supported by Ni(111) has been studied with the use of extended Huckel calculations. Experimental information on the pure Pt(111) and Ni(111) single crystals was employed to select a consistent parameter set for our bimetallic system. This gives a good description of the chemisorption bond changes between the various systems considered in our study. The CO chemisorption energy on Pt/Ni(111) was found to be lowered in comparison with Pt(111) and Ni(111), in good agreement with experimental data on Pt-rich Pt-Ni surface alloys. This observation could be justified by the electronic changes of the Pt states (valence band broadening and decreasing density at the Fermi level). Indeed, they induce, in comparison with the pure substrates, a repulsion between Pt and CO although the 2π* population of the chemisorbed molecule increases. This points to the necessity of going beyond arguments based on an analysis of the 5σ donation and 2π* backdonation for a complete description of the chemisorption bond.

  6. Performance of the PdNi and PdNiSe as cathodes in PEM fuel cells; Desempeno de PdNi y PdNiSe como catodos en celdas de combustible tipo PEM

    Energy Technology Data Exchange (ETDEWEB)

    Santana, A.; Ramos-Sanchez, G.; Vazquez, G.; Solorza-Feria, O. [Centro de Investigaciones y de Estudios Avanzados del IPN, Mexico D.F. (Mexico)]. E-mail: gramos@cinvestav.mx

    2009-09-15

    The search for new materials capable of catalyzing oxygen reactions in low temperature fuel cells continues to be one of the key issues in the development of a hydrogen economy. Electrochemical and physical characterization studies have demonstrated that the PdNi and PdNiSe catalysts have adequate properties for use as cathodes in fuel cells. Nevertheless, the performance of the materials in proton exchange membrane (PEM) fuel cells depends not only on the catalytic properties but also on the adequate preparation of the electrocatalyst membrane interface (EMI). This work presents the results of the search for optimal conditions to prepare the EMIs with PdNi and PdNiSe cathodes. There are many variables for handling the preparation of the interfaces, nevertheless our search focuses on two: catalyst ratio/Vulcan Carbon® and the catalyst amount. Interfaces were prepared with an active area of 5 cm{sup 2} with PdNi and PdNiSe cathodes and carbon fabric anode with Pt E-tek®. These interfaces were tested with an ElectroChem model under different gas pressure and temperature conditions. The optimization method was carried out using a simplex method with the variables mentioned above and power density per unit mass and catalyst area as response variables. [Spanish] La busqueda de nuevos materiales capaces de catalizar la Reaccion de Oxigeno (RRO) en celdas de combustible de baja temperatura, sigue siendo uno de los temas clave para el desarrollo de una Economia del Hidrogeno. Estudios electroquimicos y de caracterizacion fisica han demostrado que los catalizadores PdNi y PdNiSe, tienen las propiedades adecuadas para poder ser utilizados como catodos en celdas de combustible; sin embargo el desempeno de los materiales en celdas de combustible de membrana de intercambio protonico (PEM), no solo depende de las propiedades del catalizador, sino tambien de la preparacion adecuada del Ensamble Membrana Electrocatalizador (EME). En este trabajo se presentan los resultados de la

  7. High-performance core-shell PdPt@Pt/C catalysts via decorating PdPt alloy cores with Pt

    Science.gov (United States)

    Wu, Yan-Ni; Liao, Shi-Jun; Liang, Zhen-Xing; Yang, Li-Jun; Wang, Rong-Fang

    A core-shell structured low-Pt catalyst, PdPt@Pt/C, with high performance towards both methanol anodic oxidation and oxygen cathodic reduction, as well as in a single hydrogen/air fuel cell, is prepared by a novel two-step colloidal approach. For the anodic oxidation of methanol, the catalyst shows three times higher activity than commercial Tanaka 50 wt% Pt/C catalyst; furthermore, the ratio of forward current I f to backward current I b is high up to 1.04, whereas for general platinum catalysts the ratio is only ca. 0.70, indicating that this PdPt@Pt/C catalyst has high activity towards methanol anodic oxidation and good tolerance to the intermediates of methanol oxidation. The catalyst is characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The core-shell structure of the catalyst is revealed by XRD and TEM, and is also supported by underpotential deposition of hydrogen (UPDH). The high performance of the PdPt@Pt/C catalyst may make it a promising and competitive low-Pt catalyst for hydrogen fueled polymer electrolyte membrane fuel cell (PEMFC) or direct methanol fuel cell (DMFC) applications.

  8. Synergetic effect of host-guest chemistry and spin crossover in 3D Hofmann-like metal-organic frameworks [Fe(bpac)M(CN)4] (M=Pt, Pd, Ni).

    Science.gov (United States)

    Bartual-Murgui, Carlos; Salmon, Lionel; Akou, Amal; Ortega-Villar, Norma A; Shepherd, Helena J; Muñoz, M Carmen; Molnár, Gábor; Real, José Antonio; Bousseksou, Azzedine

    2012-01-09

    The synthesis and characterization of a series of three-dimensional (3D) Hofmann-like clathrate porous metal-organic framework (MOF) materials [Fe(bpac)M(CN)(4)] (M=Pt, Pd, and Ni; bpac=bis(4-pyridyl)acetylene) that exhibit spin-crossover behavior is reported. The rigid bpac ligand is longer than the previously used azopyridine and pyrazine and has been selected with the aim to improve both the spin-crossover properties and the porosity of the corresponding porous coordination polymers (PCPs). The 3D network is composed of successive {Fe[M(CN)(4)]}(n) planar layers bridged by the bis-monodentate bpac ligand linked in the apical positions of the iron center. The large void between the layers, which represents 41.7% of the unit cell, can accommodate solvent molecules or free bpac ligand. Different synthetic strategies were used to obtain a range of spin-crossover behaviors with hysteresis loops around room temperature; the samples were characterized by magnetic susceptibility, calorimetric, Mössbauer, and Raman measurements. The complete physical study reveals a clear relationship between the quantity of included bpac molecules and the completeness of the spin transition, thereby underlining the key role of the π-π stacking interactions operating between the host and guest bpac molecules within the network. Although the inclusion of the bpac molecules tends to increase the amount of active iron centers, no variation of the transition temperature was measured. We have also investigated the ability of the network to accommodate the inclusion of molecules other than water and bpac and studied the synergy between the host-guest interaction and the spin-crossover behavior. In fact, the clathration of various aromatic molecules revealed specific modifications of the transition temperature. Finally, the transition temperature and the completeness of the transition are related to the nature of the metal associated with the iron center (Ni, Pt, or Pd) and also to the

  9. Adsorption of aromatics on the (111) surface of PtM and PtM3 (M = Fe, Ni) alloys

    Energy Technology Data Exchange (ETDEWEB)

    Hensley, Alyssa; Schneider, Sebastian; Wang, Yong; McEwen, Jean-Sabin

    2015-09-18

    The adsorption of benzene and phenol was studied on PtM and PtM3 (111) surfaces, with M being either Ni or Fe. Under vacuum, the most favorable near surface structures showed an enrichment in Pt over the M species. An analysis of the electronic structure of the metal species in the clean surfaces with different near surface structures was done with the d-band model and showed that the Pt's d-states are significantly shifted away from the Fermi level due to the Pt-M interactions while the M species' d-states were less affected, with Ni's d-band shifting closer to the Fermi level and Fe's d-band shifting away from the Fermi level. The adsorption of aromatics, benzene and phenol, on several near surface structures for the PtM and PtM3 (111) surfaces showed that higher surface M concentrations resulted in a stronger adsorption due to the larger amount of charge transferred between the adsorbate and surface. However, compared to the adsorption of benzene and phenol on monometallic surfaces, the adsorption of these species on the PtM and PtM3 (111) surfaces was significantly weakened. Overall, our results show that the observed behavior of these Pt/Fe and Pt/Ni alloys is similar to that seen for the previously studied Pd/Fe surfaces. Furthermore, balancing the weakly adsorbing Pt surface species with the more strongly interacting Fe or Ni species can lead to the tailored adsorption of aromatics with applications in both hydrodeoxygenation and hydrogenation reactions by increasing the desorption rate of wanted aromatic products.

  10. Effects of Stoichiometry on Transformation Temperatures and Actuator-Type Performance of NiTiPd and NiTiPdX High-Temperature Shape Memory Alloys

    Science.gov (United States)

    Bigelow, Glen S.; Gaydosh, Darrell; Garg, Anita; Padula, Santo A., II; Noebe, Ronald D.

    2007-01-01

    High-temperature shape memory NiTiPd and NiTiPdX (X=Au, Pt, Hf) alloys were produced with titanium equivalent (Ti+Hf) compositions of 50.5, 50.0, 49.5, and 49.0 at.%. Thermo-mechanical testing in compression was used to evaluate the transformation temperatures, transformation strain, work output, and permanent deformation behavior of each alloy to study the effects of quaternary alloying and stoichiometry on high-temperature shape memory alloy behavior. Microstructural evaluation showed the presence of second phases for all alloy compositions. No load transformation temperatures in the stoichiometric alloys were relatively unchanged by Au and Pt substitutions, while the substitution of Hf for Ti causes a drop in transformation temperatures. The NiTiPd, NiTiPdAu and NiTiPdHf alloys exhibited transformation temperatures that were highest in the Ti-rich compositions, slightly lower at stoichiometry, and significantly reduced when the Ti equivalent composition was less than 50 at.%. For the NiTiPdPt alloy, transformation temperatures were highest for the Ti-rich compositions, lowest at stoichiometry, and slightly higher in the Ni-rich composition. When thermally cycled under constant stresses of up to 300 MPa, all of the alloys had transformation strains, and therefore work outputs, which increased with increasing stress. In each series of alloys, the transformation strain and thus work output was highest for stoichiometric or Ti-rich compositions while permanent strain associated with the constant-load thermal cycling was lowest for alloys with Ni-equivalent-rich compositions. Based on these results, basic rules for optimizing the composition of NiTiPd alloys for actuator performance will be discussed.

  11. PT AND PT/NI "NEEDLE" ELETROCATALYSTS ON CARBON NANOTUBES WITH HIGH ACTIVITY FOR THE ORR

    Energy Technology Data Exchange (ETDEWEB)

    Colon-Mercado, H.

    2011-11-10

    Platinum and platinum/nickel alloy electrocatalysts supported on graphitized (gCNT) or nitrogen doped carbon nanotubes (nCNT) are prepared and characterized. Pt deposition onto carbon nanotubes results in Pt 'needle' formations that are 3.5 nm in diameter and {approx}100 nm in length. Subsequent Ni deposition and heat treatment results in PtNi 'needles' with an increased diameter. All Pt and Pt/Ni materials were tested as electrocatalysts for the oxygen reduction reaction (ORR). The Pt and Pt/Ni catalysts showed excellent performance for the ORR, with the heat treated PtNi/gCNT (1.06 mA/cm{sup 2}) and PtNi/nCNT (0.664 mA/cm{sup 2}) showing the highest activity.

  12. Fabrication of MgAl2Si2O8 : M0.01 (M = Ni2+, Cu2+, Pd2+, Pt2+ and Ru3+): catalytic effects for the reduction of 2- or 4-nitroanilines in water

    Indian Academy of Sciences (India)

    Serkan Dayan; Sevgi Öztürk; Nilgün Kayaci; Nilgun Kalaycioglu Ozpozan; Esra Öztürk

    2015-10-01

    Five new MgAl2Si2O8 : M0.01 (M = Ni2+, Cu2+, Pd2+, Pt2+ and Ru3+) materials were developed for the reduction of nitroarenes as catalysts by conventional solid state reaction at 1300°C. The prepared materials were characterized by thermal analysis, Fourier transform infrared spectroscopy, X-ray powder diffraction analysis, scanning electron microscopy, energy-dispersive X-ray analysis and nitrogen adsorption–desorption analysis. The catalytic activities of the prepared catalysts were tested in the reduction of 2- or 4-nitroanilines in aqueous media at ambient temperature in the presence of NaBH4 by UV–vis spectrophotometer. Furthermore, the MgAl2Si2O8 : M0.01 catalysts can be recovered by filtration and reused for five cycles for the reduction of 2-nitroaniline. These results show that the MgAl2Si2O8 : M0.01 catalysts can be used in practical applications in the reduction of nitroanilines.

  13. Surface composition of Pt-Pd alloys treated in hydrogen

    Science.gov (United States)

    Szabo, A.; Paál, Z.; Szász, A.; Kojnok, J.; Fabian, D. J.

    1989-11-01

    Pd enrichment is observed in Pd-Pt alloy sheets when heated in He and in H 2. The surface composition was monitored by soft X-ray emission spectroscopy (SXES) and by work function measurements. A regular solution model is used to calculate the expected composition of the surface atomic layers, with and without adsorbed hydrogen, and the calculated and measured values for Pd-enrichment are compared. The possible effect of subsurface adsorbed hydrogen is discussed.

  14. Simple preparation of Pd-Pt nanoalloy catalysts for methanol-tolerant oxygen reduction

    Science.gov (United States)

    He, Wei; Liu, Juanying; Qiao, Yongjin; Zou, Zhiqing; Zhang, Xiaogang; Akins, Daniel L.; Yang, Hui

    Carbon-supported Pd-Pt bimetallic nanoparticles of different atomic ratios (Pd-Pt/C) have been prepared by a simple procedure involving the complexing of Pd and Pt species with sodium citrate followed by ethylene glycol reduction. As-prepared Pd-Pt alloy nanoparticles evidence a single-phase fcc disordered structure, and the degree of alloying is found to increase with Pd content. Both X-ray diffraction and transmission electron microscopy characterizations indicate that all the Pd-Pt/C catalysts possess a similar mean particle size of ca. 2.8 nm. The highest mass and specific activity of the oxygen reduction reaction (ORR) using the Pd-Pt/C catalysts are found with a Pd:Pt atomic ratio of 1:2. Moreover, all Pd-Pt alloy catalysts exhibit significantly enhanced methanol tolerance during the ORR than the Pt/C catalyst, ensuring a higher ORR performance while diminishing Pt utilization.

  15. Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of formic acid: Towards tuning the reaction pathway

    Indian Academy of Sciences (India)

    Sourov Ghosh; C Retna Raj

    2015-05-01

    Synthesis of highly efficient functional electrocatalyst that favours the electrochemical oxidation of formic acid via CO-free dehydrogenation pathway is required for direct formic acid fuel cells. Traditional catalysts favour the dehydration pathway involving the generation of poisonous CO. Herein we demonstrate the superior electrocatalytic performance of Pt-Pd bimetallic nanoelectrocatalyst of ultralow Pt content and tuning the reaction pathway by controlling the Pt content. Bimetallic nanoparticles of Pt4Pd96, Pt7Pd93 and Pt47Pd53 compositions are synthesized by electrochemical co-deposition method in aqueous solution. The nanoparticles of ultralow Pt content, Pt4Pd96, favour the CO-free dehydrogenation pathway for formic acid oxidation with an onset potential of 0 V (SHE) whereas the Pt47Pd53 nanoparticles favour the dehydration pathway involving the formation of CO at high positive potential. The Pt content of the bimetallic nanoparticles actually controls the oxidation peak potential and catalytic activity. Significant negative shift (∼350 mV) in the oxidation peak potential and remarkable enhancement in the current density (2.6 times) are observed for Pt4Pd96 nanoparticles with respect to Pt47Pd53. The absence of three adjacent Pt and Pd atoms could be the reason for the suppression of CO pathway. The electrochemical impedance measurements indirectly support the CO-free pathway for the formic acid oxidation on Pt4Pd96 nanoparticles.

  16. 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.

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

    Science.gov (United States)

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

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

  18. Structures of Pd(CN)2 and Pt(CN)2: intrinsically nanocrystalline materials?

    Science.gov (United States)

    Hibble, Simon J; Chippindale, Ann M; Bilbé, Edward J; Marelli, Elena; Harris, Peter J F; Hannon, Alex C

    2011-01-03

    Analysis and modeling of X-ray and neutron Bragg and total diffraction data show that the compounds referred to in the literature as "Pd(CN)(2)" and "Pt(CN)(2)" are nanocrystalline materials containing small sheets of vertex-sharing square-planar M(CN)(4) units, layered in a disordered manner with an intersheet separation of ~3.44 Å at 300 K. The small size of the crystallites means that the sheets' edges form a significant fraction of each material. The Pd(CN)(2) nanocrystallites studied using total neutron diffraction are terminated by water and the Pt(CN)(2) nanocrystallites by ammonia, in place of half of the terminal cyanide groups, thus maintaining charge neutrality. The neutron samples contain sheets of approximate dimensions 30 Å × 30 Å. For sheets of the size we describe, our structural models predict compositions of Pd(CN)(2)·xH(2)O and Pt(CN)(2)·yNH(3) (x ≈ y ≈ 0.29). These values are in good agreement with those obtained from total neutron diffraction and thermal analysis, and are also supported by infrared and Raman spectroscopy measurements. It is also possible to prepare related compounds Pd(CN)(2)·pNH(3) and Pt(CN)(2)·qH(2)O, in which the terminating groups are exchanged. Additional samples showing sheet sizes in the range ~10 Å × 10 Å (y ~ 0.67) to ~80 Å × 80 Å (p = q ~ 0.12), as determined by X-ray diffraction, have been prepared. The related mixed-metal phase, Pd(1/2)Pt(1/2)(CN)(2)·qH(2)O (q ~ 0.50), is also nanocrystalline (sheet size ~15 Å × 15 Å). In all cases, the interiors of the sheets are isostructural with those found in Ni(CN)(2). Removal of the final traces of water or ammonia by heating results in decomposition of the compounds to Pd and Pt metal, or in the case of the mixed-metal cyanide, the alloy, Pd(1/2)Pt(1/2), making it impossible to prepare the simple cyanides, Pd(CN)(2), Pt(CN)(2), or Pd(1/2)Pt(1/2)(CN)(2), by this method.

  19. Pd-Pt random alloy nanocubes with tunable compositions and their enhanced electrocatalytic activities.

    Science.gov (United States)

    Yuan, Qiang; Zhou, Zhiyou; Zhuang, Jing; Wang, Xun

    2010-03-07

    Monodisperse, highly-selective sub-10 nm Pd-Pt random alloy nanocubes have been successfully synthesized in aqueous solution, and the electrocatalytic activity of these Pd-Pt alloys towards formic acid oxidation was investigated and compared with the activity of Pd sub-10 nm nanocubes, and the commercial Pd and Pt black.

  20. Ternary rare-earth aluminium intermetallics RE10TAl3 (RE = Y, Ho, Tm, Lu; T = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) with an ordered anti-Co2Al5 structure.

    Science.gov (United States)

    Benndorf, Christopher; Eckert, Hellmut; Janka, Oliver

    2017-01-24

    Twenty new rare-earth metal rich intermetallic aluminium compounds, RE10TAl3 (RE = Y, Ho, Tm, Lu; T = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt), were synthesized by arc melting the elements. The compounds crystallize, in analogy to e.g. the respective Cd representatives, with a ternary ordered structure as anti-type to the hexagonal Co2Al5 type, with the space group P63/mmc. The three crystallographically independent rare-earth metal sites occupy the aluminium positions of the aristotype, while the transition metal and aluminium atoms are ordered on the two cobalt sites. Like other rare-earth rich compounds the RE10TX3 members also exhibit transition-metal-centred T@RE6 trigonal prisms as striking structural building units. The prepared compounds have been investigated by susceptibility measurements and (27)Al solid-state MAS-NMR measurements conducted on the Pauli-paramagnetic Y and Lu compounds. Some compounds show a certain amount of disorder as seen from the single crystal structure analysis and from signal broadening in the NMR investigations. By separating Knight shifts from second-order quadrupolar shifts via field dependent measurements, monotonic trends can be discerned regarding the effect of the T atom valence electron concentration and period number, as well as the effect of the closed 4f shell contributed in the Lu compounds. The results confirm that a comparison of Knight shifts within a series of isotypic compounds can reveal important electronic structure information in intermetallic systems.

  1. B-Site Metal (Pd, Pt, Ag, Cu, Zn, Ni Promoted La1−xSrxCo1−yFeyO3–δ Perovskite Oxides as Cathodes for IT-SOFCs

    Directory of Open Access Journals (Sweden)

    Shaoli Guo

    2015-03-01

    Full Text Available Perovskite oxides La1−xSrxCo1−yFeyO3–δ (LSCF have been extensively investigated and developed as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs due to mixed ionic–electronic conductivity and high electrooxygen reduction activity for oxygen reduction. Recent literature investigations show that cathode performances can be improved by metal surface modification or B-site substitution on LSCF. Although the specific reaction mechanism needs to be further investigated, the promoting effect of metal species in enhancing oxygen surface exchange and oxygen bulk diffusion is well recognized. To our knowledge, no previous reviews dealing with the effect of metal promotion on the cathodic performances of LSCF materials have been reported. In the present review, recent progresses on metal (Pd, Pt, Ag, Cu, Zn, Ni promotion of LSCF are discussed focusing on two main aspects, the different synthesis approaches used (infiltration, deposition, solid state reaction, one pot citrate method and the effects of metal promotion on structural properties, oxygen vacancies content and cathodic performances. The novelty of the work lies in the fact that the metal promotion at the B-site is discussed in detail, pointing at the effects produced by two different approaches, the LSCF surface modification by the metal or the metal ion substitution at the B-site of the perovskite. Moreover, for the first time in a review article, the importance of the combined effects of oxygen dissociation rate and interfacial oxygen transfer rate between the metal phase and the cathode phase is addressed for metal-promoted LSCF and compared with the un-promoted oxides. Perspectives on new research directions are shortly given in the conclusion.

  2. Concave Pd-Pt Core-Shell Nanocrystals with Ultrathin Pt Shell Feature and Enhanced Catalytic Performance.

    Science.gov (United States)

    Zhang, Ying; Bu, Lingzheng; Jiang, Kezhu; Guo, Shaojun; Huang, Xiaoqing

    2016-02-10

    One-pot creation of unique concave Pd-Pt core-shell polyhedra has been developed for the first time using an efficient approach. Due to the concave feature and ultrathin Pt shell, the created Pd-Pt core-shell polyhedra exhibit enhanced catalytic performance in both the electrooxidation of methanol and hydrogenation of nitrobenzene, as compared with commercial Pt black and Pd black catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Indian Academy of Sciences (India)

    Hitesh Sharma; S Prakash

    2003-01-01

    The strain field due to body centered substitutional transition metal impurities in Ni and Pd metals are investigated. The calculations are carried out in the discrete lattice model of the metal using Kanzaki lattice static method. The effective ion–ion interaction potential due to Wills and Harrison is used to evaluate dynamical matrix and the impurity-induced forces. The results for atomic displacements due to 3d, 4d and 5d impurities (Fe, Co, Cu, Nb, Mo, Pd, Pt and Au) in Ni and (Fe, Co, Cu, Ni, Nb, Mo, Pt and Au) impurities in Pd are given up to 25 NN’s of impurity and these are compared with the available experimental data. The maximum displacements of 4.6% and 3.8% of 1NN distance are found for NiNb and PdNb alloys respectively, while the minimum displacements of 0.63% and 0.23% of 1NN distance are found for NiFe and PdFe alloys respectively. Except for Cu, the atomic displacements are found to be proportional to the core radii and d state radius. The relaxation energies for 3d impurities are found less than those for 4d and 5d impurities in Ni and Pd metals. Therefore, 3d impurities may easily be solvable in these metals.

  4. Ternary Pd-Ni-P hybrid electrocatalysts derived from Pd-Ni core-shell nanoparticles with enhanced formic acid oxidation activity.

    Science.gov (United States)

    Liang, Xin; Liu, Bo; Zhang, Juntao; Lu, Siqi; Zhuang, Zhongbin

    2016-09-25

    Ternary Pd-Ni-P hybrid electrocatalysts were synthesized through low temperature phosphidation of Pd-Ni core-shell nanoparticles. They show enhanced formic acid electro-oxidation activity compared to Pd, Pd-Ni and Pd-P nanoparticles, which is ascribed to the synergistic effect of the Ni and P components with Pd.

  5. One-pot synthesis of Pd-Pt@Pd core-shell nanocrystals with enhanced electrocatalytic activity for formic acid oxidation

    KAUST Repository

    Yuan, Qiang

    2014-01-01

    Well-defined Pd-Pt@Pd core-shell nanocrystals with a Pd-Pt alloy core and a conformal Pd shell of ~2-3 nm were directly synthesized through a one-pot, aqueous solution approach without any preformed Pd or Pt seeds. These Pd-Pt@Pd core-shell nanocrystals show an enhanced electrocatalytic activity for formic acid oxidation compared with commercial Pd black. This journal is © 2014 The Royal Society of Chemistry.

  6. London penetration depth measurements in Ba (Fe1-xTx)2As2(T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, Ryan T. [Iowa State Univ., Ames, IA (United States)

    2011-01-01

    The London penetration depth has been measured in various doping levels of single crystals of Ba(Fe1-xTx)2As2 (T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors by utilizing a tunnel diode resonator (TDR) apparatus. All in-plane penetration depth measurements exhibit a power law temperature dependence of the form Δλab(T) = CTn, indicating the existence of low-temperature, normal state quasiparticles all the way down to the lowest measured temperature, which was typically 500 mK. Several different doping concentrations from the Ba(Fe1-xTx)2As2 (T=Co,Ni) systems have been measured and the doping dependence of the power law exponent, n, is compared to results from measurements of thermal conductivity and specific heat. In addition, a novel method has been developed to allow for the measurement of the zero temperature value of the in-plane penetration depth, λab(0), by using TDR frequency shifts. By using this technique, the doping dependence of λab(0) has been measured in the Ba(Fe1-xCox)2As2 series, which has allowed also for the construction of the doping-dependent superfluid phase stiffness, ρs(T) = [λ(0)/λ(T)]2. By studying the effects of disorder on these superconductors using heavy ion irradiation, it has been determined that the observed power law temperature dependence likely arises from pair-breaking impurity scattering contributions, which is consistent with the proposed s±-wave symmetry of the superconducting gap in the dirty scattering limit. This hypothesis is supported by the measurement of an exponential temperature dependence of the penetration depth in the intrinsically clean LiFeAs, indicative of a nodeless superconducting gap.

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

    Science.gov (United States)

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

    2016-05-01

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

  8. Influence of Pt atoms on the low temperature formation of epitaxial Pd monosilicide

    Science.gov (United States)

    Kawarada, H.; Mizugaki, K.; Ohdomari, I.

    1985-01-01

    The effect of Pt concentration in Pd thin films on the nucleation and growth of PdSi and PdxPt1-xSi (ternary monosilicide) has been investigated by transmission electron microscopy (TEM). Low concentration of Pt (10 at. %) in Pd film enhances PdSi formation at lower temperature than previously reported. It has been proposed that PdSi formation is governed by its slow nucleation. However, in our studies, the nucleation of PtSi, which is substituted for that of PdSi, triggers the subsequent PdSi growth at low temperatures. High concentration of Pt (55 at. %) in Pd-Pt alloy film lowers the temperature of the phase transformation from metal-rich silicide to monosilicide (PdxPt1-xSi). The temperature is the same as that of PtSi formation. In both cases, the monosilicide layers (about 20 nm) have an epitaxial relationship with (111) Si substrates.

  9. Synthesis of Pt, Pd, Pt/Ag and Pd/Ag nanoparticles by microwave-polyol method

    Indian Academy of Sciences (India)

    Kirti Patel; Sudhir Kapoor; Devilal Purshottam Dave; Tulsi Mukherjee

    2005-07-01

    Pt, Pd, Pt-Ag and Pd-Ag bimetallic nanoparticles were synthesized in ethylene glycol and glycerol using the microwave technique in the presence of a stabilizer poly(N-vinylpyrrolidone) (PVP). It has been observed that PVP is capable of complexing and stabilizing nanoparticles. Mixed clusters were formed by simultaneous reduction of the metal ions. The clusters were characterized using UV-Vis spectra, XRD and dynamic light scattering. To understand the mechanism of formation of mixed nanoparticles, several experimental parameters such as in situ irradiation of mixed metal salts and mixing of individual sols were attempted.

  10. Microemulsion prepared Ni88Pt12 for methane cracking

    KAUST Repository

    Zhou, Lu

    2017-01-16

    Monodispersed NiPt nanoparticles of 10 nm were synthesized by water-in-oil microemulsion. The Ni-Pt alloy structure was stable during the thermal treatment between 330 and 1037 °C, whereas the relatively low temperature range of 600-700 °C was favorable for methane cracking to produce hydrogen and carbon nanotubes.

  11. PdNi hollow nanoparticles for improved electrocatalytic oxygen reduction in alkaline environments.

    Science.gov (United States)

    Wang, Meng; Zhang, Weimin; Wang, Jiazhao; Wexler, David; Poynton, Simon D; Slade, Robert C T; Liu, Huakun; Winther-Jensen, Bjorn; Kerr, Robert; Shi, Dongqi; Chen, Jun

    2013-12-11

    Palladium-nickel (PdNi) hollow nanoparticles were synthesized via a modified galvanic replacement method using Ni nanoparticles as sacrificial templates in an aqueous medium. X-ray diffraction and transmission electron microscopy show that the as-synthesized nanoparticles are alloyed nanostructures and have hollow interiors with an average particle size of 30 nm and shell thickness of 5 nm. Compared with the commercially available Pt/C or Pd/C catalysts, the synthesized PdNi/C has superior electrocatalytic performance towards the oxygen reduction reaction, which makes it a promising electrocatalyst for alkaline anion exchange membrane fuel cells and alkali-based air-batteries. The electrocatalyst is finally examined in a H2/O2 alkaline anion exchange membrane fuel cell; the results show that such electrocatalysts could work in a real fuel cell application as a more efficient catalyst than state-of-the-art commercially available Pt/C.

  12. Tunable Architecture of Rhombic Dodecahedral Pt-Ni Nanoframe Electrocatalysts.

    Energy Technology Data Exchange (ETDEWEB)

    Becknell, Nigel; Son, Yoonkook; Kim, Dohyung; Li, Dongguo; Yu, Yi; Niu, Zhiqiang; Lei, Teng; Sneed, Brian T.; More, Karren L.; Markovic, Nenad M.; Stamenkovic, Vojislav R.; Yang, Peidong

    2017-08-30

    Platinum-based alloys are known to demonstrate advanced properties in electrochemical reactions that are relevant for proton exchange membrane fuel cells and electrolyzers. Further development of Pt alloy electrocatalysts relies on the design of architectures with highly active surfaces and optimized utilization of the expensive elpment, Pt. Here, we show that the three-dimensional Pt anisotropy of Pt-Ni rhombic dodecahedra can be tuned by controlling the ratio between Pt and Ni precursors such that either a completely hollow nanoframe or a new architecture, the excavated nanoframe, can be obtained. The excavated nanoframe showed similar to 10 times higher specific and similar to 6 times higher mass activity for the oxygen reduction reaction than Pt/C, and twice the mass activity of the hollow nanoframe. The high activity is attributed to enhanced Ni content in the near-surface region and the extended two-dimensional sheet structure within the nanoframe that minimizes the number of buried Pt sites.

  13. Pt monolayer shell on hollow Pd core electrocatalysts: Scale up synthesis, structure, and activity for the oxygen reduction reaction

    Directory of Open Access Journals (Sweden)

    Vukmirovic Miomir B.

    2013-01-01

    Full Text Available We report on synthesis, characterization and the oxygen reduction reaction (ORR kinetics of Pt monolayer shell on Pd(hollow, or Pd-Au(hollow core electrocatalysts. Comparison between the ORR catalytic activity of the electrocatalysts with hollow cores and those of Pt solid and Pt hollow nanoparticles has been obtained using the rotating disk electrode technique. Hollow nanoparticles were made using Ni or Cu nanoparticles as sacrificial templates. The Pt ORR specific and mass activities of the electrocatalysts with hollow cores were found considerably higher than those of the electrocatalysts with the solid cores. We attribute this enhanced Pt activity to the smooth surface morphology and hollow-induced lattice contraction, in addition to the mass-saving geometry of hollow particles.

  14. Electrochemical study of the Pt and Pt-Ni upon multiwalled carbon nanotubes

    Science.gov (United States)

    Mohammed, Norani Muti; Mumtaz, Asad; Ansari, Muhammad Shahid; Ahmad, Riaz

    2016-11-01

    Direct methanol fuel cells have attracted great interest in the recent development of portable devices. New routes are being developed for synthesizing the catalysts used in the methanol oxidation. In this work, the electrochemical behavior of the Pt and Pt-Ni upon multiwalled carbon nanotubes, synthesized via a new modified route, has been studied. The results showed that Pt-Ni 10% has the comparable current density to the Pt 20%-loading which is nearly 3 times greater than 10% Pt loading. The transfer of the polarization curve of Pt-Ni 10% towards lower polarization region following the catalyst with 20% Pt loading indicates the higher activity of the nano-electro-catalysts in the alkaline media. Also the long term efficiency and activity of the Pt-Ni with 10% loading is nearly reaching the 20% Pt-loading which is almost 10 folds greater than the 10% Pt loading. The study revealed that Ni in Pt-based nanoalloy impart not only an enhanced activity but also better durability of catalyst in direct methanol fuel cell applications.

  15. Microbial synthesis of bimetallic PdPt nanoparticles for catalytic reduction of 4-nitrophenol.

    Science.gov (United States)

    Tuo, Ya; Liu, Guangfei; Dong, Bin; Yu, Huali; Zhou, Jiti; Wang, Jing; Jin, Ruofei

    2017-02-01

    Bimetallic nanoparticles are generally believed to have improved catalytic activity and stability due to geometric and electronic changes. In this work, biogenic-Pd (bio-Pd), biogenic-Pt (bio-Pt), and biogenic-PdPt (bio-PdPt) nanoparticles were synthesized by Shewanella oneidensis MR-1 in the absence or presence of quinone. Compared with direct microbial reduction process, the addition of anthraquinone-2,6-disulfonate (AQDS) could promote the reduction efficiency of Pd(II) or/and Pt(IV) and result in decrease of particles size. All kinds of nanoparticles could catalyze 4-nitrophenol reduction by NaBH4 and their catalytic activities took the following order: bio-PdPt (AQDS) ∼ bio-PdPt > bio-Pd (AQDS) > bio-Pd > bio-Pt (AQDS) ∼ bio-Pt. Moreover, the bio-PdPt (AQDS) nanoparticles could be reused for 6 cycles. We believe that this simple and efficient biosynthesis approach for synthesizing bimetallic bio-PdPt nanocatalysts is important for preparing active and stable catalysts.

  16. Miniature Fuel Cell With Monolithically Fabricated Si Electrodes - Au-Pd-Pt Multilayer Catalyst -

    Science.gov (United States)

    Shirai, Ryo; Vasiljevic, N.; Hayase, Masanori

    2016-11-01

    A novel catalyst layer structure is proposed for our miniature fuel cells. In our fuel cells, conventionally porous Pt was used as a catalyst layer. In order to reduce the Pt amount, instead of porous Pt, porous Pd was formed on a Si chip and Pt was deposited atomically on the Pd by UPD-SLRR(Under Potential Deposition - Surface Limited Redox Replacement). The Pd- Pt catalyst showed satisfying performance, besides high CO tolerance was observed. Though the Pd-Pt catalyst is quite promising, Pd is also a rare metal and reduction of Pd amount is necessary. In this study, a novel Au-Pd-Pt catalyst formation strategy is proposed by UPD-SLRR, and the layered structure is preliminary fabricated.

  17. A Review of TiNiPdCu Alloy System for High Temperature Shape Memory Applications

    Science.gov (United States)

    Khan, M. Imran; Kim, Hee Young; Miyazaki, Shuichi

    2015-06-01

    High temperature shape memory alloys (HTSMAs) are important smart materials and possess a significant potential to improve many engineering systems. Many TiNi-based high temperature ternary alloy systems have been reported in literature including TiNiPd, TiNiPt, TiNiZr, TiNiAu, TiNiHf, etc. Some quaternary additions of certain elements in the above systems have been successful to further improve many important shape memory and mechanical properties. The success criteria for an HTSMA become strict in terms of its cyclic stability, maximum recoverable strain, creep resistance, and corrosion resistance at high temperatures. TiNiPdCu alloy system has been recently proposed as a promising HTSMA. Unique nanoscaled precipitates formed in TiNiPdCu-based HTSMAs are found to be stable at temperatures above 773 K, while keeping the benefits of ease of fabrication. It is expected that this alloy system possesses significant potential especially for the high temperature shape memory applications. Till now many research reports have been published on this alloy system. In the present work, a comprehensive review of the TiNiPdCu system is presented in terms of thermomechanical behavior, nanoscale precipitation mechanism, microstructural features, high temperature shape memory and mechanical properties, and the important parameters to control the high temperature performance of these alloys.

  18. 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.

  19. Pd-Pt bimetallic nanodendrites with high activity for oxygen reduction.

    Science.gov (United States)

    Lim, Byungkwon; Jiang, Majiong; Camargo, Pedro H C; Cho, Eun Chul; Tao, Jing; Lu, Xianmao; Zhu, Yimei; Xia, Younan

    2009-06-05

    Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K2PtCl4 with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.

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

    Science.gov (United States)

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

    2016-09-01

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

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

    Science.gov (United States)

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

    2015-09-01

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

  2. Electrochemical impedance study and performance of PdNi nanoparticles as cathode catalyst in a polymer electrolyte membrane fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Ramos-Sanchez, G.; Santana-Salinas, A.; Vazquez-Huerta, G.; Solorza-Feria, O. [Inst. Politenico Nacional, Centro de Investigacion y de Estudios Avanzados, Mexico City (Mexico). Dept. de Quimica

    2010-07-15

    Polymer electrolyte membrane fuel cells (PEMFC) convert the energy stored in hydrogen and oxygen molecules directly into electricity. However, technical and economic challenges must be overcome to address cost, performance and stability issues associated with membrane electrode assemblies (MEA). The oxygen reduction reaction (ORR) which takes place in the cathode is the limiting reaction due to the slow kinetics of ORR on metals, including platinum (Pt). For that reason, much research has gone into finding catalyst materials with a similar or greater performance than Pt. Bimetallic palladium (Pd) based catalysts have been considered as alternative materials for ORR. In this study, a carbon-dispersed bimetallic PdNi was prepared by borohydride reduction using PdCl{sub 2} and NiCl{sub 2} as precursors in a tetrahydrofuran (THF) solution. The PdNi loading and weight percentage were optimized using the Simplex method. The MEA performance was evaluated at optimum conditions using the PdNi electrocatalyst as the cathode and a Pt-Etek carbon cloth as the anode. The maximum power density of 122 mW per cm{sup 2} was reached with 45 percent of PdNi wt percent at 30 psi and 80 degrees C. The catalytic activity and the mechanism of the ORR on PdNi, in 0.5M H{sub 2}SO{sub 4} was investigated using electrochemical impedance spectroscopy. The Tafel slope and the charge transfer coefficient were obtained from the impedance spectra at optimum condition of PdNi loading and PdNi wt percent. 24 refs., 2 tabs., 5 figs.

  3. Evaluation of Pt{sub 40}Pd{sub 60}/MWCNT electrocatalyst as ethylene glycol-tolerant oxygen reduction cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Morales-Acosta, D.; Arriaga, L.G. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Parque Tecnologico Queretaro, Sanfandila, Pedro Escobedo, C.P. 76703 Queretaro (Mexico); Alvarez-Contreras, L. [Centro de Investigacion en Materiales Avanzados S.C., Complejo Industrial Chihuahua, C. P. 31109, Chihuahua, Chih. (Mexico); Luna, S. Fraire; Varela, F.J. Rodriguez [Cinvestav Unidad Saltillo, Carr. Saltillo-Monterrey Km. 13.5, Ramos Arizpe, Coahuila, C.P. 25900 (Mexico)

    2009-07-15

    Pt-Pd/MWCNT with Pt:Pd atomic ratio 40:60 and Pt/MWCNT electrocatalyst were synthesized and evaluated as oxygen reduction reaction (ORR) cathodes for Direct Ethylene Glycol Fuel Cells (DEGFC) applications. As reference, a commercial Pt/C material was also tested. We found that Pt-Pd/MWCNT has high tolerance capability to EG and higher selectivity for the ORR compared to the Pt-alone materials. As a result, the shift in onset potential for the ORR, E{sub onset}, at Pt-Pd/MWCNT was considerably smaller than the shift at Pt/MWCNT or Pt/C. The average particle size (from XRD) was 3.5 and 4 nm for Pt/MWCNT and Pt-Pd/MWCNT, respectively. A moderate degree of alloying was determined for the Pt-Pd material. An advantageous application of Pt-Pd electrocatalysts should be in DEGFCs. (author)

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

    Science.gov (United States)

    Hou, Linxi; Qiu, Huajun

    2012-10-01

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

  5. Localized Pd overgrowth on cubic Pt nanocrystals for enhanced electrocatalytic oxidation of formic acid.

    Science.gov (United States)

    Lee, Hyunjoo; Habas, Susan E; Somorjai, Gabor A; Yang, Peidong

    2008-04-23

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

  6. Electrochemically deposited Pd-Pt and Pd-Au codeposits on graphite electrodes for electrocatalytic H2O2 reduction.

    Science.gov (United States)

    Nagaiah, Tharamani Chikka; Schäfer, Dominik; Schuhmann, Wolfgang; Dimcheva, Nina

    2013-08-20

    Improved electrocatalytic activity and selectivity for the reduction of H2O2 were obtained by electrodepositing Pd-Pt and Pd-Au on spectrographic graphite from solutions containing salts of the two metals at varying ratio. The electrocatalytic activity of the resulting binary codeposits for H2O2 reduction was evaluated by means of the redox-competition mode of scanning electrochemical microscopy (SECM) and voltammetric methods. In a potential range from 0 to -600 mV (vs. Ag/AgCl/3 M KCl) at pH 7.0 in 0.1 M phosphate citrate buffer, the electrocatalytic activity of both Pd-Pt and Pd-Au codeposits was substantially improved as compared with the identically deposited single metals suggesting an electrocatalytic synergy of the codeposits. Pd-Pt and Pd-Au codeposits were characterized by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). Codepositing with Au caused a change of hedgehog-like shaped Pd nanoparticles into cauliflower-like nanoparticles with the particle size decreasing with increasing Au concentration. Codepositing Pd with Pt caused the formation of oblong structures with the size initially increasing with increasing Pt content. However, the particle size decreases with further increase in Pt concentration. The improved electrocatalytic capability for H2O2 reduction of the Pd-Pt electrodeposits on graphite was further demonstrated by immobilizing glucose oxidase as a basis for the development of an interference-free amperometric glucose biosensor.

  7. {sup 27}Al and {sup 45}Sc NMR spectroscopy on ScT{sub 2}Al and Sc(T{sub 0.5}T{sup '}{sub 0.5}){sub 2}Al (T = T{sup '} = Ni, Pd, Pt, Cu, Ag, Au) Heusler phases and superconductivity in Sc(Pd{sub 0.5}Au{sub 0.5}){sub 2}Al

    Energy Technology Data Exchange (ETDEWEB)

    Benndorf, Christopher [Institut fuer Anorganische und Analytische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany); Institut fuer Physikalische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany); Niehaus, Oliver; Janka, Oliver [Institut fuer Anorganische und Analytische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany); Eckert, Hellmut [Institut fuer Physikalische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany)

    2015-02-15

    The intermetallic Heusler compounds with ScT{sub 2}Al and Sc(T{sub 0.5}T{sup '}{sub 0.5}){sub 2}Al composition with T = T{sup '} = Ni, Pd, Pt, Cu, Ag, Au were synthesized from the elements by arc melting. They crystallize in the cubic MnCu{sub 2}Al type structure, space group Fm anti 3m. The unit cell parameters were determined by powder X-ray diffraction and the structure of Sc(Pd{sub 0.5}Au{sub 0.5}){sub 2}Al was refined on the basis of single-crystal X-ray diffraction. While the majority of the compounds show Pauli-paramagnetism, ScAu{sub 2}Al and the newly synthesized solid solution Sc(Pd{sub 0.5}Au{sub 0.5}){sub 2}Al exhibit superconductivity with transition temperatures of T{sub C} = 4.4 K and T{sub C} = 3.0(1) K, respectively. The superconducting state of Sc(Pd{sub 0.5}Au{sub 0.5}){sub 2}Al was also investigated by electrical resistivity measurements. All the synthesized compounds were furthermore studied by {sup 27}Al and {sup 45}Sc MAS-NMR spectroscopy. The resonance shifts of the synthesized compounds were determined and in Sc(Pd{sub 1-x}Au{sub x}){sub 2}Al a linear relationship between the resonance shifts and the composition was found. Line broadening effects and enhanced quadrupolar interaction strengths observed in the mixed samples can be attributed to the effect of Pd/Au mixing on the 8c Wyckoff site. The NMR spectroscopic data give no clear evidence for or against Sc/Al site disordering. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

    Science.gov (United States)

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

    2014-05-01

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

  9. Partial Thermodynamic Properties of gamma-(Ni,Pt)3Al in the Ni-Al-Pt System (Preprint)

    Science.gov (United States)

    2006-02-01

    phases belonging to the Cu family, Journal of Alloys and Compounds , 353, 2003, 207. 4. J. Kamm, W. Milligan, Phase stability in (Ni, Pt)3Al alloys...in the Al-Ni-Ru system by direct reaction synthesis calorimetry, Journal of Alloys and Compounds , 403(1-2), 2005, 217-222. 15 Tables Table 1

  10. A first-principle calculation of sulfur oxidation on metallic Ni(111) and Pt(111), and bimetallic Ni@Pt(111) and Pt@Ni(111) surfaces.

    Science.gov (United States)

    Yeh, Chen-Hao; Ho, Jia-Jen

    2012-09-17

    Sulfur, a pollutant known to poison fuel-cell electrodes, generally comes from S-containing species such as hydrogen sulfide (H(2)S). The S-containing species become adsorbed on a metal electrode and leave atomic S strongly bound to the metal surface. This surface sulfur is completely removed typically by oxidation with O(2) into gaseous SO(2). According to our DFT calculations, the oxidation of sulfur at 0.25 ML surface sulfur coverage on pure Pt(111) and Ni(111) metal surfaces is exothermic. The barriers to the formation of SO(2) are 0.41 and 1.07 eV, respectively. Various metals combined to form bimetallic surfaces are reported to tune the catalytic capabilities toward some reactions. Our results show that it is more difficult to remove surface sulfur from a Ni@Pt(111) surface with reaction barrier 1.86 eV for SO(2) formation than from a Pt@Ni(111) surface (0.13 eV). This result is in good agreement with the statement that bimetallic surfaces could demonstrate more or less activity than to pure metal surfaces by comparing electronic and structural effects. Furthermore, by calculating the reaction free energies we found that the sulfur oxidation reaction on the Pt@Ni(111) surface exhibits the best spontaneity of SO(2) desorption at either room temperature or high temperatures.

  11. Adhesion and bonding of Pt/Ni and Pt/Co overlayers: Density functional calculations

    Science.gov (United States)

    Cabeza, Gabriela F.; Castellani, Norberto J.; Légaré, Pierre

    2006-04-01

    The electronic and energetic properties of bimetallic surfaces Pt/Ni(111) and Pt/Co(111) are examined using the FP-LAPW (Full-PotentialLinearized Augmented Plane Wave) method by means of spin-polarized and non-polarized calculations. We present both the results of the shifts in the d-band centers when one metal (Pt) is pseudomorfically deposited on another with smaller lattice constant (Ni, Co) and those corresponding to the surface and adhesion energies. The surface is modeled by a seven layer slab separated in z direction by a vacuum region of six substrate layers. The results obtained for pure Ni, Co and Pt surfaces are presented in order to compare with experimental and theoretical data reported in the literature

  12. Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO2 reforming of methane

    KAUST Repository

    Biausque, Gregory

    2015-09-24

    Embodiments of the present disclosure provide for NiPt nanoparticles, compositions and supports including NiPt nanoparticles, methods of making NiPt nanoparticles, methods of supporting NiPt nanoparticles, methods of using NiPt nanoparticles, and the like.

  13. Dissociative adsorption of methane on surface oxide structures of Pd-Pt alloys

    CERN Document Server

    Dianat, Arezoo; Ciacchi, Lucio Colombi; Pompe, Wolfgang; Cuniberti, Gianaurelio; Bobeth, Manfred; 10.1021/jp905689t

    2010-01-01

    The dissociative adsorption of methane on variously oxidized Pd, Pt and Pd-Pt surfaces is investigated using density-functional theory, as a step towards understanding the combustion of methane on these materials. For Pd-Pt alloys, models of surface oxide structures are built on the basis of known oxides on Pd and Pt. The methane adsorption energy presents large variations depending on the oxide structure and composition. Adsorption is endothermic on the bare Pd(111) metal surface as well as on stable thin layer oxide structures such as the ($\\sqrt{5}\\times\\sqrt{5}$) surface oxide on Pd(100) and the PtO$_2$-like oxide on Pt(111). Instead, large adsorption energies are obtained for the (100) surface of bulk PdO, for metastable mixed Pd$_{1-x}$Pt$_x$O$_{4/3}$ oxide layers on Pt(100), and for Pd-Pt(111) surfaces covered with one oxygen monolayer. In the latter case, we find a net thermodynamic preference for a direct conversion of methane to methanol, which remains adsorbed on the oxidized metal substrates via w...

  14. Pd-Pt Catalysts on Fluorinated Alumina Support Studied by X-Ray Absorption Fine Structure

    Science.gov (United States)

    Yan, Wensheng; Li, Zhongrui; Wei, Zheng; Wei, Shiqiang

    2007-02-01

    A series of bi-metallic Pd-Pt catalysts supported on both pristine and fluorinated alumina supports were investigated with x-ray absorption spectroscopy. It was found that Pd and Pt form small alloy particles on the pristine alumina support; the composition and the cluster size of the PdPt bimetallic alloys, and the electronic properties of the metals were significantly altered on the fluorinated support. The remarkable increase in sulfur tolerance of the PdPt metallic clusters supported on the fluorine pretreated alumina can be attributed to an electronic depletion of the metals, large particle size and direct participation of the acid sites in the reaction.

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

    Science.gov (United States)

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

    2013-10-01

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

  16. Carbon supported Pd-Ni and Pd-Ru-Ni nanocatalysts for the alkaline direct ethanol fuel cell (DEFC)

    CSIR Research Space (South Africa)

    Mathe, MK

    2011-08-01

    Full Text Available Carbon supported Pd-Ni and Pd-Ru-Ni nanocatalysts were prepared by the chemical reduction method, using sodium borohydride and ethylene glycol mixture as the reducing agent. The catalytic activity towards ethanol electro-oxidation in alkaline medium...

  17. Single-phase aqueous approach toward Pd sub-10 nm nanocubes and Pd-Pt heterostructured ultrathin nanowires.

    Science.gov (United States)

    Yuan, Qiang; Zhuang, Jing; Wang, Xun

    2009-11-21

    Monodisperse, highly-selective sub-10 nm Pd and Rh nanocubes have been successfully synthesized and, for the first time, bimetallic Pd-Pt heterostructured ultrathin nanowires have been achieved through using Pd nanocubes as seeds by a one-pot, single-phase aqueous method.

  18. Structure Changes of Pd-Ni Alloy and Catchment Gauzes%Pd-Ni合金及其捕集网的结构变化

    Institute of Scientific and Technical Information of China (English)

    宁远涛

    2001-01-01

    采用扫描电镜(SEM)、微区域电子探针(EPMA)和X射线衍射(XRD)等分析方法研究了Pd-5Ni合金捕集网在回收铂过程中形貌和结构的变化。该过程是由气相沉积(吸附)和扩散—再合金化控制的再结晶过程,并导致Pd(Ni)合金网发生结构再造。原始的Pd(Ni)固溶体转变为Pd(Pt)固溶体,Ni逐渐被氧化形成NiO直至Ni完全消失。Pd(Pt)固溶体晶格常数随Pt/Pd比值增大。在再结晶新的晶面和晶体形成过程中,阶梯式(层状)生长是主要机制;而在新晶体长大过程中,螺旋式生长具有重要作用。%The structure reconstruction of Pd-Ni alloy catchment gauzes in the platinum recovery process in the nitric acid plant was studied by SEM,EPMA and XRD,etc.It is a recrystallization process controlled by the vapour deposition,difussion and realloying mechanism.The initial Pd(Ni) solid solution turned into Pd(Pt) solid solution,and the lattice parameters of Pd(Pt)solid solution increased with increase of the Pt/Pd ratio.In the formation process of the recrystallization crystals,the ladder-like growth is the main mechanism,and in the growing process of the crystals,the screw growth plays an important role.The real recrystallization crystals are of tetrakaidecahedron structure(l4-faced body)made up of quadrilaterals and hexagones,and are grains ranging from several micrometers to tens of micrometers in size.

  19. Corrosion resistance of amorphous and crystalline Pd40Ni40P20 alloys in aqueous solutions

    DEFF Research Database (Denmark)

    Wu, Y.F.; Chiang, Wen-Chi; Chu, J.;

    2006-01-01

    The corrosion behaviors of amorphous and crystalline Pd40Ni40P20 alloys in various aqueous solutions are reported in this paper. The corrosion resistance of crystalline (annealed) Pd40Ni40P20 is better than that of amorphous Pd40Ni40P20 in various corrosive solutions, due to crystalline Pd40Ni40P20...... and mainly consists of inert Pd5P2, NI3P, Ni2Pd2P and noble Pd phases. These inert and noble properties result in a higher corrosion resistance in crystalline Pd40Ni40P20....

  20. 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.

  1. Molecular Dynamics Simulation Study of Atomic Segregation of (PdPt)147 during the Heating Process

    Science.gov (United States)

    Xiao, X. Y.; Cheng, Z. F.; Xia, J. H.

    Research on the influence of alloy concentration and distribution on bimetallic cluster plays a key role in exploring new structural material. This paper studies the melting process of icosahedral bimetallic cluster (PdPt)147 with different Pt concentrations and different atomic distributions by using molecular dynamics with an embedded atom method. The results indicate that the mixed Pd-Pt cluster shows an irregular phenomenon between 580 and 630 K, i.e. the atomic energy decreases with the increase of temperature. This is because the surface energy of Pd is lower than that of Pt; the decreased energy due to Pd atomic segregation is larger than the increased energy due to heating during the segregation process. In addition, the temperature of Pd atomic segregation is strongly related to Pt concentration. This leads to that Pd atoms prefer to remain on the surface even after the cluster melted.

  2. Synergistic Effects in CNTs-PdAu/Pt Trimetallic Nanoparticles with High Electrocatalytic Activity and Stability

    Science.gov (United States)

    Cai, Xin-Lei; Liu, Chang-Hai; Liu, Jie; Lu, Ying; Zhong, Ya-Nan; Nie, Kai-Qi; Xu, Jian-Long; Gao, Xu; Sun, Xu-Hui; Wang, Sui-Dong

    2017-10-01

    We present a straightforward physical approach for synthesizing multiwalled carbon nanotubes (CNTs)-PdAu/Pt trimetallic nanoparticles (NPs), which allows predesign and control of the metal compositional ratio by simply adjusting the sputtering targets and conditions. The small-sized CNTs-PdAu/Pt NPs ( 3 nm, Pd/Au/Pt ratio of 3:1:2) act as nanocatalysts for the methanol oxidation reaction (MOR), showing excellent performance with electrocatalytic peak current of 4.4 A mg Pt -1 and high stability over 7000 s. The electrocatalytic activity and stability of the PdAu/Pt trimetallic NPs are much superior to those of the corresponding Pd/Pt and Au/Pt bimetallic NPs, as well as a commercial Pt/C catalyst. Systematic investigation of the microscopic, crystalline, and electronic structure of the PdAu/Pt NPs reveals alloying and charge redistribution in the PdAu/Pt NPs, which are responsible for the promotion of the electrocatalytic performance.

  3. Highly Sensitive Hydrazine Chemical Sensor Based on CNT-PdPt Nanocomposites

    Directory of Open Access Journals (Sweden)

    Sung Phil Kim

    2015-01-01

    Full Text Available Bimetallic PdPt nanoparticles were prepared using the chemical reduction method. The PdPt nanoparticles were successfully deposited on thiolated carbon nanotubes (CNTs to form a CNT-PdPt nanocomposite as an electron mediator for the fabrication of a hydrazine sensor. The PdPt nanoparticles had an average particle size of 2.3 nm and were well dispersed on the surfaces of the CNTs in the prepared CNT-PdPt nanocomposite, as demonstrated using transmission electron microscopy (TEM, energy dispersive X-ray spectroscopy (EDX, and X-ray diffraction (XRD. Based on X-ray photoelectron spectroscopy (XPS results, the estimated proportions of Pd and Pt in the CNT-PdPt nanocomposite were approximately 3.0% and 3.2%, respectively. A fabricated chemical sensor based on CNT-PdPt was found to exhibit better amperometric activity with respect to the hydrazine oxidation reaction than CNT-Pd, CNT-Pt, and commercial Pd/C and Pt/C catalysts. This sensor exhibited a linear range of 0.55–1,200 μM and a detection limit of 0.28 μM (S/N = 3 with a fast response time (within 5 s. Furthermore, the sensor could be used repeatedly for the consecutive detection of hydrazine with good reusability and storage stability. These properties demonstrate that the CNT-PdPt nanocomposite is a promising electron mediator for the fabrication of amperometric hydrazine sensors.

  4. Corrosion resistance of amorphous and crystalline Pd40Ni40P20 alloys in aqueous solutions

    DEFF Research Database (Denmark)

    Wu, Y.F.; Chiang, Wen-Chi; Chu, J.

    2006-01-01

    The corrosion behaviors of amorphous and crystalline Pd40Ni40P20 alloys in various aqueous solutions are reported in this paper. The corrosion resistance of crystalline (annealed) Pd40Ni40P20 is better than that of amorphous Pd40Ni40P20 in various corrosive solutions, due to crystalline Pd40Ni40P20...

  5. Study of hyperfine interactions in intermetallic compounds Gd(Ni,Pd,Cu)In, Tb(Ni,Pd)In, Dy(Ni,Pd)In and Ho(Ni,Pd)In; Estudo de interacoes hiperfinas em compostos intermetalicos Gd(Ni,Pd,Cu)In, Tb(Ni,Pd)In, Dy(Ni,Pd)In e Ho(Ni,Pd)In

    Energy Technology Data Exchange (ETDEWEB)

    Lapolli, Andre Luis

    2006-07-01

    Systematic behavior of magnetic hyperfine field (B{sub hf}) in the intermetallic compounds Gd(Ni,Pd,Cu)In Tb(Ni,Pd)In, Dy(Ni,Pd)In and Ho(Ni,Pd)In was studied by Perturbed Gamma-Gamma Angular Correlation spectroscopy. The measurements of B{sub hf} were carried out at the rare earth atom and in sites using the nuclear probes {sup 140}Ce and {sup 11}'1Cd respectively. The variation of hyperfine field with temperature, in most cases, follows the Brillouin function predicted from the molecular field theory. The hyperfine field values at rare earth atom sites obtained from {sup 140}Ce probe as well as at in sites obtained from {sup 111}Cd probe for each series of compounds were extrapolated to zero Kelvin B{sub hf}(T=0) from these curves. These values were compared with the values of the literature for other compounds containing the same rare earth element and all of them show a linear relationship with the ordering temperature. This indicates that the main contribution to B{sub hf} comes from the conduction electron polarization (CEP) through Fermi contact interaction and the principal mechanism of magnetic interaction in these compounds can be described by the RKKY type interaction. The values of B{sub hf}(T=0) for each family of intermetallic compounds RNiIn and RPdIn when plotted as a function of 4f spin projection of rare earth element also shows a linear relationship. Exceptions are the results for the compounds RNiIn obtained with {sup 111}Cd probe where a small deviation from linearity is observed. The results of the measurements carried out with the {sup 111}Cd probe were also analyzed to obtain the hyperfine parameters of the quadrupole interaction as a function of temperature for RPdln and GdNiIn compounds. The results show that for the compound GdPdIn there might be some Gd-In disorder at high temperature. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Flynn-Sanders, D.

    1990-09-21

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

  7. Preparation and characterization of MgB2 with Pd, Pt and Re doping

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude; Pitillas, A.; Namazkar, Shahla;

    2016-01-01

    of the MgB2 superconductor. Impurity phases are formed by reaction mostly with Mg. The microstructure of the Pt, Pd and Re-based phases depends on the elements. Re-rich particles with large sizes up to 8 μm form, whereas Pt- and Pd-containing impurities are finely dispersed with a particle size that does...

  8. Structural characterization of Pt-Pd and Pd-Pt core-shell nanoclusters at atomic resolution.

    Science.gov (United States)

    Sanchez, Sergio I; Small, Matthew W; Zuo, Jian-min; Nuzzo, Ralph G

    2009-06-24

    We describe the results of a study at atomic resolution of the structures exhibited by polymer-capped monometallic and bimetallic Pt and Pd nanoclusters--models for nanoscale material electrocatalysts--as carried out using an aberration-corrected scanning transmission electron microscope (STEM). The coupling of sub-nanometer resolution with Z-contrast measurements provides unprecedented insights into the atomic structures and relative elemental speciation of Pt and Pd within these clusters. The work further defines the nature of deeply quenched states that prevent facile conversions of core-shell motifs to equilibrium alloys and the nature of nonidealities such as twinning (icosahedral cores) and atomic segregation that these structures can embed. The nature of the facet structure present in these model systems is revealed by theory directed modeling in which experimental intensity profiles obtained in Z-contrast measurements at atomic resolution are compared to simulated intensity profiles using theoretically predicted cluster geometries. These comparisons show close correspondences between experiment and model and highlight striking structural complexities in these systems that are compositionally sensitive and subject to amplification by subsequent cluster growth processes. The work demonstrates an empowering competency in nanomaterials research for STEM measurements carried out using aberration corrected microscopes, approaches that hold considerable promise for characterizing the structure of these and other important catalytic materials systems at the atomic scale.

  9. Low Pt-content ternary PdCuPt nanodendrites: an efficient electrocatalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-01-01

    Dendritic nanostructures are capturing increasing attentions in electrocatalysis owing to their unique structural features and low density. Herein, we report for the first time bromide ions mediated synthesis of low-Pt-content PdCuPt ternary nanodendrites via galvanic replacement reaction between Pt precursor and PdCu template in aqueous solution. The experimental results show that the ternary PdCuPt nanodendrites present enhanced electrocatalytic performance for oxygen reduction reaction in acid solution compared with commercial Pt/C as well as some state-of-the-art catalysts. In details, the mass activity of the PdCuPt catalyst with optimized composition is 1.73 A/mgPt at 0.85 V vs RHE, which is 14 times higher than that of commercial Pt/C catalyst. Moreover, the long-term stability test demonstrates its better durability in acid solution. After 5k cycles, there is still 70% electrochemical surface area maintained. This method provides an efficient way to synthesize trimetallic alloys with controllable composition and specific structure for oxygen reduction reaction.

  10. Pt-Ni and Pt-M-Ni (M = Ru, Sn Anode Catalysts for Low-Temperature Acidic Direct Alcohol Fuel Cells: A Review

    Directory of Open Access Journals (Sweden)

    Ermete Antolini

    2017-01-01

    Full Text Available In view of a possible use as anode materials in acidic direct alcohol fuel cells, the electro-catalytic activity of Pt-Ni and Pt-M-Ni (M = Ru, Sn catalysts for methanol and ethanol oxidation has been widely investigated. An overview of literature data regarding the effect of the addition of Ni to Pt and Pt-M on the methanol and ethanol oxidation activity in acid environment of the resulting binary and ternary Ni-containing Pt-based catalysts is presented, highlighting the effect of alloyed and non-alloyed nickel on the catalytic activity of these materials.

  11. Platinum-group minerals from the Jinbaoshan Pd-Pt deposit, SW China: evidence for magmatic origin and hydrothermal alteration

    Science.gov (United States)

    Wang, Christina Yan; Prichard, Hazel M.; Zhou, Mei-Fu; Fisher, Peter C.

    2008-09-01

    The Jinbaoshan Pt-Pd deposit in Yunnan, SW China, is hosted in a wehrlite body, which is a member of the Permian (˜260 Ma) Emeishan Large Igneous Province (ELIP). The deposit is reported to contain one million tonnes of Pt-Pd ore grading 0.21% Ni and 0.16% Cu with 3.0 g/t (Pd + Pt). Platinum-group minerals (PGM) mostly are ˜10 μm in diameter, and are commonly Te-, Sn- and As-bearing, including moncheite (PtTe2), atokite (Pd3Sn), kotulskite (PdTe), sperrylite (PtAs2), irarsite (IrAsS), cooperite (PtS), sudburyite (PdSb), and Pt-Fe alloy. Primary rock-forming minerals are olivine and clinopyroxene, with clinopyroxene forming anhedral poikilitic crystals surrounding olivine. Primary chromite occurs either as euhedral grains enclosed within olivine or as an interstitial phase to the olivine. However, the intrusion has undergone extensive hydrothermal alteration. Most olivine grains have been altered to serpentine, and interstitial clinopyroxene is often altered to actinolite/tremolite and locally biotite. Interstitial chromite grains are either partially or totally replaced by secondary magnetite. Base-metal sulfides (BMS), such as pentlandite and chalcopyrite, are usually interstitial to the altered olivine. PGM are located with the BMS and are therefore also interstitial to the serpentinized olivine grains, occurring within altered interstitial clinopyroxene and chromite, or along the edges of these minerals, which predominantly altered to actinolite/tremolite, serpentine and magnetite. Hydrothermal fluids were responsible for the release of the platinum-group elements (PGE) from the BMS to precipitate the PGM at low temperature during pervasive alteration. A sequence of alteration of the PGM has been recognized. Initially moncheite and atokite have been corroded and recrystallized during the formation of actinolite/tremolite, and then, cooperite and moncheite were altered to Pt-Fe alloy where they are in contact with serpentine. Sudburyite occurs in veins

  12. The synthesis of PdPt/carbon paper via surface limited redox replacement reactions for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Motsoeneng, RG

    2015-09-01

    Full Text Available Surface-limited redox replacement reactions using the electrochemical atomic layer deposition (EC-ALD) technique were used to synthesize PdPt bimetallic electrocatalysts on carbon paper substrate. Electrocatalysts having different Pd:Pt ratio were...

  13. PT L 3 near edge structure of halogen-bridged mixed-valence pt complexes and pd-pt mixed-metal complexes

    Science.gov (United States)

    Tanino, H.; Oyanagi, H.; Yamashita, M.; Kobayashi, K.

    1985-03-01

    X-ray absorption near edge structure (XANES) of halogen-bridged mixed-valence Pt complexes and halogen-bridged Pd-Pt mixed-metal complexes have been measured using synchrotron radiation with a high energy resolution. In Pd-Pt mixed metal complexes, we demonstrate that the degree of the valence is estimated from the intensity of the white line at the Pt L 3 edge. In the mixed-valence complexes, the electron system is proved to be the Peierls insulator with a charge density wave of renormalized d electrons of Pt, where the total valence of Pt IV- and Pt 11 is conserved without excess electrons from ligands or anions.

  14. Molecular dynamics simulation study of the melting of Pd-Pt nanoclusters

    Science.gov (United States)

    Sankaranarayanan, Subramanian K. R. S.; Bhethanabotla, Venkat R.; Joseph, Babu

    2005-05-01

    Bimetallic nanoclusters are of interest because of their utility in catalysis and sensors. The thermal characteristics of bimetallic Pt-Pd nanoclusters of different sizes and compositions were investigated through molecular dynamics simulations using quantum Sutton-Chen (QSC) many-body potentials. Monte Carlo simulations employing the bond order simulation model were used to generate minimum energy configurations, which were utilized as the starting point for molecular dynamics simulations. The calculated initial configurations of the Pt-Pd system consisted of surface segregated Pd atoms and a Pt-rich core. Melting characteristics were studied by following the changes in potential energy and heat capacity as functions of temperature. Structural changes accompanying the thermal evolution were studied by the bond order parameter method. The Pt-Pd clusters exhibited a two-stage melting: surface melting of the external Pd atoms followed by homogeneous melting of the Pt core. These transitions were found to depend on the composition and size of the nanocluster. Melting temperatures of the nanoclusters were found to be much lower than those of bulk Pt and Pd. Bulk melting temperatures of Pd and Pt simulated using periodic boundary conditions compare well with experimental values, thus providing justification for the use of QSC potentials in these simulations. Deformation parameters were calculated to characterize the structural evolution resulting from diffusion of Pd and Pt atoms. The results indicate that in Pd-Pt clusters, Pd atoms prefer to remain at the surface even after melting. In addition, Pt also tends to diffuse to the surface after melting due to reduction of its surface energy with temperature. This mixing pattern is different from those reported in some of the earlier studies on melting of bimetallics.

  15. Reversal mechanism of submicron patterned CoNi/Pt multilayers

    NARCIS (Netherlands)

    Haast, M.A.M.; Schuurhuis, J.R.; Abelmann, L.; Lodder, J.C.; Popma, Th.J.A.

    1998-01-01

    With laser interference lithography Co50Ni50/Pt multilayers with perpendicular magnetic anisotropy have been patterned into regular matrices of submicron sized dots. Their magnetic properties have been studied with Vibrating Sample Magnetometry. Compared to continuous multilayers (Hc=15 kA/m) the co

  16. Ternary Pt-Ru-Ni catalytic layers for methanol electrooxidation prepared by electrodeposition and galvanic replacement

    OpenAIRE

    Athanasios ePapaderakis; Nikolaos ePliatsikas; Chara eProchaska; Kalliopi M. Papazisi; Balomenou, Stella P.; Dimitrios eTsiplakides; Panagiotis ePatsalas; Sotiris eSotiropoulos

    2014-01-01

    Ternary Pt-Ru-Ni deposits on glassy carbon substrates, Pt-Ru(Ni)/GC, have been formed by initial electrodeposition of Ni layers onto glassy carbon electrodes, followed by their partial exchange for Pt and Ru, upon their immersion into equimolar solutions containing complex ions of the precious metals. The overall morphology and composition of the deposits has been studied by SEM microscopy and EDS spectroscopy. Continuous but nodular films have been confirmed, with a Pt ÷ Ru ÷ Ni % bulk atomi...

  17. Controlled synthesis of Pd-Pt alloy hollow nanostructures with enhanced catalytic activities for oxygen reduction.

    Science.gov (United States)

    Hong, Jong Wook; Kang, Shin Wook; Choi, Bu-Seo; Kim, Dongheun; Lee, Sang Bok; Han, Sang Woo

    2012-03-27

    Pd-Pt alloy nanocrystals (NCs) with hollow structures such as nanocages with porous walls and dendritic hollow structures and Pd@Pt core-shell dendritic NCs could be selectively synthesized by a galvanic replacement method with uniform Pd octahedral and cubic NCs as sacrificial templates. Fine control over the degree of galvanic replacement of Pd with Pt allowed the production of Pd-Pt NCs with distinctly different morphologies. The synthesized hollow NCs exhibited considerably enhanced oxygen reduction activities compared to those of Pd@Pt core-shell NCs and a commercial Pt/C catalyst, and their electrocatalytic activities were highly dependent on their morphologies. The Pd-Pt nanocages prepared from octahedral Pd NC templates exhibited the largest improvement in catalytic performance. We expect that the present work will provide a promising strategy for the development of efficient oxygen reduction electrocatalysts and can also be extended to the preparation of other hybrid or hetero-nanostructures with desirable morphologies and functions. © 2012 American Chemical Society

  18. Carbon-supported Pd-Pt cathode electrocatalysts for proton exchange membrane fuel cells

    Science.gov (United States)

    Tang, Yongfu; Zhang, Huamin; Zhong, Hexiang; Xu, Ting; Jin, Hong

    A series of carbon-supported Pd-Pt alloy (Pd-Pt/C) catalysts for oxygen reduction reaction (ORR) with low-platinum content are synthesized via a modified sodium borohydride reduction method. The structure of as-prepared catalysts is characterized by powder X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements. The prepared Pd-Pt/C catalysts with alloy form show face-centered-cubic (FCC) structure. The metal particles of Pd-Pt/C catalysts with mean size of around 4-5 nm are uniformly dispersed on the carbon support. The electrocatalytic activities for ORR of these catalysts are investigated by rotating disk electrode (RDE), cyclic voltammetry (CV), single cell measurements and electrochemical impedance spectra (EIS) measurements. The results suggest that the electrocatalytic activities of Pd-Pt/C catalysts with low platinum are comparable to that of the commercial Pt/C with the same metal loading. The maximum power density of MEA with a Pd-Pt/C catalyst, the Pd/Pt mass ratio of which is 7:3, is about 1040 mW cm -2.

  19. Mixed-PtPd-shell PtPdCu nanoparticle nanotubes templated from copper nanowires as efficient and highly durable electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hui-Hui; Cui, Chun-Hua; Zhao, Shuo; Yao, Hong-Bin; Gao, Min-Rui; Fan, Feng-Jia; Yu, Shu-Hong [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230026 (China); Div. of Nanomaterials and Chemistry, Heifei National Lab. for Physical, Sciences at Microscale (China)

    2012-10-15

    The controlled synthesis of mixed-PtPd-shell PtPdCu-alloy nanoparticle nanotubes (ANNTs) is demonstrated by galvanic displacement with partially sacrificial copper-nanowire templates, and following the electrochemical leaching of the non-noble metal Cu in the acidic electrolyte. These core-shell catalysts significantly reduce the amount of expensive Pt and highly improve the electrocatalytic activity and durability through their modified electronic structure, atomic distribution, and 1D structure property. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Formation and Characterization of Pd, Pt and Pd-Pt Alloy Films on Polyimide by Catalyst-Enhanced Chemical Vapor Deposition

    Institute of Scientific and Technical Information of China (English)

    ZHOU Jinlan; CHENG Yinhua; Yousuf Hamadan; YU Kaichao

    2007-01-01

    Platinum, palladium and their alloy films on polyimide were formed by catalyst-enhanced chemical vapor deposition (CVD) in the carrier gas (N2, O2) at 220-300 ℃ under reduced pressure and normal pressure. The deposition of palladium complexes [ Pd((η3-allyl)(hfac) and Pd(hfac)2 ] gives pure palladium film,while the deposition of platinum needs the enhancement of palladium complex by mixing precursor platinum complex Pt(COD)Me2 and palladium complex in the same chamber. The co-deposition of Pd and Pt metals was used for the deposition of alloy films. During the CVD of palladium-platinum alloy, the Pd/Pt atomic ratios vary under different co-deposition conditions. These metal films were characterized by XPS and SEM, and show a good adhesive property.

  1. Pt-Ni and Pt-Co Catalyst Synthesis Route for Fuel Cell Applications

    Science.gov (United States)

    Firdosy, Samad A.; Ravi, Vilupanur A.; Valdez, Thomas I.; Kisor, Adam; Narayan, Sri R.

    2013-01-01

    Oxygen reduction reactions (ORRs) at the cathode are the rate-limiting step in fuel cell performance. The ORR is 100 times slower than the corresponding hydrogen oxidation at the anode. Speeding up the reaction at the cathode will improve fuel cell efficiency. The cathode material is generally Pt powder painted onto a substrate (e.g., graphite paper). Recent efforts in the fuel cell area have focused on replacing Pt with Pt-X alloys (where X = Co, Ni, Zr, etc.) in order to (a) reduce cost, and (b) increase ORR rates. One of these strategies is to increase ORR rates by reducing the powder size, which would result in an increase in the surface area, thereby facilitating faster reaction rates. In this work, a process has been developed that creates Pt-Ni or Pt-Co alloys that are finely divided (on the nano scale) and provide equivalent performance at lower Pt loadings. Lower Pt loadings will translate to lower cost. Precursor salts of the metals are dissolved in water and mixed. Next, the salt mixtures are dried on a hot plate. Finally, the dried salt mixture is heattreated in a furnace under flowing reducing gas. The catalyst powder is then used to fabricate a membrane electrode assembly (MEA) for electrochemical performance testing. The Pt- Co catalyst-based MEA showed comparable performance to an MEA fabri cated using a standard Pt black fuel cell catalyst. The main objective of this program has been to increase the overall efficiencies of fuel cell systems to support power for manned lunar bases. This work may also have an impact on terrestrial programs, possibly to support the effort to develop a carbon-free energy source. This catalyst can be used to fabricate high-efficiency fuel cell units that can be used in space as regenerative fuel cell systems, and terrestrially as primary fuel cells. Terrestrially, this technology will become increasingly important when transition to a hydrogen economy occurs.

  2. Numerical Prediction of the Thermodynamic Properties of Ternary Al-Ni-Pd Alloys

    Science.gov (United States)

    Zagula-Yavorska, Maryana; Romanowska, Jolanta; Kotowski, Sławomir; Sieniawski, Jan

    2016-01-01

    Thermodynamic properties of ternary Al-Ni-Pd system, such as exGAlNPd, µAl(AlNiPd), µNi(AlNiPd) and µPd(AlNiPd) at 1,373 K, were predicted on the basis of thermodynamic properties of binary systems included in the investigated ternary system. The idea of predicting exGAlNiPd values was regarded as calculation of values of the exG function inside a certain area (a Gibbs triangle) unless all boundary conditions, that is values of exG on all legs of the triangle are known (exGAlNi, exGAlPd, exGNiPd). This approach is contrary to finding a function value outside a certain area, if the function value inside this area is known. exG and LAl,Ni,Pd ternary interaction parameters in the Muggianu extension of the Redlich-Kister formalism were calculated numerically using the Excel program and Solver. The accepted values of the third component xx differed from 0.01 to 0.1 mole fraction. Values of LAlNiPd parameters in the Redlich-Kister formula are different for different xx values, but values of thermodynamic functions: exGAlNiPd, µAl(AlNiPd), µNi(AlNiPd) and µPd(AlNiPd) do not differ significantly for different xx values. The choice of xx value does not influence the accuracy of calculations.

  3. Chemical bonding in transition metal complexes with beryllium ligands [(PMe(3))(2)M-BeCl(2)], [(PMe(3))(2)M-BeClMe], and [(PMe(3))(2)M-BeMe(2)] (M = Ni, Pd, Pt).

    Science.gov (United States)

    Parameswaran, Pattiyil; Frenking, Gernot

    2010-08-26

    The equilibrium geometries and bond dissociation energies of the 14 valence electron (VE) complexes [(PMe(3))(2)M-BeCl(2)], [(PMe(3))(2)M-BeClMe], and [(PMe(3))(2)M-BeMe(2)] with M = Ni, Pd, and Pt have been calculated using density functional theory at the BP86/TZ2P level. The nature of the M-Be bond was analyzed with the NBO charge decomposition analysis and the EDA energy decomposition analysis. The theoretical results predict the equilibrium structures with a T-shaped geometry at the transition metal where the PMe(3) ligands are in the axial positions. The calculated bond dissociation energies show that the M-E bond strengths are in the range of donor-acceptor complexes of divalent beryllium compounds with ammonia. The bond strength decreases when the substituent at beryllium changes from Cl to CH(3). The NBO analysis shows a negative charge at the BeX(2) fragment, which indicates a net charge flow from the transition metal fragment to the beryllium fragment. The energy decomposition analysis of the M-Be bonds suggests two donor-acceptor bonds with sigma and pi symmetry where the transition metal fragment is a double donor with respect to the beryllium ligand. The pi component of the [Ni]-->BeXX' donation is much smaller than the sigma component.

  4. Tailoring of Pd-Pt bimetallic clusters with high stability for oxygen reduction reaction

    Science.gov (United States)

    Cheng, Daojian; Wang, Wenchuan

    2012-03-01

    The composition-dependent equilibrium structure and thermal stability of Pd-Pt clusters with the size of 55 atoms, and CO, O, OH, and O2 adsorption on these clusters have been studied using molecular simulation based on the Gupta empirical potential and density functional theory (DFT) calculations. It is found that Pd43Pt12 with a three-shell onionlike structure (TS-cluster) exhibits the highest relative stability in both DFT and Gupta levels and also the highest melting point at the Gupta level among these Pd-Pt clusters. In addition, the Pd43Pt12 TS-cluster possesses the weakest CO, O, OH, and O2 adsorption strength, compared to the Pt55, Pd55, and Pd13Pt42 clusters, indicating good catalytic activities toward the oxygen reduction reaction (ORR) among these Pd-Pt clusters considered. We expect that this kind of DFT-guided strategy by controlling the composition could provide a simple way for possibly searching new electrocatalysts.

  5. Effect of NiO crystallinity on forming characteristics in Pt/NiO/Pt cells as resistive switching memories

    Science.gov (United States)

    Nishi, Yusuke; Kimoto, Tsunenobu

    2016-09-01

    Resistive switching (RS) in metal/oxide/metal stack structures plays a key role in resistive RAM. The formation and rupture of conductive filaments have been widely accepted as an origin of RS mechanism especially in binary transition metal oxides. Forming exhibits some analogies with a dielectric breakdown of SiO2 thin films. In this study, Time-Dependent Forming (TDF) characteristics of Pt/NiO/Pt stack structures have been investigated. The results revealed that the formation of conductive filaments at the forming process by applying constant voltage followed a weakest-link theory and that the weakest spots were almost randomly distributed in NiO thin films according to the Poisson statistics. Furthermore, the distribution of TDF characteristics depends on NiO crystallinity. A small variation of initial resistance tends to result in a large variation of time to forming and vice versa.

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

    Science.gov (United States)

    Cheng, Daojian; Huang, Shiping; Wang, Wenchuan

    2006-11-01

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

  7. Ternary Pt-Ru-Ni catalytic layers for methanol electrooxidation prepared by electrodeposition and galvanic replacement

    Directory of Open Access Journals (Sweden)

    Athanasios ePapaderakis

    2014-06-01

    Full Text Available Ternary Pt-Ru-Ni deposits on glassy carbon substrates, Pt-Ru(Ni/GC, have been formed by initial electrodeposition of Ni layers onto glassy carbon electrodes, followed by their partial exchange for Pt and Ru, upon their immersion into equimolar solutions containing complex ions of the precious metals. The overall morphology and composition of the deposits has been studied by SEM microscopy and EDS spectroscopy. Continuous but nodular films have been confirmed, with a Pt÷Ru÷Ni % bulk atomic composition ratio of 37÷12÷51 (and for binary Pt-Ni control systems of 47÷53. Fine topographical details as well as film thickness have been directly recorded using AFM microscopy. The composition of the outer layers as well as the interactions of the three metals present have been studied by XPS spectroscopy and a Pt÷Ru÷Ni % surface atomic composition ratio of 61÷12÷27 (and for binary Pt-Ni control systems of 85÷15 has been found, indicating the enrichment of the outer layers in Pt; a shift of the Pt binding energy peaks to higher values was only observed in the presence of Ru and points to an electronic effect of Ru on Pt. The surface electrochemistry of the thus prepared Pt-Ru(Ni/GC and Pt(Ni/GC electrodes in deaerated acid solutions (studied by cyclic voltammetry proves the existence of a shell consisting exclusively of Pt-Ru or Pt. The activity of the Pt-Ru(Ni deposits towards methanol oxidation (studied by slow potential sweep voltammetry is higher from that of the Pt(Ni deposit and of pure Pt; this enhancement is attributed both to the well-known Ru synergistic effect due to the presence of its oxides but also (based on the XPS findings to a modification effect of Pt electronic properties.

  8. Structural transition and melting of onion-ring Pd Pt bimetallic clusters

    Science.gov (United States)

    Cheng, Daojian; Cao, Dapeng

    2008-08-01

    We use canonical Monte Carlo simulations to study the melting of icosahedral and decahedral onion-ring Pd-Pt bimetallic clusters consisting of 147 atoms. Structural transition from decahedron to icosahedron-like is found for the decahedral onion-ring 147-atom Pd-Pt cluster before melting. Also, the melting point of the decahedral onion-ring 147-atom Pd-Pt cluster is lower than the corresponding icosahedral cluster. In addition, at the higher temperatures after melting, the four-shell onion-ring structure becomes unstable, and can be transformed into the three-shell onion-like structure.

  9. Surface structure and relaxation during the oxidation of carbon monoxide on Pt Pd bimetallic surfaces

    Science.gov (United States)

    Lucas, C. A.; Markovic, N. M.; Ball, M.; Stamenkovic, V.; Climent, V.; Ross, P. N.

    2001-05-01

    The atomic structure and surface relaxation of Pd monolayer on Pt(1 1 1) has been studied by surface X-ray scattering, in an aqueous environment under electrostatic potential control, during the adsorption and oxidation of carbon monoxide. The results show that the Pd-Pt layer spacing contracts at the onset of CO oxidation before the Pd adlayer forms an oxide structure that is incommensurate with the Pt lattice. Both the oxide formation and the lattice contraction are fully reversible over many cycles of the applied electrode potential.

  10. Graphene supported nano particles of Pt-Ni for CO oxidation

    Science.gov (United States)

    Zhang, Cheng; Lv, Wei; Yang, Quanhong; Liu, Yuan

    2012-08-01

    In this study, a series of graphene supported Pt, Ni and Pt-Ni nano particles were successfully synthesized by a simple impregnation method. The resultant composites were characterized using SEM, XRD, HRTEM, XPS and TPR techniques and their catalytic performance for the oxidation of carbon monoxide was tested. It was shown that in the prepared metal/graphene composite, metal particles were highly dispersed on the graphene sheets (GS) with an average particle size of 1-3 nm. The results of catalytic performance tests indicate that the activity decreases in the order of Pt-Ni/GS, Pt/GS and Ni/GS. In the sample of Pt-Ni/GS, Pt-Ni alloy was formed, which contributed to the high activity of Pt-Ni/GS for CO oxidation.

  11. Oxide Scales Formed on NiTi and NiPtTi Shape Memory Alloys

    Science.gov (United States)

    Smialek, James L.; Garg, Anita; Rogers, Richard B.; Noebe, Ronald D.

    2011-01-01

    Ni-49Ti and Ni-30Pt-50Ti (at.%) shape memory alloys were oxidized isothermally in air over the temperature range of 500 to 900 C. The microstructure, composition, and phase content of the scales were studied by SEM, EDS, XRD, and metallography. Extensive plan view SEM/EDS identified various features of intact or spalled scale surfaces. The outer surface of the scale was a relatively pure TiO2 rutile structure, typified by a distinct highly striated and faceted crystal morphology. Crystal size increased significantly with temperature. Spalled regions exhibited some porosity and less distinct features. More detailed information was obtained by correlation of SEM/EDS studies of 700 C/100 hr cross-sections with XRD analyses of serial or taper-polishing of plan surfaces. Overall, multiple layers exhibited graded mixtures of NiO, TiO2, NiTiO3, Ni(Ti) or Pt(Ni,Ti) metal dispersoids, Ni3Ti or Pt3Ti depletion zones, and substrate, in that order. The NiTi alloy contained a 3 at.% Fe impurity that appeared in embedded localized Fe-Ti-rich oxides, while the NiPtTi alloy contained a 2 v/o dispersion of TiC that appeared in lower layers. The oxidation kinetics of both alloys (in a previous report) indicated parabolic growth and an activation energy (250 kJ/mole) near those reported in other Ti and NiTi studies. This is generally consistent with TiO2 existing as the primary scale constituent, as described here.

  12. Structural and magnetic properties of Ni/Pt multilayers

    Science.gov (United States)

    Quiroga, Matías A.; Cabeza, Gabriela F.; Castellani, Norberto J.

    2007-10-01

    In this work, the variation of the magnetic moments of the Ni/Pt multilayers are studied using the linearized augmented plane waves (LAPW) method in the framework of the density functional theory (DFT) implemented in the version of WIEN2K program. The systems have been modeled by seven layers slab separated in z direction by a vacuum region of four substrate layers. We present the results of the dependence of the magnetic properties with respect to the thickness variation of the different multilayers. The modeling of these systems finds an important empirical support. Experiment and theory show the same trends for the magnetic moments: hybridization effects between Ni and Pt are mostly localized at the interface.

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

    Science.gov (United States)

    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

    2017-02-27

    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. 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

    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.

  15. Correlation between Mechanical Behavior and Actuator-type Performance of Ni-Ti-Pd High-temperature Shape Memory Alloys

    Science.gov (United States)

    Bigelow, Glen S.; Padula, Santo A., II; Garg, Anita; Noebe, Ronald D.

    2007-01-01

    High-temperature shape memory alloys in the NiTiPd system are being investigated as lower cost alternatives to NiTiPt alloys for use in compact solid-state actuators for the aerospace, automotive, and power generation industries. A range of ternary NiTiPd alloys containing 15 to 46 at.% Pd has been processed and actuator mimicking tests (thermal cycling under load) were used to measure transformation temperatures, work behavior, and dimensional stability. With increasing Pd content, the work output of the material decreased, while the amount of permanent strain resulting from each load-biased thermal cycle increased. Monotonic isothermal tension testing of the high-temperature austenite and low temperature martensite phases was used to partially explain these behaviors, where a mismatch in yield strength between the austenite and martensite phases was observed at high Pd levels. Moreover, to further understand the source of the permanent strain at lower Pd levels, strain recovery tests were conducted to determine the onset of plastic deformation in the martensite phase. Consequently, the work behavior and dimensional stability during thermal cycling under load of the various NiTiPd alloys is discussed in relation to the deformation behavior of the materials as revealed by the strain recovery and monotonic tension tests.

  16. Structural study of radiolytic catalysts Ni-Ce/Al2O3 and Ni-Pt/Al2O3

    Science.gov (United States)

    Seridi, F.; Chettibi, S.; Keghouche, N.; Beaunier, P.; Belloni, J.

    2017-01-01

    Ni-Ce and Ni-Pt bimetallic catalysts supported over α-Al2O3 are synthesized by using co-impregnation method, and then reduced, each via radiolytic process or thermal H2-treatment. For Ni-Ce/Al2O3, the structural study reveals that Ce is alloyed with Ni as Ce2Ni7 nanoparticles in the radiation-reduced catalysts, while it segregates to the surface in the form of CeO2 in the H2-reduced catalysts. For Ni-Pt/Al2O3 radiolytic catalysts, Ni, Pt, NiPt and Ni3Pt nanoparticles, which size is 3.5 nm, are observed. When the radiation-reduced samples are tested in the benzene hydrogenation, they both display high conversion rate. However, the Ni-Pt/Al2O3 is more efficient than Ni-Ce/Al2O3. The performance of the catalysts is correlated with the high dispersion of the metal and the presence of intermetallic Ni-Pt and Ni-Ce phases. It is compared to that of other radiolytic monometallic/oxide catalysts of the literature.

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

    Science.gov (United States)

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

    2001-10-01

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

  18. Stability and ordering properties of fcc alloys based on Rh, Ir, Pd, and Pt

    Science.gov (United States)

    Turchi, P. E. A.; Drchal, V.; Kudrnovský, J.

    2006-08-01

    Stability properties and ordering trends for the six face-centered cubic binary combinations of the four transition metals Rh, Ir, Pd, and Pt are examined in the context of electronic structure calculations. The method is based on a Green’s function description of the electronic structure of random alloys. Configurational order is treated within the generalized perturbation method. On one hand, the three alloys Pd-Rh, Pd-Ir, and Pt-Ir that have been studied experimentally are confirmed to behave like phase-separating systems. On the other hand, the other three mixtures Pd-Pt, Rh-Ir, and Pt-Rh, for which phase-separating trends have been inferred from experiments, are found to display chemical order with ordering of the (1 0 0) and (11/20) family types and a mixture of both, respectively. The origin of these results is discussed in terms of electronic structure properties.

  19. Energetic and structural analysis of 102-atom Pd-Pt nanoparticles

    Science.gov (United States)

    Pacheco-Contreras, Rafael; Arteaga-Guerrero, Alvaro; Borbon-Gonzalez, Dora Julia; Posada-Amarillas, Alvaro; Schoen, J. Christian; Johnston, Roy L.

    2009-03-01

    We present an extensive study of the structural and energetic changes of 102-atom PdmPt102-m nanoparticles as a function of composition m, where the interatomic interactions are modeled with the many-body Gupta potential. The minimum energy structures are obtained through a genetic algorithm. The excess energy is calculated, as well as the pair distribution function g(r). The radial distribution of the atoms is computed for each composition; the result indicates a multi-layer segregation for some compositions, with a shell growth sequence as follows: a core with a small number of Pd atoms is followed by an intermediate shell of Pt atoms and the external shell consists of Pd atoms. A region where Pd and Pt atoms are mixed is observed between the outermost and intermediate shells. Furthermore, the pure Pd102 and Pt102 nanoparticles have the same structure, while a variety of different structures are observed for the bimetallic clusters.

  20. Fabrication of monometallic (Co, Pd, Pt, Au) and bimetallic (Pt/Au, Au/Pt) thin films with hierarchical architectures as electrocatalysts

    Science.gov (United States)

    Qiu, Cuicui; Zhang, Jintao; Ma, Houyi

    2010-05-01

    Co thin films with novel hierarchical structures were controllably fabricated by simple electrochemical deposition in the absence of hard and soft templates, which were used as sacrificial templates to further prepare noble metal (Pd, Pt, Au) hierarchical micro/nanostructures via metal exchange reactions. SEM characterization demonstrated that the resulting noble metal thin films displayed hierarchical architectures. The as-prepared noble metal thin films could be directly used as the anode catalysts for the electro-oxidation of formic acid. Moreover, bimetallic catalysts (Pt/Au, Au/Pt) fabricated based on the monometallic Au, Pt micro/nanostructures exhibited the higher catalytic activity compared to the previous monometallic catalysts.

  1. Effect of Ni Core Structure on the Electrocatalytic Activity of Pt-Ni/C in Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Vladimir Linkov

    2013-07-01

    Full Text Available Methanol oxidation catalysts comprising an outer Pt-shell with an inner Ni-core supported on carbon, (Pt-Ni/C, were prepared with either crystalline or amorphous Ni core structures. Structural comparisons of the two forms of catalyst were made using transmission electron microscopy (TEM, X-ray diffraction (XRD and X-ray photoelectron spectroscopy (XPS, and methanol oxidation activity compared using CV and chronoamperometry (CA. While both the amorphous Ni core and crystalline Ni core structures were covered by similar Pt shell thickness and structure, the Pt-Ni(amorphous/C catalyst had higher methanol oxidation activity. The amorphous Ni core thus offers improved Pt usage efficiency in direct methanol fuel cells.

  2. Factors influencing the charge distribution on Pd x Pt y bimetallic nanoparticles

    Directory of Open Access Journals (Sweden)

    Carlos M. Celis-Cornejo

    2013-12-01

    Full Text Available We performed quantum mechanics calculations to elucidate the electronic behavior of Pd-Pt bimetallic nanoparticles, using density functional theory, in response to particle size and stoichiometric composition. Using neutrally charged nanoparticles and the Bader charge analysis, we found that external Pd atoms were positively charged, which agrees with previous XPS observations of supported Pd-Pt nanoparticles. From the calculations, unsupported nanoparticles exhibit an electron transfer from Pd to Pt. This result supports the idea that Pd electron-deficient species are possibly responsible of the hydrogenating function of these catalysts, in the hydrodesulfurization of dibenzothiophene. Additionally, it was found that the particle size does not affect the electronic charge distribution and the stoichiometric composition is the factor that greatly influences this property in nanoparticles.

  3. PEFC catalytic properties of Pt - Ni nanoparticles prepared by a plasma-gas-condensation

    Science.gov (United States)

    Umezawa, Michihisa; Ishikawa, Ryoichi; Miyazaki, Reona; Hihara, Takehiko

    2017-01-01

    Pt - Ni nanoparticles were fabricated via the gas phase method. Their performance as anode catalysts for the proton exchange membrane fuel cell was investigated as a function of Ni concentration. The microscopic configurations of the nanoparticles were rather heterogeneous; Pt-rich alloys existed in the core region of particles while a part of the surface layer was composed of the Ni-rich layer. Despite the Ni-rich layer in the shell region, the anode catalyst performance of the Pt - Ni nanoparticles was never deteriorated compared with that of the Pt ones. When the anode catalyst was composed of the Pt nanoparticles, a maximum power density of 112 mW/cm2 was obtained. However, 90% of the power density was still kept even when 40 at. % of Pt was replaced with Ni. The results suggest that a further decrease of Pt composition with maintaining its catalyst performance can be feasible by effective particle dispersing.

  4. East Scandinavian and Noril'sk plume mafic large igneous provinces of Pd-Pt ores: Geological and metallogenic comparison

    Science.gov (United States)

    Mitrofanov, F. P.; Bayanova, T. B.; Korchagin, A. U.; Groshev, N. Yu.; Malitch, K. N.; Zhirov, D. V.; Mitrofanov, A. F.

    2013-09-01

    This paper compares the geological, geophysical, and isotopic geochemical data on the Paleoproterozoic East Scandinavian Pd-Pt province in the Baltic Shield and the Late Paleozoic Noril'sk Pd-Pt province in the Siberian Craton. Both provinces contain large magmatic PGE deposits: low-sulfide in the Baltic Shield and high-sulfide in the Siberian Craton. Multidisciplinary evidence shows that the East Scandinavian mafic large igneous province, which has a plume nature, is intracratonic and was not subjected to the crucial effect of subduction-related and other contamination processes, whereas the Noril'sk province is pericratonic with substantial crustal contamination of the intrusive processes. Low-sulfide Pd-Pt deposits dominate in the East Scandinavian province, while high-sulfide Ni-Cu-PGE deposits play the leading role in the Noril'sk province. The U-Pb, Sm-Nd, and Rb-Sr isotopic data indicate multistage and long-term (tens of millions of years) geological history of mafic large igneous provinces. The plume magmatism with specific geochemistry and metallogeny is probably related to lower mantle sources.

  5. Study of PtPd Bimetallic Nanoparticles for Fuel Cell Applications

    OpenAIRE

    Esparza, Rodrigo; Santoveña,Alan; Ruíz-Baltazar, Alvaro; Angeles-Pascual,Alvaro; Bahena,Daniel; Maya-Cornejo,Jose; Ledesma-García, Janet; Pérez,Ramiro

    2017-01-01

    Bimetallic nanoparticles are of special interest for their potential applications for fuel cells, mainly for portable power applications. Among the bimetallic systems, Pt-Pd bimetallic nanoparticles have received great interest as they can be widely used as effective catalysts for various electrochemical reactions. In this work, Pt-Pd alloy bimetallic nanoparticles were synthesized through a chemical reduction method. The nanoparticles were characterized using aberration-corrected scanning/tr...

  6. Solid-solid transitions in Pd-Pt nanoalloys

    Science.gov (United States)

    Panizon, Emanuele; Ferrando, Riccardo

    2015-11-01

    Solid-solid transformations in Pd-Pt nanoalloys in the size range 32-38 atoms and for different compositions are computationally studied by the superposition approximation to the partition function, and by molecular dynamics simulations. A broad spectrum of transition types is shown to take place. These transition types are: (i) one-to-one type, in which the global minimum, which is dominant at low temperatures, transforms into another single isomer with increasing temperature; (ii) one-to-many type, in which the transition is from a single isomer to a family of other isomers; (iii) many-to-many type, in which the transition is between two different families of isomers; (iv) many-to-one type, in which the effect of vibrational entropy is to greatly reduce the number of relevant structures with increasing temperatures. We provide a rationale for these behaviors, which stem from the interplay between energetics and vibrational entropy effects. The vibrational entropy is explained by analyzing the vibrational density of states and the specific features of the normal modes. Quantum effects on the structural transitions are also discussed.

  7. Pt/Pd electrocatalyst electrons for fuel cells

    Science.gov (United States)

    Stonehart, P.

    1981-11-03

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

  8. Crystallization in Pd40Ni40P20 glass

    DEFF Research Database (Denmark)

    Jiang, Jianzhong; Saksl, K.; Nishiyama, N.

    2002-01-01

    Phase segregation and the effect of pressure on crystallization of bulk and ribbon Pd40Ni40P20 glasses have been studied by means of differential scanning calorimetry (DSC) and x-ray diffraction. The DSC measurements show only one glass transition event in the samples annealed at different...... temperatures in the supercooled liquid region. Phase analyses reveal at least five crystalline phases crystallized from the glass: monoclinic; body-centered tetragonal; orthorhombic; Ni2Pd2P and fcc-(Ni,Pd) solid solution phases. In the pressure range from 0 to 4.2 GPa, the crystallization temperature...... increases with pressure having a slope of 11 K/GPa. The eutectic crystallization reaction mode and crystalline phases formed are unchanged in the pressure range used. The enhancement of the crystallization temperature with increasing pressure in the glass can be explained by the suppression of atomic...

  9. Molybdenum-Doped PdPt@Pt Core-Shell Octahedra Supported by Ionic Block Copolymer-Functionalized Graphene as a Highly Active and Durable Oxygen Reduction Electrocatalyst.

    Science.gov (United States)

    Cho, Kie Yong; Yeom, Yong Sik; Seo, Heun Young; Kumar, Pradip; Lee, Albert S; Baek, Kyung-Youl; Yoon, Ho Gyu

    2017-01-18

    Development of highly active and durable electrocatalysts that can effectively electrocatalyze oxygen reduction reactions (ORR) still remains one important challenge for high-performance electrochemical conversion and storage applications such as fuel cells and metal-air batteries. Herein, we propose the combination of molybdenum-doped PdPt@Pt core-shell octahedra and the pyrene-functionalized poly(dimethylaminoethyl methacrylate)-b-poly[(ethylene glycol) methyl ether methacrylate] ionic block copolymer-functionalized reduced graphene oxide (Mo-PdPt@Pt/IG) to effectively augment the interfacial cohesion of both components using a tunable ex situ mixing strategy. The rationally designed Mo-PdPt@Pt core-shell octahedra have unique compositional benefits, including segregation of Mo atoms on the vertexes and edges of the octahedron and 2-3 shell layers of Pt atoms on a PdPt alloy core, which can provide highly active sites to the catalyst for ORR along with enhanced electrochemical stability. In addition, the ionic block copolymer functionalized graphene can facilitate intermolecular charge transfer and good stability of metal NPs, which arises from the ionic block copolymer interfacial layer. When the beneficial features of the Mo-PdPt@Pt and IG are combined, the Mo-PdPt@Pt/IG exhibits substantially enhanced activity and durability for ORR relative to those of commercial Pt/C. Notably, the Mo-PdPt@Pt/IG shows mass activity 31-fold higher than that of Pt/C and substantially maintains high activities after 10 000 cycles of intensive durability testing. The current study highlights the crucial strategies in designing the highly active and durable Pt-based octahedra and effective combination with functional graphene supports toward the synergetic effects on ORR.

  10. Synthesis of cubic PtPd alloy nanoparticles as anode electrocatalysts for methanol and formic acid oxidation reactions.

    Science.gov (United States)

    Lee, Jin-Yeon; Kwak, Da-Hee; Lee, Young-Woo; Lee, Seul; Park, Kyung-Won

    2015-04-14

    The electrocatalytic properties for electro-oxidation reactions of shape-controlled Pt-based catalysts have been improved by alloying with 2nd elements. In this study, we demonstrate cubic PtPd alloy nanoparticles synthesized using a thermal decomposition method. The cubic PtPd nanoparticles exhibit a homogeneous distribution of alloy nanostructures in the presence of Pt and Pd metallic phases. The improved electrocatalytic activity for the electro-oxidation reactions of methanol and formic acid as chemical fuels might be attributed to the cubic alloy nanostructures. Furthermore, the cubic PtPd alloy nanoparticles as electrocatalysts exhibit excellent stability for electro-oxidation reactions.

  11. Magnetic studies in evaporated Ni/Pd multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Chafai, K. [Laboratoire de Physique des Materiaux, Micro-electronique, Automatique et Thermique (LPMMAT), Faculte des Sciences Ain Chock, Universite Hassan II, B.P. 5366 Maarif, Casablanca (Morocco); Salhi, H. [Laboratoire de Physique des Materiaux, Micro-electronique, Automatique et Thermique (LPMMAT), Faculte des Sciences Ain Chock, Universite Hassan II, B.P. 5366 Maarif, Casablanca (Morocco); Laboratoire de Mecanique, Productique et Genie industriel (LMPG), Ecole superieure de technologie, Universite Hassan II, B.P. 5366 Maarif, Casablanca (Morocco); Lassri, H., E-mail: lassrih@hotmail.co [Laboratoire de Physique des Materiaux, Micro-electronique, Automatique et Thermique (LPMMAT), Faculte des Sciences Ain Chock, Universite Hassan II, B.P. 5366 Maarif, Casablanca (Morocco); Yamkane, Z.; Lassri, M. [Laboratoire de Physique des Materiaux, Micro-electronique, Automatique et Thermique (LPMMAT), Faculte des Sciences Ain Chock, Universite Hassan II, B.P. 5366 Maarif, Casablanca (Morocco); Abid, M. [Laboratoire de Physique Fondamentale et Appliquee (LPFA), Faculte des Sciences Ain Chock, Universite Hassan II, B.P. 5366 Maarif, Casablanca (Morocco); Hlil, E.K. [Institut Neel, CNRS-Universite J. Fourier, BP 166, 38042 Grenoble (France); Krishnan, R. [Laboratoire de Magnetisme et d' Optique, URA 1531, 45 Avenue des Etats Unis, 78035 Versailles Cedex (France)

    2011-03-15

    The magnetic properties of Ni/Pd multilayers, prepared by sequential evaporation in ultrahigh vacuum, have been studied. The Ni thickness dependence of the magnetization and magnetic anisotropy is discussed. The temperature dependence of the spontaneous magnetization is well described by a T{sup 3/2} law in all multilayers. A spin-wave theory has been used to explain the temperature dependence of the spontaneous magnetization, and the approximate values for the exchange interactions for various Ni layer thicknesses have been obtained. - Research highlights: The magnetic properties of Ni/Pd multilayers, prepared by sequential evaporation in ultrahigh vacuum, have been studied. The temperature dependence of the spontaneous magnetization is well described by a T{sup 3/2} law in Ni/Pd multilayers. The spin-wave constant B was observed to depend on t{sub Ni} nonmonotonically. A spin-wave theory has been used to explain the temperature dependence of the spontaneous magnetization. The approximate values for the exchange interactions for various Ni layer thicknesses have been obtained.

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

    Science.gov (United States)

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

    2005-05-01

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

  13. Solvothermal synthesis of Pt-Pd alloys with selective shapes and their enhanced electrocatalytic activities

    Science.gov (United States)

    Zhang, Zhi-Cheng; Hui, Jun-Feng; Guo, Zhen-Guo; Yu, Qi-Yu; Xu, Biao; Zhang, Xin; Liu, Zhi-Chang; Xu, Chun-Ming; Gao, Jin-Sen; Wang, Xun

    2012-03-01

    Pt-Pd bimetallic alloy nanostructures with highly selective morphologies such as cube, bar, flower, concave cube, and dendrite have been achieved through a facile one-pot solvothermal synthesis. The effects of shape-controllers (sodium dodecyl sulfate (SDS), ethylenediamine-tetraacetic acid disodium salt (EDTA-2Na), NaI) and solvents (water/DMF) on the morphologies were systematically investigated. The electrocatalytic activities of these Pt-Pd alloy nanostructures toward formic acid oxidation were tested. The results indicated that these alloy nanocrystals exhibited enhanced and shape-dependent electrocatalytic activity toward formic acid oxidation compared to commercial Pt black and Pt/C catalysts.Pt-Pd bimetallic alloy nanostructures with highly selective morphologies such as cube, bar, flower, concave cube, and dendrite have been achieved through a facile one-pot solvothermal synthesis. The effects of shape-controllers (sodium dodecyl sulfate (SDS), ethylenediamine-tetraacetic acid disodium salt (EDTA-2Na), NaI) and solvents (water/DMF) on the morphologies were systematically investigated. The electrocatalytic activities of these Pt-Pd alloy nanostructures toward formic acid oxidation were tested. The results indicated that these alloy nanocrystals exhibited enhanced and shape-dependent electrocatalytic activity toward formic acid oxidation compared to commercial Pt black and Pt/C catalysts. Electronic supplementary information (ESI) available: See DOI: 10.1039/c2nr12135b

  14. Properties of the [M(dppm)2M']2+ building blocks (M, M' = Pd or Pt): site selectivity, emission features, and frontier orbital analysis.

    Science.gov (United States)

    Clément, Sébastien; Aly, Shawkat M; Bellows, Diana; Fortin, Daniel; Strohmann, Carsten; Guyard, Laurent; Abd-El-Aziz, Alaa S; Knorr, Michael; Harvey, Pierre D

    2009-05-04

    The homodinuclear [ClM(mu-dppm)(2)MCl] complexes 1 (M = Pd) and 2 (M = Pt) react with RNC ligands (R = Ph, xylyl, p-tolyl, p-C(6)H(4)iPr) to provide the A-frame [ClPd(mu-dppm)(2)(mu-C=N-R)PdCl] (R = Ph (5a), xylyl (5b)), [ClPt(mu-dppm)(2)(mu-C=N-R)PtCl] (R = p-tolyl (4a); p-C(6)H(4)iPr (4b)), and the d(9)-d(9) M(2)-bonded [ClPt(mu-dppm)(2)Pt(CN-R)]Cl (R = xylyl (3a); p-C(6)H(4)iPr (3b)) complexes. The heterodinuclear [XPd(mu-dppm)(2)PtX] complexes 6a (X = Cl) and 6b (X = I) react with RNC (R = o-anisyl) to form the A-frame [XPd(mu-dppm)(2)(mu-C=N-R)PtX] (X = Cl (9); I (10a)) and M(2)-bonded [ClPt(mu-dppm)(2)Pt(CN-R)]Cl (10b) complexes. The dangling ligand-containing complex [ClPd(mu-dppm)(2)Pt(eta(1)-dppm=O)](BF(4)) (7) reacts with xylyl-NC stoichiometrically to produce the dicationic salt [(xylyl-NC)Pd(mu-dppm)(2)Pt(eta(1)-dppm=O)](BF(4))(2) (8). Parameters ruling the coordination site terminal versus bridging are discussed. The precursor 10a reacts with RNC (R = o-anisyl, tBu) to form the heterobimetallic bis(isonitrile) [IPd(mu-dppm)(2)(mu-C=N-o-anisyl)Pt(CN-R)]I complexes 11b and 12, respectively, demonstrating the site selectivity of the second CNR ligand coordination, Pd versus Pt. The X-ray structures of 11b and 12 were obtained. Complex 12 is the first example of an A-frame system of the Ni-triad bearing two different isocyanide ligands. Several d(9)-d(9) terminal and d(8)-d(8) A-frame homo- and heterodinuclear complexes in 2-MeTHF at 77 K were studied by UV-vis and luminescence spectroscopy. Assignments for the lowest energy absorption and emission bands are made on the basis of density functional theory and time-dependent density functional theory computations.

  15. Structural stability and masnetism of metastable Ni-Pt intermetallic compounds studied by ab initio calculation

    Institute of Scientific and Technical Information of China (English)

    CHE XingLai; LI diaHao; DAI Ye; LIU BaiXin

    2009-01-01

    The self-consistent electronic structure calculations were carried out with the accurate frozen-core full-potential projector augmented-wave method on 13 Ni-Pt intermetallic compounds of simple crys-talline structures, i.e. A15, D019, D03 and L12 Ni3Pt and NiPt3, and α-NiAs, B1, B2, L28, and L10 NiPt. The calculations reveal that the L12 Ni3Pt, L10 NiPt and L12 NiPt3 are energetically more stable than their respective competitive structures, indicating that the three structures may be formed in some appro-priate conditions. The obtained results match well with the experimental observation or other theory predictions. It is found that there is hybridization between Ni 3d and Pt 5d states, which may signifi-cantly affect the structural stability and magnetism of metastable Ni-Pt intermetallic compounds.

  16. Structural stability and magnetism of metastable Ni-Pt intermetallic compounds studied by ab initio calculation

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The self-consistent electronic structure calculations were carried out with the accurate frozen-core full-potential projector augmented-wave method on 13 Ni-Pt intermetallic compounds of simple crystalline structures,i.e. A15,D019,D03 and L12 Ni3Pt and NiPt3,and α-NiAs,B1,B2,L2a,and L10 NiPt. The calculations reveal that the L12 Ni3Pt,L10 NiPt and L12 NiPt3 are energetically more stable than their respective competitive structures,indicating that the three structures may be formed in some appropriate conditions. The obtained results match well with the experimental observation or other theory predictions. It is found that there is hybridization between Ni 3d and Pt 5d states,which may significantly affect the structural stability and magnetism of metastable Ni-Pt intermetallic compounds.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-01-01

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

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

    Science.gov (United States)

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

    2011-04-01

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

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

    Science.gov (United States)

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

    2015-09-01

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

  20. Optical switching properties of Pd-Ni thin-film top-capped switchable mirrors

    Science.gov (United States)

    Zhang, Xiao-Li; Bao, Shan-Hu; Xin, Yun-Chuan; Cao, Xun; Jin, Ping

    2015-09-01

    Switchable mirrors based on magnesium-nickel alloy thin films capped with catalytic Pd-Ni alloy thin films were prepared by a DC magnetron sputtering method. Their composition, structure and surface morphology were studied by XPS, XRD and AFM. Herein, the optical switching properties and durability of the switchable mirrors were investigated by varying the Ni content in the Pd-Ni alloys. Comparing pure Pd catalyst with Pd-Ni top-capped switchable mirrors, the latter show better hydrogenation and dehydrogenation kinetics, and the speed of hydrogen desorption is obviously improved with increasing Ni content in the Pd-Ni alloy. The Pd-Ni capped switchable mirrors also have better optical switching durability. The catalytic Pd layer with the addition of Ni does not influence the transmittance (hydride state) and reflectance (metallic state) of the switchable mirrors. In addition, replacing Pd with Pd-Ni alloy decreases the cost of the switchable mirrors: employing nickel in the alloy Pd89.2Ni10.8 can save about 11% use of Pd. Therefore, the Pd-Ni alloy can provide a cheaper catalytic thin film, and it is expected to have applications in energy-saving windows, hydrogen sensors and hydrogen storage materials.

  1. Structure, chemical ordering and thermal stability of Pt-Ni alloy nanoclusters.

    Science.gov (United States)

    Cheng, Daojian; Yuan, Shuai; Ferrando, Riccardo

    2013-09-01

    Equilibrium structures, chemical ordering and thermal properties of Pt-Ni nanoalloys are investigated by using basin hopping-based global optimization, Monte Carlo (MC) and molecular dynamics (MD) methods, based on the second-moment approximation of the tight-binding potentials (TB-SMA). The TB-SMA potential parameters for Pt-Ni nanoalloys are fitted to reproduce the results of density functional theory calculations for small clusters. The chemical ordering in cuboctahedral (CO) Pt-Ni nanoalloys with 561 and 923 atoms is obtained from the so called semi-grand-canonical ensemble MC simulation at 100 K. Two ordered phases of L12 (PtNi3) and L10 (PtNi) are found for the CO561 and CO923 Pt-Ni nanoalloys, which is in good agreement with the experimental phase diagram of the Pt-Ni bulk alloy. In addition, the order-disorder transition and thermal properties of these nanoalloys are studied by using MC and MD methods, respectively. It is shown that the typical perfect L10 PtNi structure is relatively stable, showing high order-disorder transition temperature and melting point among these CO561 and CO923 Pt-Ni nanoalloys.

  2. Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation.

    Science.gov (United States)

    Feng, Yue; Bin, Duan; Yan, Bo; Du, Yukou; Majima, Tetsuro; Zhou, Weiqiang

    2017-05-01

    Porous bimetallic PdNi catalysts were fabricated by a novel method, namely, reduction of Pd and Ni oxides prepared via calcining the complex chelate of PdNi-dimethylglyoxime (PdNi-dmg). The morphology and composition of the as-prepared PdNi were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Furthermore, the electrochemical properties of PdNi catalysts towards ethanol electrooxidation were also studied by electrochemical impedance spectrometry (EIS), cyclic voltammetry (CV) and chronoamperometry (CA) measurement. In comparison with porous Pd and commercial Pd/C catalysts, porous structural PdNi catalysts showed higher electrocatalytic activity and durability for ethanol electrooxidation, which may be ascribed to Pd and Ni property, large electroactive surface area and high electron transfer property. The Ni exist in the catalyst in the form of the nickel hydroxides (Ni(OH)2 and NiOOH) which have a high electron and proton conductivity enhances the catalytic activity of the catalysts. All results highlight the great potential application of the calcination-reduction method for synthesizing high active porous PdNi catalysts in direct ethanol fuel cells.

  3. PdCuPt Nanocrystals With Multi-branches for Enzyme-free Glucose Detection

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-05

    By carefully controlling the synthesis condition, branched PtCu bimetallic templates were synthesized in aqueous solution. After the galvanic replacement reaction between PtCu templates and the Pt precursors, PdCuPt trimetallic nanocrystals with branched structures were obtained. Owing to the open structure and the optimized composition, the electrochemical experimental results reveal that the PdCuPt trimetallic nanocrystals exhibit high electrocatalytic activity, selectivity and stability for the oxidation of glucose in alkaline solution. In details, a sensitivity of 378 μA/mM/cm2 and a detection limit of 1.29 μM can be achieved. The good electrocatalytic performance should be attributed to the unique branched nanostructure as well as the synergistic effect among metals. The superior catalytic properties suggest that these nanocrystals are promising for enzyme-free detection of glucose.

  4. Effects of Ni vacancy, Ni antisite, Cr and Pt on the third-order elastic constants and mechanical properties of NiAl

    KAUST Repository

    Wu, Shaohua

    2014-12-01

    Effects of Ni vacancy, Ni antisite in Al sublattice, Cr in Al sublattice, Pt in Ni sublattice on the second-order elastic constants (SOECs) and third-order elastic constants (TOECs) of the B2 NiAl have been investigated using the first-principles methods. Lattice constant and the SOECs of NiAl are in good agreement with the previous results. The brittle/ductile transition map based on Pugh ratio G/B and Cauchy pressure Pc shows that Ni antisite, Cr, Pt and pressure can improve the ductility of NiAl, respectively. Ni vacancy and lower pressure can enhance the Vickers hardness Hv of NiAl. The density of states (DOS) and the charge density difference are also used to analysis the effects of vacancy, Ni antisite, Cr and Pt on the mechanical properties of NiAl, and the results are in consistent with the transition map. © 2014 Elsevier Ltd. All rights reserved.

  5. Electronic and magnetic properties of Pd-Ni multilayers: Study using density functional theory

    Science.gov (United States)

    Gómez, Guillermina; Cabeza, Gabriela F.; Belelli, Patricia G.

    2009-10-01

    Electronic and magnetic properties of Pd-Ni multilayers have been studied using VASP method in the framework of the density functional theory (DFT). The calculations performed for different configurations (Pd n/Ni m(1 1 1), where n Pd layers are piled up over m Ni layers with n=0 to 4 and n+m=4), reveal that the important magnetic moment of Ni is significantly enhanced according as n increases due to hybridization effects between Pd and Ni mostly localized at the interface. The results also indicate that the Pd atoms are strongly polarized in the studied systems when compared with the pure metal.

  6. Electronic and magnetic properties of Pd-Ni multilayers: Study using density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Gomez, Guillermina [Grupo de Materiales y Sistemas Cataliticos, Departamento de Fisica, Universidad Nacional del Sur, Avda. Alem 1253, Bahia Blanca, B8000CPB (Argentina); Cabeza, Gabriela F. [CONICET (Argentina)], E-mail: gcabeza@uns.edu.ar; Belelli, Patricia G. [CONICET (Argentina)

    2009-10-15

    Electronic and magnetic properties of Pd-Ni multilayers have been studied using VASP method in the framework of the density functional theory (DFT). The calculations performed for different configurations (Pd{sub n}/Ni{sub m}(1 1 1), where n Pd layers are piled up over m Ni layers with n=0 to 4 and n+m=4), reveal that the important magnetic moment of Ni is significantly enhanced according as n increases due to hybridization effects between Pd and Ni mostly localized at the interface. The results also indicate that the Pd atoms are strongly polarized in the studied systems when compared with the pure metal.

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

    Science.gov (United States)

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

    2015-05-01

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

  8. Verifying predictions of the L13 crystal structure in Cd-Pt and Pd-Pt by exhaustive enumeration

    Science.gov (United States)

    Hart, Gus L. W.

    2009-07-01

    In 2001, S. Müller and A. Zunger [Phys. Rev. Lett. 87, 165502 (2001)] predicted a never-before-observed crystal structure in Ag-Pd. Recently, Curtarolo predicted the same structure to be stable in Pt-Cd and Pt-Pd [S. Curtarolo , CALPHAD: Comput. Coupling Phase Diagrams Thermochem. 29, 163 (2005)]. The predicted structure is unique in several ways. Though never seen in any other face-centered-cubic-based intermetallic binary compound or ordered alloy, it is relatively simple—it contains only four atoms per unit cell. Furthermore, the structure is the only one of this small size, except the L12 structure, that cannot be characterized as a simple stacking of layers where each layer contains only one kind of atom. We construct a first-principles-based Hamiltonian and search it for the thermodynamically stable (lowest energy) structures. Using a (practically) exhaustive enumeration of about three million of the most likely candidate structures, we find that this new structure, designated L13 , is indeed a ground state in both Cd-Pt and Pd-Pt. Experimental efforts to validate the predictions are underway.

  9. 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.

  10. Surface-Limited Synthesis of Pt Nanocluster Decorated Pd Hierarchical Structures with Enhanced Electrocatalytic Activity toward Oxygen Reduction Reaction.

    Science.gov (United States)

    Yang, Tao; Cao, Guojian; Huang, Qingli; Ma, Yanxia; Wan, Sheng; Zhao, Hong; Li, Na; Sun, Xia; Yin, Fujun

    2015-08-12

    Exploring superior catalysts with high catalytic activity and durability is of significant for the development of an electrochemical device involving the oxygen reduction reaction. This work describes the synthesis of Pt-on-Pd bimetallic heterogeneous nanostructures, and their high electrocatalytic activity toward the oxygen reduction reaction (ORR). Pt nanoclusters with a size of 1-2 nm were generated on Pd nanorods (NRs) through a modified Cu underpotential deposition (UPD) process free of potential control and a subsequent surface-limited redox reaction. The Pt nanocluster decorated Pd nanostructure with a ultralow Pt content of 1.5 wt % exhibited a mass activity of 105.3 mA mg(-1) (Pt-Pd) toward ORR, comparable to that of the commercial Pt/C catalyst but 4 times higher than that of carbon supported Pd NRs. More importantly, the carbon supported Pt-on-Pd catalyst displays relatively small losses of 16% in electrochemical surface area (ECSA) and 32% in mass activity after 10 000 potential sweeps, in contrast to respective losses of 46 and 64% for the commercial Pt/C catalyst counterpart. The results demonstrated that Pt decoration might be an efficient way to improve the electrocatalytic activity of Pd and in turn allow Pd to be a promising substitution for commercial Pt catalyst.

  11. Effects of Pt speedlayer and Ar pressure on magnetic and structural properties of sputtered CoNi/Pt multilayers

    NARCIS (Netherlands)

    Meng, Q.; Haan, de P.; Drent, van W.P.; Lodder, J.C.; Popma, Th.J.A.

    1996-01-01

    CoNi/Pt multilayers were prepared by magnetron sputtering using Ar gas. The effects of the Pt seed layer and the Ar sputtering pressure on magnetic and structural properties are investigated. Microstructures of the multilayers were analysed using XRD and TEM. It was found that perpendicular magnetic

  12. Antisite-defect-induced surface segregation in ordered NiPt alloy

    DEFF Research Database (Denmark)

    Pourovskii, L.V.; Ruban, Andrei; Abrikosov, I.A.;

    2003-01-01

    By means of first principles simulations we demonstrate that tiny deviations from stoichiometry in the bulk composition of the NiPt-L1(0) ordered alloy have a great impact on the atomic configuration of the (111) surface. We predict that at T=600 K the (111) surface of the Ni51Pt49 and Ni50Pt50...... alloys corresponds to the (111) truncation of the bulk L1(0) ordered structure. However, the (111) surface of the nickel deficient Ni49Pt51 alloy is strongly enriched by Pt and should exhibit the pattern of the 2x2 structure. Such a drastic change in the segregation behavior is due to the presence...... of different antisite defects in the Ni- and Pt-rich alloys and is a manifestation of the so-called off-stoichiometric effect....

  13. Processing of Ni30Pt20Ti50 High-Temperature Shape-Memory Alloy Into Thin Rod Demonstrated

    Science.gov (United States)

    Noebe, Ronald D.; Draper, Susan L.; Biles, Tiffany A.; Leonhardt, Todd

    2005-01-01

    High-temperature shape-memory alloys (HTSMAs) based on nickel-titanium (NiTi) with significant ternary additions of palladium (Pd), platinum (Pt), gold (Au), or hafnium (Hf) have been identified as potential high-temperature actuator materials for use up to 500 C. These materials provide an enabling technology for the development of "smart structures" used to control the noise, emissions, or efficiency of gas turbine engines. The demand for these high-temperature versions of conventional shape-memory alloys also has been growing in the automotive, process control, and energy industries. However these materials, including the NiPtTi alloys being developed at the NASA Glenn Research Center, will never find widespread acceptance unless they can be readily processed into useable forms.

  14. Anamperometric superoxide anion radicalbiosensor based on SOD/PtPd-PDARGO modified electrode.

    Science.gov (United States)

    Tang, Jie; Zhu, Xiang; Niu, Xiangheng; Liu, Tingting; Zhao, Hongli; Lan, Minbo

    2015-05-01

    In the present work, a high-performance enzyme-based electrochemical sensor for the detection of superoxide anion radical (O2(●-)) is reported. Firstly, we employed a facile approach to synthesize PtPd nanoparticles (PtPd NPs) on chemically reduced graphene oxide (RGO) coated with polydopamine (PDA). The prepared PtPd-PDARGO composite was well characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectra, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical methods. Then the assembled composite was used as a desired electrochemcial interface for superoxide dismutase (SOD) immobilization. Owing to the PDA layer as well as the synergistic effect of PtPd NPs, the fabricated SOD/PtPd-PDARGO sensor exhibited an outstanding sensitivity of 909.7 μA mM(-1) cm(-2) upon O2(●-) in a linear range from 0.016 mM to 0.24 mM (R(2)=0.992), with a low detection limit of 2 μM (S/N=3) and excellent selectivity, good reproducibility as well as favorable long-term stability.

  15. Structure and superconducting transition in splat-cooled U–T alloys (T = Mo, Pd, Pt)

    Energy Technology Data Exchange (ETDEWEB)

    Kim-Ngan, N.-T.H., E-mail: tarnawsk@up.krakow.pl [Institute of Physics, Pedagogical University, Podchorazych 2, 30-084 Krakow (Poland); Paukov, M. [Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, 12116 Prague (Czech Republic); Sowa, S.; Krupska, M. [Institute of Physics, Pedagogical University, Podchorazych 2, 30-084 Krakow (Poland); Tkach, I.; Havela, L. [Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, 12116 Prague (Czech Republic)

    2015-10-05

    Highlights: • Splat-cooled U–6 at.% Mo, U–5 at.% Pd, U–5 at.% Pt alloys become superconducting below 1 K. • U–5 at.% Pd and U–5 at.% Pt reveal only one resistivity jump at T{sub c}. • Two distinguishable resistivity drops were observed for U–6 at.% Mo. • A broad maximum was observed at T{sub c} in the specific heat. • Those splats consist of two phases having orthorhombic α- and cubic γ-U structure. - Abstract: U–T (T = Mo, Pd, Pt) alloys were prepared by splat cooling technique and characterized by X-ray diffraction. The resistivity and specific heat measurements were performed down to 0.3 K to study their superconductivity. The superconducting transition in the alloy with 6 at.% Mo (U–6%Mo) revealed by a smooth decrease below 1.5 K and a sharp drop at 0.6 K in the resistivity, while a single sharp drop was revealed at T{sub c} ≈ 0.8 K for those with 5 at.% Pd and Pt doping (U–5%Pd and U–5%Pt). With applying magnetic fields, the resistivity drops move to lower temperatures. The superconductivity transitions were revealed by only one broad peak at T{sub c} in the C(T) curves.

  16. Preparation and characterization of MgB{sub 2} with Pd, Pt and Re doping

    Energy Technology Data Exchange (ETDEWEB)

    Grivel, J.-C., E-mail: jean@dtu.dk [Department of Energy Conversion and Storage, Technical University of Denmark, 4000-Roskilde (Denmark); Pitillas, A. [Department of Energy Conversion and Storage, Technical University of Denmark, 4000-Roskilde (Denmark); Universidad Autónoma de Barcelona, 08193 Cerdanyola (Spain); Namazkar, S. [Department of Energy Conversion and Storage, Technical University of Denmark, 4000-Roskilde (Denmark); Chemical Biological Centre, Umeå University, 90187 Umeå (Sweden); Alexiou, A.; Holte, O.J. [Department of Energy Conversion and Storage, Technical University of Denmark, 4000-Roskilde (Denmark)

    2016-01-15

    Highlights: • MgB{sub 2} samples doped with Pt, Pd or Re were prepared by solid state route. • The solubility of these elements in the MgB{sub 2} lattice is negligible. • The field dependence of the normalized J{sub c} is improved in doped samples. - Abstract: Samples with Mg{sub 1−x}D{sub x}B{sub 2.04} (D = Pt, Pd or Re) nominal compositions have been synthesised by a solid-state route. None of these doping elements can be substituted for Mg in a detectable amount and their presence in the samples has no influence on the critical temperature and on the lattice parameters of the MgB{sub 2} superconductor. Impurity phases are formed by reaction mostly with Mg. The microstructure of the Pt, Pd and Re-based phases depends on the elements. Re-rich particles with large sizes up to 8 μm form, whereas Pt- and Pd-containing impurities are finely dispersed with a particle size that does not exceed 1 μm. The field dependence of the normalised critical current density is improved when Pt, Pd or Re are present in the samples.

  17. Laser-induced in situ synthesis of Pd and Pt nanoparticles on polymer films

    Science.gov (United States)

    Mehrabanian, Mehran; Morselli, Davide; Caputo, Gianvito; Scarpellini, Alice; Palazon, Francisco; Athanassiou, Athanassia; Fragouli, Despina

    2016-12-01

    We present the localized in situ formation of Pd and Pt nanoparticles embedded in chitosan solid films. This is achieved by the photo-induced reduction of metallic precursors, previously incorporated in chitosan films, through controlled UV pulsed laser irradiation. Interestingly, at high number of laser pulses, Pd and Pt follow different formation pathways, contrary to their common photoreduction mechanism occurring at low irradiation pulses. Specifically, in the case of the Pd, a photofragmentation process takes place fracturing the previously formed nanoparticles into smaller ones; whereas in the case of Pt, the prolonged irradiation promotes the nanoparticles agglomeration. The combination of both precursors in a binary solid system results in the combined formation of both Pd and Pt nanoparticles in the polymer film upon laser irradiation. The herein reported approach is an efficient and precise tool to generate size- and density-controlled Pd and Pt nanoparticles in desired areas of polymeric films, rendering this method a potential candidate for the fabrication of flexible polymeric devices for gas-sensing or electro-catalysis applications.

  18. Synthesis and characterization of Pt-Pd nanoparticles with core-shell morphology: Nucleation and overgrowth of the Pd shells on the as-prepared and defined Pt seeds

    Energy Technology Data Exchange (ETDEWEB)

    Long, Nguyen Viet, E-mail: nguyenvietlong@yahoo.com [Department of Materials Scienceand Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Posts and Telecommunications Institute of Technology, km 10 Nguyen Trai, Hanoi (Viet Nam); Laboratory for Nanotechnology, Vietnam National University at Ho Chi Minh, Linh Trung, Thu Duc, Ho Chi Minh (Viet Nam); Department of Molecular and Material Sciences, Interdisciplinary Graduate School of Engineering Sciences, 6-1 Kasugakouen, Kasuga, Fukuoka 861-8580 (Japan); Hien, Tong Duy [Laboratory for Nanotechnology, Vietnam National University at Ho Chi Minh, Linh Trung, Thu Duc, Ho Chi Minh (Viet Nam); Asaka, Toru [Department of Materials Scienceand Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Ohtaki, Michitaka [Department of Molecular and Material Sciences, Interdisciplinary Graduate School of Engineering Sciences, 6-1 Kasugakouen, Kasuga, Fukuoka 861-8580 (Japan); Nogami, Masayuki, E-mail: nogami@nitech.ac.jp [Department of Materials Scienceand Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan)

    2011-07-21

    Highlights: > The Pt-Pd core-shell nanoparticles based on the as-prepared Pt cores are synthesized. > Not only the Pt-Pd core-shell nanoparticles are formed, but also the separate formation of Pd nanoparticles as well. > The Pt cores without the morphological changes are protected by the Pd-shell overgrowths. > There are the co-existence of the layer-by-layer and island-on-wetting-layer growth modes of the Pd shells and the latter becomes the favorable overgrowth in the formation of core-shell structures. - Abstract: In the present research, Pt-Pd core-shell nanoparticles based on the as-prepared and defined Pt-seed cores with well-controlled size and morphology were synthesized. Their characterizations were investigated by using UV-vis spectroscopy, transmission electron microscopy (TEM), and high resolution (HR)TEM measurements. The high resolution elemental mappings were performed in the operation of high angle annular dark field (HAADF) in conjunction with scanning (S)TEM mode and X-ray energy dispersive spectroscopy (XEDS). It is found that not only the Pt-Pd core-shell nanoparticles were formed, but also the nucleation, growth, and the separate formation of single Pd nanoparticles as well. Interestingly, the as-prepared Pt cores without the morphological changes were protected by the overgrowths of the Pd shells during the successive reduction of sodium tetrachloropalladate (II) hydrate. There were the co-existence of the Frank-van der Merwe (FM) layer-by-layer and Stranski-Krastanov (SK) island-on-wetting-layer growth modes of the Pd shells on the as-prepared Pt cores. It is predicted that the SK growth became the favorable growth mode in the formation of the Pd shells in the formation Pt-Pd core-shell nanoparticles.

  19. Poisoning and regeneration of Pt-Pd/WO{sub 3}-ZrO{sub 2} short paraffin isomerization catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Canavese, Sergio; Finelli, Zunilda; Busto, Mariana; Benitez, Viviana M.; Vera, Carlos R.; Yori, Juan C., E-mail: jyori@fiq.unl.edu.a [Universidad Nacional del Litoral (UNL), Santa Fe (Argentina). Inst. de Investigaciones en Catalisis y Petroquimica

    2010-07-01

    WO{sub 3}-ZrO{sub 2} catalysts promoted with Pt and Pd were tested as paraffin isomerization catalysts using n-hexane as model compound. Sulfur and amine poisoning and regeneration tests were used to assess the impact of the addition of Pt and Pd on the deactivation resistance and regenerability. Pt and Pt Pd catalysts were the most active for n-hexane isomerization. The low activity of the Pd catalyst was attributed to poor Pd metal properties when supported over WO{sub 3}-ZrO{sub 2} and to a decrease of the number of Broensted acid sites. Pt Pd was the only catalyst capable of full regeneration after S poisoning. Amine poisoning completely suppressed the isomerization activity and the original activity could only be restored by calcination and reduction. (author)

  20. Poisoning and regeneration of Pt-Pd/WO3-ZrO2 short paraffin isomerization catalysts

    Directory of Open Access Journals (Sweden)

    Sergio Canavese

    2010-01-01

    Full Text Available WO3-ZrO2 catalysts promoted with Pt and Pd were tested as paraffin isomerization catalysts using n-hexane as model compound. Sulfur and amine poisoning and regeneration tests were used to assess the impact of the addition of Pt and Pd on the deactivation resistance and regenerability. Pt and PtPd catalysts were the most active for n-hexane isomerization. The low activity of the Pd catalyst was attributed to poor Pd metal properties when supported over WO3-ZrO2 and to a decrease of the number of BrQnsted acid sites. PtPd was the only catalyst capable of full regeneration after S poisoning. Amine poisoning completely supressed the isomerization activity and the original activity could only be restored by calcination and reduction.

  1. Alloy ratio effect of Pd/Pt nanoparticles on carbon nanotubes for catalysing methanol-tolerant oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Chien-Liang, E-mail: cl_lee@url.com.t [Department of Chemical and Materials Engineering, National Kaohsiung University of Applied Science, Kaohsiung, Taiwan (China); Chiou, Hsueh-Ping; Wu, Shi-Chi; Wu, Chen-Chung [Department of Chemical and Materials Engineering, National Kaohsiung University of Applied Science, Kaohsiung, Taiwan (China)

    2010-12-30

    Pd{sub 1}Pt{sub 3}, Pd{sub 1}Pt{sub 1}, and Pd{sub 3}Pt{sub 1} nanoparticles supported on multi-wall carbon nanotubes (CNTs) were prepared by the self-regulation reduction of sodium n-dodecyl sulphate and used as catalysts in oxygen reduction reactions (ORRs). The crystal properties of these alloy nanoparticles on the CNT were measured by X-ray diffraction spectroscopy (XRD) and high-resolution transmission electron microscopy (HRTEM). The angle shifting of the XRD peak and the lattice spacing of the nanoparticles measured by HRTEM increased with an increase in Pd amount, indicating a regulable Pd-Pt ratio for the alloy nanoparticle composition. Rotating ring-disk electrode (RRDE) measurements indicate that the number of electrons catalysed by the Pd{sub 1}Pt{sub 3}/CNT, Pd{sub 1}Pt{sub 1}/CNT, and Pd{sub 3}Pt{sub 1}/CNT nanocatalysts in the ORRs were 3.98, 3.97, and 3.93, respectively. These results show that these ORRs occur via a 4-electron pathway. Linearly scanned voltammetry in the electrolyte with methanol revealed that Pd{sub 3}Pt{sub 1}/CNT has high methanol tolerance during ORRs.

  2. Effects of Ce on catalytic combustion of methane over Pd-Pt/Al2O3 catalyst.

    Science.gov (United States)

    Fan, Xing; Wang, Fan; Zhu, Tianle; He, Hong

    2012-01-01

    Activity and stability of 1%Pd-0.2%Pt/Al2O3 and 1%Pd-0.2%Pt/0.6%Ce/Al2O3 catalysts prepared by impregnation method for catalytic combustion of methane in air were investigated. The catalysts before and after reaction were characterized by BET, CO chemisorption, XRD and XP S techniques. Results showed that the presence of Ce significantly increased the activity and thermal stability of the Pd-Pt/Al2O3 catalyst towards methane combustion, which could be attributed to more highly-dispersed active PdO particles over the Pd-Pt/Ce/Al2O3 catalyst surface as well as the retarded sintering of PdO and the maintained oxidized state of surface Pd during the combustion process in the presence of Ce.

  3. Effects of Ce on catalytic combustion of methane over Pd-Pt/Al2O3 catalyst

    Institute of Scientific and Technical Information of China (English)

    Xing Fan; Fan Wang; Tianle Zhu; Hong He

    2012-01-01

    Activity and stability of 1%Pd-0.2%Pt/Al2O3 and 1%Pd-0.2%Pt/0.6%Ce/Al2O3 catalysts prepared by impregnation method for catalytic combustion of methane in air were investigated.The catalysts before and after reaction were characterized by BET,CO chemisorption,XRD and XPS techniques.Results showed that the presence of Ce significantly increased the activity and thermal stability of the Pd-Pt/Al2O3 catalyst towards methane combustion,which could be attributed to more highly-dispersed active PdO particles over the Pd-Pt/Ce/Al2O3 catalyst surface as well as the retarded sintering of PdO and the maintained oxidized state of surface Pd during the combustion process in the presence of Ce.

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

    Science.gov (United States)

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

    2016-02-21

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

  5. Shape-controlled synthesis of Pt-Pd core-shell nanoparticles exhibiting polyhedral morphologies by modified polyol method

    Energy Technology Data Exchange (ETDEWEB)

    Long, Nguyen Viet, E-mail: nguyenviet_long@yahoo.com [Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Posts and Telecommunications Institute of Technology, Nguyen Trai, Hanoi (Viet Nam); Asaka, Toru; Matsubara, Takashi [Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Nogami, Masayuki, E-mail: nogami@nitech.ac.jp [Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan)

    2011-04-15

    Pt-Pd core-shell nanoparticles were synthesized by a simple synthetic method. First, Pt nanoparticles were synthesized in a controlled manner via the reduction of chloroplantinic acid hexahydrate in ethylene glycol (EG) at 160 deg. C in the presence of silver nitrate and the stabilization of polyvinylpyrrolidon. AgNO{sub 3} used acts as a structure-modifying agent to the morphology of the Pt nanoparticles. These Pt nanoparticles function as the seeds for the successive reduction of sodium tetrachloropalladate (II) hydrate in EG under stirring for 15 min at 160 deg. C in order to synthesize Pt-Pd core-shell nanoparticles. To characterize the as-prepared Pt-Pd nanoparticles, transmission electron microscopy (TEM) and high-resolution TEM are used. The high-resolution elemental mappings were carried out using the combination of scanning TEM and X-ray energy-dispersive spectroscopy. The results also demonstrate the homogeneous nucleation and growth of the Pd metal shell on the definite Pt core. The synthesized Pt-Pd core-shell nanoparticles exhibit a sharp and polyhedral morphology. The epitaxial growth of the controlled Pd shells on the Pt cores via a polyol method was observed. It is suggested that Frank-van der Merwe and Stranski-Krastanov growth modes coexisted in the nucleation and growth of Pt-Pd core-shell nanoparticles.

  6. Surface, segregation profile for Ni50Pd50(100)

    DEFF Research Database (Denmark)

    Christensen, Asbjørn; Ruban, Andrei; Skriver, Hans Lomholt

    1997-01-01

    A recent dynamical LEED study [G.N. Derry, C.B. McVey, P.J. Rous, Surf. Sci. 326 (1995) 59] reported an oscillatory surface segregation profile in the Ni50Pd50(100) system with the surface layer enriched by Pd. We have performed ab-initio total-energy calculations for the surface of this alloy...... system using the coherent potential approximation and obtain an oscillatory segregation profile, in agreement with experiments. We discuss the energetic origin of the oscillatory segregation profile in terms of effective cluster interactions. We include relaxation effects by means of the semi...

  7. KARAKTERISASI KATALIS Pt-Pd/ZEOLIT ALAM REGENERASI PADA REAKSI HIDRODENITROGENASI PIRIDIN

    Directory of Open Access Journals (Sweden)

    Dina Asnawati

    2014-05-01

    Full Text Available Telah dilakukan penelitian tentang Karakterisasi Katalis Pt-Pd/Zeolit Alam Regenerasi pada Reaksi Hidrodenitrogenasi Piridin. Tujuan dari penelitian ini adalah untuk mempelajari karakter katalis Pt-Pd/zeolit alam baru, bekas dan hasil regenerasi pada hidrodenitrogenisasi piridin. Katalis Pt-Pd/zeolit alam terdeaktivasi diregenerasi dengan cara dioksidasi dengan gas O2 pada temperatur 350oC selama 2 jam, dan direduksi dengan gas H2 pada temperatur 400oC selama 1 jam. Karakterisasi katalis baru (fresh, terdeaktivasi dan terregenerasi meliputi penentuan luas permukaan, volume pori dan rerata jejari pori dengan alat Gas Sorption Analyzer NOVA-1000 berdasarkan adsorpsi gas N2 serta penentuan keasaman dengan metode adsorpsi gas amoniak. Hasil penelitian menunjukkan bahwa deaktivasi katalis menyebabkan penurunan luas permukaan spesifik, volume total pori dan keasaman katalis, sedangkan proses regenerasi pada katalis bekas dengan metode oksidasi dan reduksi meningkatkan luas permukaan spesifik, volume total pori, rerata jejari pori dan keasaman katalis.

  8. Comparison of Pt and Pd Modified TiO2 Gas Sensors

    Directory of Open Access Journals (Sweden)

    Maolin ZHANG

    2014-12-01

    Full Text Available Pt and Pd have been widely used to improve response properties of TiO2 based gas sensors. In this work, differences on response properties, especially the response time of Pt/TiO2 and Pd/TiO2 sensors, were carefully compared. TiO2 sensing films were modified by dipping method using H2PtCl6 and PdCl2, respectively. XRD, XPS and SEM were used to characterize the crystal structure, elemental composition and grain size of the sensing films. The defect state was characterized by the relationship between resistance and oxygen partial pressure. And the response transients to H2 and O2 were tested by voltammetry method. The difference on response properties of modified TiO2 sensors were suggested to arise from their activation energy. DOI: http://dx.doi.org/10.5755/j01.ms.20.4.6403

  9. Enhanced Activity of Supported Ni Catalysts Promoted by Pt for Rapid Reduction of Aromatic Nitro Compounds

    Directory of Open Access Journals (Sweden)

    Huishan Shang

    2016-06-01

    Full Text Available To improve the activities of non-noble metal catalysts is highly desirable and valuable to the reduced use of noble metal resources. In this work, the supported nickel (Ni and nickel-platinum (NiPt nanocatalysts were derived from a layered double hydroxide/carbon composite precursor. The catalysts were characterized and the role of Pt was analysed using X-ray diffraction (XRD, high-resolution transmission electron microscopy (HRTEM, energy dispersive X-ray spectroscopy (EDS mapping, and X-ray photoelectron spectroscopy (XPS techniques. The Ni2+ was reduced to metallic Ni0 via a self-reduction way utilizing the carbon as a reducing agent. The average sizes of the Ni particles in the NiPt catalysts were smaller than that in the supported Ni catalyst. The electronic structure of Ni was affected by the incorporation of Pt. The optimal NiPt catalysts exhibited remarkably improved activity toward the reduction of nitrophenol, which has an apparent rate constant (Ka of 18.82 × 10−3 s−1, 6.2 times larger than that of Ni catalyst and also larger than most of the reported values of noble-metal and bimetallic catalysts. The enhanced activity could be ascribed to the modification to the electronic structure of Ni by Pt and the effect of exposed crystal planes.

  10. Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

    KAUST Repository

    Biausque, Gregory

    2015-04-28

    Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

  11. Calculated orientation dependence of surface segregations in Pt50Ni50

    DEFF Research Database (Denmark)

    Abrikosov, I. A.; Ruban, Andrei; Skriver, Hans Lomholt

    1994-01-01

    We present local-density calculations of surface segregation profiles in a random Pt50Ni50 alloy. We find that the concentration profiles of the three low-index surfaces oscillate and that the two most closely packed surfaces, i.e., (111) and (100), are enriched by Pt while Ni is found to segrega...

  12. Magnetic properties of thermally reduced graphene oxide decorated with PtNi nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Huízar-Félix, A.M. [Universidad Autónoma de Nuevo León, UANL, Facultad de Ingeniería Mecánica y Eléctrica, FIME, Ave. Pedro de Alba s/n, Ciudad Universitaria, C.P.66455 San Nicolás de los Garza, N.L. (Mexico); Departamento de Electricidad y Electrónica, Universidad del País Vasco (UPV/EHU), 48940 Leioa (Spain); BC Materials, Basque Centre for Materials, Applications and Nanostructures, 48160 Derio (Spain); Cruz-Silva, R. [Research Center for Exotic NanoCarbon, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553 (Japan); Barandiarán, J.M. [Departamento de Electricidad y Electrónica, Universidad del País Vasco (UPV/EHU), 48940 Leioa (Spain); BC Materials, Basque Centre for Materials, Applications and Nanostructures, 48160 Derio (Spain); García-Gutiérrez, D.I. [Universidad Autónoma de Nuevo León, UANL, Facultad de Ingeniería Mecánica y Eléctrica, FIME, Ave. Pedro de Alba s/n, Ciudad Universitaria, C.P.66455 San Nicolás de los Garza, N.L. (Mexico); Orue, I. [SGIKER Medidas Magnéticas, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), 48940 Leioa (Spain); and others

    2016-09-05

    Nanocomposites of reduced graphene oxide (RGO) with PtNi nanoparticles were obtained by in situ thermal reduction of a physical mixture of GO and metallic precursors. RGO and PtNiRGO nanocomposites were studied by differential thermal analysis and thermogravimetry, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), as well as scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The method presented here is a one-step thermal reduction procedure that allows the deposition of bimetallic PtNi nanoparticles with tetragonal crystalline structure and particle size ranging from 3 nm to 30 nm on RGO. The magnetic properties of the RGO and PtNiRGO nanocomposites were measured by vibrating sample magnetometry, which revealed that the RGO exhibited diamagnetism at room temperature and paramagnetism at temperatures below 10 K. PtNiRGO nanocomposites show hysteresis and ferromagnetic ordering at room temperature with a Curie temperature of 658 K. In addition, its magnetic properties at low temperature were strongly influenced by the paramagnetic contribution of RGO and the morphology of the bimetallic nanoparticles. - Highlights: • Simultaneous synthesis method for growth of PtNi nanoparticles on RGO. • Microstructural features of PtNiRGO nanocomposite were studied with extensive characterization. • Diamagnetic behavior of RGO and ferromagnetic ordering for PtNiRGO nanocomposite.

  13. Pt@Pd(x)Cu(y)/C core-shell electrocatalysts for oxygen reduction reaction in fuel cells.

    Science.gov (United States)

    Cochell, T; Manthiram, A

    2012-01-17

    A series of carbon-supported core-shell nanoparticles with Pd(x)Cu(y)-rich cores and Pt-rich shells (Pt@Pd(x)Cu(y)/C) has been synthesized by a polyol reduction of the precursors followed by heat treatment to obtain the Pd(x)Cu(y)/C (1 ≤ x ≤ 3 and 0 ≤ y ≤ 5) cores and the galvanic displacement of Pd(x)Cu(y) with [PtCl(4)](2-) to form the Pt shell. The nanoparticles have also been investigated with respect to the oxygen reduction reaction (ORR) in proton-exchange-membrane fuel cells (PEMFCs). X-ray diffraction (XRD) analysis suggests that the cores are highly alloyed and that the galvanic displacement results in a certain amount of alloying between Pt and the underlying Pd(x)Cu(y) alloy core. Transmission electron microscopy (TEM) images show that the Pt@Pd(x)Cu(y)/C catalysts (where y > 0) have mean particle sizes of <8 nm. Compositional analysis by energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) clearly shows Pt enrichment in the near-surface region of the nanoparticles. Cyclic voltammograms show a positive shift of as much as 40 mV for the onset of Pt-OH formation in the Pt@Pd(x)Cu(y)/C electrocatalysts compared to that in Pt/C. Rotating disk electrode (RDE) measurements of Pt@PdCu(5)/C show an increase in the Pt mass activity by 3.5-fold and noble metal activity by 2.5-fold compared to that of Pt/C. The activity enhancements in RDE and PEMFC measurements are believed to be a result of the delay in the onset of Pt-OH formation.

  14. Pt Monolayer Electrocatalyst for Oxygen Reduction Reaction on Pd-Cu Alloy: First-Principles Investigation

    Directory of Open Access Journals (Sweden)

    Amra Peles

    2015-07-01

    Full Text Available First principles approach is used to examine geometric and electronic structure of the catalyst concept aimed to improve activity and utilization of precious Pt metal for oxygen reduction reaction in fuel cells. The Pt monolayers on Pd skin and Pd1-xCux inner core for various compositions x were examined by building the appropriate models starting from Pd-Cu solid solution. We provided a detailed description of changes in the descriptors of catalytic behavior, d-band energy and binding energies of reaction intermediates, giving an insight into the underlying mechanism of catalytic activity enhancement based on the first principles density functional theory (DFT calculations. Structural properties of the Pd-Cu bimetallic were determined for bulk and surfaces, including the segregation profile of Cu under different environment on the surface.

  15. Ten metal complexes of vitamin B3/niacin: Spectroscopic, thermal, antibacterial, antifungal, cytotoxicity and antitumor studies of Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Cd(II), Pt(IV) and Au(III) complexes

    Science.gov (United States)

    Al-Saif, Foziah A.; Refat, Moamen S.

    2012-08-01

    Ten coordination compounds, namely Mn(NA)2Cl2·4H2O (1), Fe(NA)Cl3(H2O)2 (2), Co(NA)2(NO3)2·6H2O (3), Ni(NA)Cl2·5H2O (4), Cu(NA)Cl2·3H2O (5), Zn(NA)(NO3)2·H2O (6), Pd(NA)2Cl2·H2O (7), Cd(NA)Cl2·H2O (8), Pt(NA)2Cl4·5H2O (9) and Au(NA)Cl3 (10) were obtained by the reactions of the corresponding transition metal salts with vitamin B3/niacin (NA) in the presence of 1:4 (v:v) distilled water: methanol solvent at 70 °C for about 30 min, and their suggested structures were determined by elemental analyses, molar conductivity, (infrared, UV-vis) spectra, effective magnetic moment in Bohr magnetons, electron spin resonance (ESR), thermal analysis (TG), X-ray powder diffraction (XRD) as well as scanning electron microscopy (SEM). The results revealed that in complexes 1, 3, 7, and 9 both of two NA ligand coordinates one metal ion to form four or six coordinated structures, while in compound 10, one NA ligand coordinate to Au+++ ion to form a square-planar geometry with N-bonded pyridine ligand is suggested, and (2, 4, 5, 6 and, 8) complexes have 1:1 structures. Antimicrobial and antitumor activities were assessment against some kind of (G+ and G-) bacteria, fungi and breast carcinoma cells (MCF-7-cell line).

  16. CO adsorption on ionic Pt, Pd and Cu sites in Ce1−MxO2− (M=Pt2+, Pd2+, Cu2+)

    Indian Academy of Sciences (India)

    Gargi Dutta; Asha Gupta; Umesh V Waghmare; M S Hegde

    2011-07-01

    Noble metal ion substituted CeO2 in the form of Ce0.98M0.02O2− solid solution (where M=Pt, Pd, Cu) are the new generation catalysts with applications in three-way exhaust catalysis. While adsorption of CO on noble metals ions is well-known, adsorption of CO on noble metal ions has not been studied because creating exclusive ionic sites has been difficult. Using first-principles density functional theory (DFT) we have shown that CO gets adsorbed on the noble metal Pt2+, Pd2+, Cu2+ ionic sites in the respective compounds, and the net energy of the overall system decreases. Adsorption of CO on metal ions is also confirmed by Fourier transform infrared spectroscopy (FTIR).

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

    DEFF Research Database (Denmark)

    Andersen, O. Krogh

    1970-01-01

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

  18. Pd-Pt Alloy with Coral-Like Nanostructures Showing High Performance for Oxygen Electrocatalytic Reduction.

    Science.gov (United States)

    Liu, Xing-Quan; Chen, Xue-Song; Wu, Jian; Yao, Lei

    2016-03-01

    Three-dimensional (3D) Pd-Pt alloy with coral-like nanostructures were synthesized via bubble dynamic templated electrodeposition method at room temperature. The morphology of the as-prepared nanostructures was characterized using scanning electron microscopy (SEM), EDS, high-resolution transmission electron microscopy (HRTEM), respectively. Cyclic voltammetry method was adopted to evaluate the electrocatalytic activities of the synthesized electrodes toward oxygen reduction in KCl solution. The electrochemical results indicated that the Pd-Pt alloy with coral-like nanostructures hold the high performance for oxygen reduction.

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

    Science.gov (United States)

    Bell, A.; Simon, A.

    2009-05-01

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

  20. Self-Decoration of PtNi Alloy Nanoparticles on Multiwalled Carbon Nanotubes for Highly Efficient Methanol Electro-Oxidation

    Institute of Scientific and Technical Information of China (English)

    Yu-Yan Zhou; Chang-Hai Liu; Jie Liu; Xin-Lei Cai; Ying Lu; Hui Zhang; Xu-Hui Sun; Sui-Dong Wang

    2016-01-01

    A simple one-pot method was developed to prepare PtNi alloy nanoparticles, which can be self-decorated on multiwalled carbon nanotubes in [BMIm][BF4] ionic liquid. The nanohybrids are targeting stable nanocatalysts for fuel cell applications. The sizes of the supported PtNi nanoparticles are uniform and as small as 1–2 nm. Pt-to-Ni ratio was controllable by simply selecting a PtNi alloy target. The alloy nanoparticles with Pt-to-Ni ratio of 1:1 show high catalytic activity and stability for methanol electro-oxidation. The performance is much higher compared with those of both Pt-only nanoparticles and commercial Pt/C catalyst. The electronic structure characterization on the PtNi nanoparticles demon-strates that the electrons are transferred from Ni to Pt, which can suppress the CO poisoning effect.

  1. Physical properties of polycrystalline Sm₂PdGe₆ and Sm₂PtGe₆.

    Science.gov (United States)

    Troć, R; Wawryk, R; Gofryk, K; Gribanov, A V; Seropegin, Yu D

    2011-04-13

    The compounds Sm₂TGe₆ (T = Pd, Pt,) were synthesized and characterized by x-ray diffraction, magnetization, electrical resistivity, thermoelectric power, and specific heat measurements performed in the temperature range 2-300 K. Additional resistivity and thermoelectric power measurements performed down to 0.35 K have not indicated superconductivity. These compounds crystallize in the orthorhombic structure of Ce₂NiGe₆ type and order antiferromagnetically at 23(1) and 30(1) K, respectively, showing localized magnetism of a Sm(3+) ion with a crystal field doublet level being the ground state. Below T(N), the electrical resistivity, the thermoelectric power, and the specific heat are dominated by electron-magnon scattering with an antiferromagnetic spin-wave spectrum typical of anisotropic antiferromagnetic systems. The thermoelectric power, S, achieves medium positive values at high temperatures, indicating a hole domination in electrical transport in both samples. At low temperatures, S changes its sign and becomes negative. At about 10 K a small negative maximum in S(T) occurs for both studied compounds. All the measurements carried out point to well-localized 4f-electrons in these two compounds, being strongly influenced by the crystal-electric-field effect with a significant admixture of two J-multiplets (5/2 and 7/2), typical for Sm-containing compounds.

  2. Structure and thermomechanical behavior of NiTiPt shape memory alloy wires.

    Science.gov (United States)

    Lin, Brian; Gall, Ken; Maier, Hans J; Waldron, Robbie

    2009-01-01

    The objective of this work is to understand the structure-property relationships in polycrystalline NiTiPt (Ti 42.7 at.% Ni 7.5 at %Pt) with a composition showing pseudoelasticity at ambient temperatures. Structural characterization of the alloy includes grain size determination and texture analysis while the thermomechanical properties are explored using tensile testing. Variation in heat treatment is used as a vehicle to modify microstructure. The results are compared to experiments on Ni-rich NiTi alloy wires (Ti-51.0 at.% Ni), which are in commercial use in various biomedical applications. With regards to microstructure, both alloys exhibit a fiber texture along the wire drawing axis; however, the NiTiPt alloy grain size is smaller than that of the Ni-rich NiTi wires, while the latter materials contain second-phase precipitates. Given the nanometer-scale grain size in NiTiPt and the dispersed, nanometer-scale precipitate size in NiTi, the overall strength and ductility of the alloys are essentially identical when given appropriate heat treatments. Property differences include a much smaller stress hysteresis and smaller temperature dependence of the transformation stress for NiTiPt alloys compared to NiTi alloys. Potential benefits and implications for use in vascular stent applications are discussed.

  3. Monte Carlo Simulations of Segregation in Pt-Ni Catalyst Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Guofeng; Van Hove, Michel A.; Ross, Philip N.; Baskes, M.I.

    2004-04-01

    We have investigated the segregation of Pt atoms in the surfaces of Pt-Ni nanoparticles, using Modified Embedded Atom Model potentials and the Monte Carlo method. The nanoparticles are assumed to have disordered fcc configurations at two fixed overall concentrations (50 at. percent Pt and 75 at. percent Pt). We use four kinds of nanoparticle shapes [cube, tetrahedron, octahedron, and cubo-octahedron] terminated by {l_brace}111{r_brace} and {l_brace}100{r_brace} facets to examine the extent of the Pt segregation to the nanoparticle surfaces and determine the equilibrium structures of Pt-Ni nanoparticles at T=600 K. The model particles contain between 560 and 4631 atoms (particle size ranging from 2.5 to 5 nm). Our results imply that a complete (100)-facet reconstruction could make the cubo-octahendral Pt-Ni nanoparticles most energetically favorable, consistent with experimental observations. We predict that at 600 K due to segregation the equilibrium Pt50Ni50 nanoparticles with fewer than 2000 atoms and Pt75Ni25 nano particles with fewer than 4000 atoms would achieve a surface-sandwich structure, in which the Pt atoms are enriched in the outermost and third atomic shells while the Ni atoms are enriched in the second atomic shell. We also find that due to an order-disorder transition the Pt50Ni50 cubo-octahedral nanoparticles containing more than 2000 atoms would form a core-shell structure with a Pt-enriched surface and a Pt-deficient homogeneous core.

  4. Bulk metallic glass formation in the Pd-Ni-P and Pd-Cu-P alloy systems

    Energy Technology Data Exchange (ETDEWEB)

    Schwarz, R.B.; He, Y. [Los Alamos National Lab., NM (United States). Center for Materials Science

    1996-12-11

    Bulk metallic glasses were prepared in the Pd-Ni-P and Pd-Cu-P systems using a fluxing technique. The formation of bulk amorphous Pd-Cu-P alloys was reported here for the first time. For both alloy systems, bulk glass formation requires maintaining the phosphorus content near 20 at.%. In the Pd-Ni-P system, 10-mm diameter amorphous Pd{sub x}Ni{sub 80{minus}x}P{sub 20} rods can be formed for 25 {le} x {le} 60. In the Pd-Cu-P system, 7-mm diameter amorphous Pd{sub x}Cu{sub 80{minus}x}P{sub 20} rods can be produced for 40 {le} x {le} 60. From all the ternary alloys studied, Pd{sub 40}Ni{sub 40}P{sub 20} has the highest glass formability, and 25-mm diameter amorphous cylinders, 50 mm in length, can be easily fabricated. The glass stability of the Pd-Ni-P system is wider than that of the Pd-Cu-P system. For most bulk Pd-Ni-P glasses, {Delta}T > 90 K. The {Delta}T values of bulk amorphous Pd-Cu-P alloys are considerably smaller, ranging from 27 to 73 K. The elastic constants of bulk amorphous Pd-Ni-P and Pd-Cu-P alloys were determined using a resonant ultrasound spectroscopy technique. The Pd-Ni-P glasses are slightly stiffer than the Pd-Cu-P glasses. Within each alloy system, the Young`s modulus and the bulk modulus show little change with alloy composition. Of all the bulk glass forming systems so far investigated, the ternary Pd-Ni-P system has the best glass formability. This alloy was one of the first bulk glasses discovered, yet it still remains the best in terms of glass formability. Upon replacing part of Ni by Cu, the critical cooling rates are expected to be further reduced.

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

    Science.gov (United States)

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

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

    Science.gov (United States)

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

  7. Structures and energetics of 98 atom Pd-Pt nanoalloys: potential stability of the Leary tetrahedron for bimetallic nanoparticles.

    Science.gov (United States)

    Paz-Borbón, Lauro Oliver; Mortimer-Jones, Thomas V; Johnston, Roy L; Posada-Amarillas, Alvaro; Barcaro, Giovanni; Fortunelli, Alessandro

    2007-10-14

    The energetics of 98 atom bimetallic Pd-Pt clusters are studied using a combination of: a genetic algorithm technique (to explore vast areas of the configurational space); a basin-hopping atom-exchange routine (to search for lowest-energy homotops at fixed composition); and a shell optimisation approach (to search for high symmetry isomers). The interatomic interactions between Pd and Pt are modelled by the Gupta many-body empirical potential. For most compositions, the putative global minima are found to have structures based on defective Marks decahedra, but in the composition range from Pd46Pt52 to Pd63Pt35, the Leary tetrahedron (LT)--a structure previously identified for 98 atom Lennard-Jones clusters--is consistently found as the most stable structure. Based on the excess energy stability criterion, Pd56Pt42 represents the most stable cluster across the entire composition range. This structure, a Td-symmetry LT, exhibits multi-layer segregation with an innermost core of Pd atoms, an intermediate layer of Pt atoms and an outermost Pd surface shell (Pd-Pt-Pd). The stability of the Leary tetrahedron is compared against other low-energy competing structural motifs: the Marks decahedron (Dh-M), a "quasi" tetrahedron (a closed-packed structure) and two other closed-packed structures. The stability of LT structures is rationalized in terms of their spherical shape and the large number of nearest neighbours.

  8. Issues Concerning the Oxidation of Ni(Pt)Ti Shape Memory Alloys

    Science.gov (United States)

    Smialek, James

    2011-01-01

    The oxidation behavior of the Ni-30Pt-50Ti high temperature shape memory alloy is compared to that of conventional NiTi nitinol SMAs. The oxidation rates were 1/4 those of NiTi under identical conditions. Ni-Ti-X SMAs are dominated by TiO2 scales, but, in some cases, the activation energy diverges for unexplained reasons. Typically, islands of metallic Ni or Pt(Ni) particles are embedded in lower scale layers due to rapid selective growth of TiO2 and low oxygen potential within the scale. The blocking effect of Pt-rich particles and lower diffusivity of Pt-rich depletion zones are proposed to account for the reduction in oxidation rates.

  9. Study of PtNi/C catalyst for direct ethanol fuel cell; Estudo do catalisador PtNi/C para celula a combustivel de etanol direto

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, L.P.R. de; Silva, E.L. da; Amico, S.C.; Malfatti, C.F., E-mail: eticiaprm@gmail.com [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil)

    2014-07-01

    In this work, PtNi binary catalyst and pure platin catalyst were synthesized by the impregnation-reduction method, using Vulcan XC72R as support, for direct ethanol fuel cells. The composition and structure of the catalysts were analyzed by X-ray diffraction, the electrochemical behavior was evaluated by cyclic voltammetry and morphology of the catalysts was studied by high-resolution transmission electron microscopy. The results showed that the addition of Ni to Pt led to the contraction of the crystal lattice, increased the catalytic activity compared to pure Pt and initiated the electrooxidation of ethanol at lower potential. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Huang, T. [State Key Laboratory for Turbulence and Complex System, College of Engineering, Peking University, Beijing 100871 (China); Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871 (China); Cheng, J. [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Zheng, Y.F., E-mail: yfzheng@pku.edu.cn [State Key Laboratory for Turbulence and Complex System, College of Engineering, Peking University, Beijing 100871 (China); Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871 (China); Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China)

    2014-02-01

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

  11. Three-dimensional PtNi Hollow Nanochains as Enhanced Electrocatalyst for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Shaofang; Zhu, Chengzhou; Song, Junhua; Engelhard, Mark H.; He, Yang; Du, Dan; Wang, Chong M.; Lin, Yuehe

    2016-05-05

    Three-dimensional porous PtNi hollow nanochains are successfully synthesized via galvanic replacement method using Ni nanosponges as sacrificial templates in an aqueous solution. It is found that the composition and shell thickness of the 3D PtNi hollow nanochains can be easily controlled by tuning the concentration of Pt precursors. The as-prepared PtNi hollow nanochains with optimized composition present high electrochemical surface area (70.8 m2 g-1), which is close to that of commercial Pt/C (83 m2 g-1). Moreover, the PtNi catalyst with Pt content of ~77% presents superior electrocatalytic performance for oxygen reduction reaction compared to commercial Pt/C. It shows a mass activity of 0.58 A mgPt-1, which is around 3 times higher than that of Pt/C. This strategy may be extended to the preparation of other multimetallic nanocrystals with 3D hollow nanostructures, which are expected to present high catalytic properties.

  12. Methanol oxidation reaction activity of microwave irradiated and heat-treated Pt/Co and Pt/Ni nano-electrocatalysts

    CSIR Research Space (South Africa)

    Mathe, NR

    2014-11-01

    Full Text Available Bimetallic Pt nanoparticles were prepared by alloying Pt with the non-noble transition metals, Co and Ni, using a conventional heat-treatment (HT) method and microwaveirradiation (MW). The resulting samples were PteCo-Ht, PteNi-HT, PteCo, MW and Pt...

  13. Magnetic properties of BaM /Pd-Pt double-layered thin film deposited at various substrate temperatures

    Science.gov (United States)

    Nahar Shams, Nazmun; Liu, Xiaoxi; Matsumoto, Mitsunori; Morisako, Akimitsu

    2005-05-01

    Crystallographic and magnetic properties of barium ferrite (BaM) thin films deposited onto Pt, Pd, and an alloy of Pd-Pt underlayers by sputtering at different substrate temperatures (Ts) from 400to600°C have been studied. It is found that the coercivity values in the perpendicular direction (Hcperp) of the BaM /Pd-Pt films are higher than those of the BaM films deposited on Pd and Pt underlayers. C-axis orientation of BaM /Pd-Pt film can be achieved at very low Ts of 450°C with a Hcperp of 2.1kOe for 30-nm BaM.

  14. Quantitative Prediction of Surface Segregation in Bimetallic Pt-MAlloy Nanoparticles (M=Ni, Re, Mo)

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Guofeng; Van Hove, Michel A.; Ross, Phil N.; Baskes,Michael I.

    2005-06-20

    This review addresses the issue of surface segregation inbimetallic alloy nanoparticles, which are relevant to heterogeneouscatalysis, in particular for electro-catalysts of fuel cells. We describeand discuss a theoretical approach to predicting surface segregation insuch nanoparticles by using the Modified Embedded Atom Method and MonteCarlo simulations. In this manner it is possible to systematicallyexplore the behavior of such nanoparticles as a function of componentmetals, composition, and particle size, among other variables. We choseto compare Pt75Ni25, Pt75Re25, and Pt80Mo20 alloys as example systems forthis discussion, due to the importance of Pt in catalytic processes andits high-cost. It is assumed that the equilibrium nanoparticles of thesealloys have a cubo-octahedral shape, the face-centered cubic lattice, andsizes ranging from 2.5 nm to 5.0 nm. By investigating the segregation ofPt atoms to the surfaces of the nanoparticles, we draw the followingconclusions from our simulations at T= 600 K. (1) Pt75Ni25 nanoparticlesform a surface-sandwich structure in which the Pt atoms are stronglyenriched in the outermost and third layers while the Ni atoms areenriched in the second layer. In particular, a nearly pure Pt outermostsurface layer can be achieved in those nanoparticles. (2) EquilibriumPt75Re25 nanoparticles adopt a core-shell structure: a nearly pure Ptshell surrounding a more uniform Pt-Re core. (3) In Pt80Mo20nanoparticles, the facets are fully occupied by Pt atoms, the Mo atomsonly appear at the edges and vertices, and the Pt and Mo atoms arrangethemselves in an alternating sequence along the edges and vertices. Oursimulations quantitatively agree with previous experimental andtheoretical results for the extended surfaces of Pt-Ni, Pt-Re, and Pt-Moalloys. We further discuss the reasons for the different types of surfacesegregation found in the different alloys, and some of theirimplications.

  15. Bimetallic Ni/Pd finite systems: Structure and thermodynamics of bimetallic Ni/Pd nanostructures in two and three dimensions

    Energy Technology Data Exchange (ETDEWEB)

    Nieves-Torres, Stephanie [Department of Chemistry, University of Puerto Rico at Mayagueez, Mayagueez 00681 (Puerto Rico); Mo, Elizabeth [Department of Chemistry, Lehman College-CUNY, Bronx, NY 10468 (United States); Lopez, Gustavo E., E-mail: glopez@uprm.edu [Department of Chemistry, University of Puerto Rico at Mayagueez, Mayagueez 00681 (Puerto Rico); Department of Chemistry, Lehman College-CUNY, Bronx, NY 10468 (United States)

    2011-09-15

    Highlights: {yields} Structure and thermodynamic of Ni/Pd bimetallic clusters as a function of composition. {yields} Melting and low temperature order-disorder transitions in Ni/Pd bimetallic clusters. {yields} Implementation of efficient classical Monte Carlo techniques. - Abstract: By implementing replica-exchange Monte Carlo simulations within the multihistogram reweighting techniques, the structural and thermodynamic changes in bimetallic nickel-palladium nanostructured systems were studied as a function of composition. Specifically, two- and three-dimensional clusters composed of seven and thirteen atoms, respectively, were described using the embedded atom potential. The lowest energy equilibrium structures were determined, and associated to the degree of mixing in the material. In all cases, melting and order-disorder transitions were revealed by calculating the average constant volume heat capacity as a function of temperature. The change in Helmholtz free energy for the order-disorder transition was determined as a function of composition for each system.

  16. Facile synthesis of Pd-Pt alloy nanocages and their enhanced performance for preferential oxidation of CO in excess hydrogen.

    Science.gov (United States)

    Zhang, Hui; Jin, Mingshang; Liu, Hongyang; Wang, Jinguo; Kim, Moon J; Yang, Deren; Xie, Zhaoxiong; Liu, Jingyue; Xia, Younan

    2011-10-25

    This article describes a new method for the facile synthesis of Pd-Pt alloy nanocages with hollow interiors and porous walls by using Pd nanocubes as sacrificial templates. Differing from our previous work (Zhang, H.; Jin, M. S.; Wang, J. G.; Li, W. Y.; Camargo, P. H. C.; Kim, M. J.; Yang, D. R.; Xie, Z. X.; Xia, Y. Synthesis of Pd-Pt Bimetallic Nanocrystals with a Concave Structure through a Bromide-Induced Galvanic Replacement Reaction. J. Am. Chem. Soc.2011, 133, 6078-6079), we complemented the galvanic replacement (between Pd nanocubes and PtCl(4)(2-)) with a coreduction process (for PdCl(4)(2-) from the galvanic reaction and PtCl(4)(2-) from the feeding) to generate Pd-Pt alloy nanocages in one step. We found that the rate of galvanic replacement (as determined by the concentrations of Br(-) and PtCl(4)(2-) and temperature) and the rates of coreduction (as determined by the type of reductant and temperature) played important roles in controlling the morphology of resultant Pd-Pt alloy nanocages. The Pd-Pt nanocages exhibited both enhanced activity and selectivity for the preferential oxidation (PROX) of CO in excess hydrogen than those of Pd nanocubes and the commercial Pt/C thanks to the alloy composition and hollow structure. In addition, as the sizes of the Pd-Pt nanocages decreased, they exhibited higher CO conversion rates and lower maximum conversion temperatures due to the increase in specific surface area.

  17. Electronic and structural properties of Fe3Pd-Pt ferromagnetic shape memory alloys

    Science.gov (United States)

    Stern, R. A.; Willoughby, S. D.; Ramirez, A.; MacLaren, J. M.; Cui, J.; Pan, Q.; James, R. D.

    2002-05-01

    Ferromagnetic shape memory (FSM) alloys are scientifically and technologically interesting materials that combine ferromagnetism with a reversible martensitic phase transformation. Fe70Pd30 has recently been shown to display a FSM effect at usable temperatures and low fields. Reported here are results of experimental studies on Fe70Pd30 and electronic structure calculations on Fe70Pd30-xPtx. The calculations show that additions of Pt by 6 at % to Fe70Pd30 can triple the magnetocrystalline anisotropy. There is, however, a large discrepancy between the measured and calculated anisotropy values of Fe70Pd30, suggesting the presence of significant disorder in the measured samples. Other calculated structural and magnetic properties are in close agreement with experimental values.

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

    Science.gov (United States)

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

    2006-05-21

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

  19. Analisis Sistem Pengukuran Kinerja dengan Metode Integrated Performance Measurement Systems (IPMS) Pada PT. PD. Paya Pinang

    OpenAIRE

    Alda, Tania

    2016-01-01

    Dalam era globalisasi saat ini, industri pengolahan kelapa sawit di Indonesia mengalami perkembangan yang cukup pesat. Pengukuran kinerja sangat penting bagi perusahaan, dapat membantu perusahaan untuk mengetahui tingkat performansi kerja yang baik. Saat ini, cara terbaik dalam mengukur kinerja adalah dengan mempertimbangkan stakeholder perusahaan dan mengidentifikasi kebutuhan stakeholder tersebut. PT. PD. Paya Pinang adalah salah satu perusahaan kelapa sawit swasta nasional yang melakukan p...

  20. Green and Facile Synthesis of Pd-Pt Alloy Nanoparticles by Laser Irradiation of Aqueous Solution.

    Science.gov (United States)

    Nakamura, Takahiro; Sato, Shunichi

    2015-01-01

    Solid-solution palladium-platinum (Pd-Pt) alloy nanoparticles (NPs) with fully tunable compositions were directly fabricated through high-intensity laser irradiation of an aqueous solution of palladium and platinum ions without using any reducing agents or thermal processes. Transmission electron microscopy (TEM) observations showed that nanometer-sized particles were fabricated by laser irradiation of mixed aqueous solutions of palladium and platinum ions with different feeding ratios. The crystalline nature of the NPs was precisely characterized by X-ray diffraction (XRD). Despite the fact that, for the bulk systems, a pair of XRD peak was detected between the palladium and platinum peaks because of the large miscibility gap in the Pd-Pt binary phase diagram, only a single XRD peak was seen for the Pd-Pt NPs fabricated in the present study. Moreover, the peak position shifted from that of pure palladium towards platinum with increasing fraction of platinum ions in solution. Consequently, the interplanar spacings of the alloy NPs agreed well with the estimated values obtained from Vegard's law. These observations strongly indicate the formation of solid-solution Pd-Pt alloy NPs with fully tunable compositions. This technique is not only a "green" (environmentally-friendly) and facile process, but is also widely applicable to other binary and ternary systems.

  1. Nucleation and growth mechanisms for Pd-Pt bimetallic nanodendrites and their electrocatalytic properties

    National Research Council Canada - National Science Library

    Lim, Byungkwon; Jiang, Majiong; Yu, Taekyung; Camargo, Pedro H. C; Xia, Younan

    2010-01-01

    .... These nanostructures can be easily prepared by a one-step, seeded growth method that involves the reduction of K2PtCl4 by L-ascorbic acid in the presence of 9-nm truncated octahedral Pd seeds in an aqueous solution...

  2. Structural characterization of Pt-Pd core-shell nanoparticles by Cs-corrected STEM

    Energy Technology Data Exchange (ETDEWEB)

    Esparza, R., E-mail: resparza@fata.unam.mx [Universidad Nacional Autonoma de Mexico, Centro de Fisica Aplicada y Tecnologia Avanzada (Mexico); Garcia-Ruiz, Amado F. [UPIICSA-COFAA, Instituto Politecnico Nacional (Mexico); Velazquez Salazar, J. J. [University of Texas at San Antonio, Department of Physics and Astronomy (United States); Perez, R. [Universidad Nacional Autonoma de Mexico, Centro de Fisica Aplicada y Tecnologia Avanzada (Mexico); Jose-Yacaman, M. [The University of Texas at San Antonio, Department of Physics and Astronomy (United States)

    2013-01-15

    Pt-Pd core-shell nanoparticles were synthesized using a modified polyol method. A thermal method under refluxing, carrying on the reaction up to 285 Degree-Sign C, has been performed to reduce metallic salts using ethylene glycol as reducer and poly(N-vinyl-2-pyrrolidone) as protective reagent of the formed bimetallic nanoparticles. According to other works, this type of structure has been studied and utilized to successfully increase the catalytic properties of monometallic nanoparticles Pt or Pd. Core-shell bimetallic nanoparticles were structurally characterized using aberration-corrected scanning transmission electron microscopy (Cs-STEM) equipped with a high-angle annular dark field detector, energy-dispersive X-ray spectrometry (EDS), and electron energy-loss spectroscopy (EELS). The high-resolution elemental line scan and mappings were carried out using a combination of STEM-EDS and STEM-EELS. The obtained results show the growth of the Pd shell on the Pt core with polyhedral morphology. The average size of the bimetallic nanoparticles was 13.5 nm and the average size of the core was 8.5 nm; consequently, the thickness of the shell was around 2.5 nm. The growth of the Pd shell on the Pt core is layer by layer, suggesting a Frank-van der Merwe growth mechanism.

  3. Atomic Structure of Pt3Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy.

    Science.gov (United States)

    Becknell, Nigel; Kang, Yijin; Chen, Chen; Resasco, Joaquin; Kornienko, Nikolay; Guo, Jinghua; Markovic, Nenad M; Somorjai, Gabor A; Stamenkovic, Vojislav R; Yang, Peidong

    2015-12-23

    Understanding the atomic structure of a catalyst is crucial to exposing the source of its performance characteristics. It is highly unlikely that a catalyst remains the same under reaction conditions when compared to as-synthesized. Hence, the ideal experiment to study the catalyst structure should be performed in situ. Here, we use X-ray absorption spectroscopy (XAS) as an in situ technique to study Pt3Ni nanoframe particles which have been proven to be an excellent electrocatalyst for the oxygen reduction reaction (ORR). The surface characteristics of the nanoframes were probed through electrochemical hydrogen underpotential deposition and carbon monoxide electrooxidation, which showed that nanoframe surfaces with different structure exhibit varying levels of binding strength to adsorbate molecules. It is well-known that Pt-skin formation on Pt-Ni catalysts will enhance ORR activity by weakening the binding energy between the surface and adsorbates. Ex situ and in situ XAS results reveal that nanoframes which bind adsorbates more strongly have a rougher Pt surface caused by insufficient segregation of Pt to the surface and consequent Ni dissolution. In contrast, nanoframes which exhibit extremely high ORR activity simultaneously demonstrate more significant segregation of Pt over Ni-rich subsurface layers, allowing better formation of the critical Pt-skin. This work demonstrates that the high ORR activity of the Pt3Ni hollow nanoframes depends on successful formation of the Pt-skin surface structure.

  4. Structure and reactivity of Pd-Pt clusters produced by laser vaporization of bulk alloys

    Science.gov (United States)

    Rousset, J. L.; Cadrot, A. M.; Lianos, L.; Renouprez, A. J.

    Pd-Pt nanoclusters are obtained by the focusing of an Nd:YAG laser onto rods of alloys. The aggregates, which are produced by plasma cooling via short helium bursts synchronized with the laser pulses, are collected on amorphous carbon or silicon substrates, in a UHV chamber. Transmission electron microscopy (TEM) experiments show that the diameters of the clusters range between 1.5 and 4.5 nm, and analytical microscopy indicates that they have the same composition as the vaporized rods. Low-energy ion scattering (LEIS) also shows that the surface of the obtained clusters is Pd enriched: the Pd concentration in the first atomic layer is found to be equal to 38% for a Pd17Pt83 rod composition and 87% for the Pd65 Pt35 alloy. The catalytic activity of these clusters in the hydrogenation of 1,3-butadiene to butenes and butane is measured in static mode, with mass spectrometry detection. The reactivity of the bimetallic clusters is explained by the atomic local order and low-coordination sites considered as ``hot sites''.

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

    Science.gov (United States)

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

    2008-08-15

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

  6. The onion-ring structure for Pd-Pt bimetallic clusters.

    Science.gov (United States)

    Cheng, Daojian; Wang, Wenchuan; Huang, Shiping

    2006-08-24

    The onion-ring structure is validated in the Pd-Pt bimetallic clusters of total atom numbers 147 and 309 through the Monte Carlo method by using the second-moment approximation of the tight-binding (TB-SMA) potentials, which is conceived in predicting the possible structures of the bimetallic clusters by He et al. [J. Am. Chem. Soc. 2003, 125, 11034] and Hwang et al. [J. Am. Chem. Soc. 2005, 127, 11140]. In the onion-ring structure, Pd atoms and Pt atoms occupy alternate layers of the clusters. The formation of the onion-ring structure can be associated with the fact that the single Pt impurity is favorable to stay in the subsurface layer and the central part of bimetallic clusters.

  7. Potential oscillations in a proton exchange membrane fuel cell with a Pd-Pt/C anode

    Science.gov (United States)

    Lopes, Pietro P.; Ticianelli, Edson A.; Varela, Hamilton

    We report in this paper the occurrence of potential oscillations in a proton exchange membrane fuel cell (PEMFC) with a Pd-Pt/C anode, fed with H 2/100 ppm CO, and operated at 30 °C. We demonstrate that the use of Pd-Pt/C anode enables the emergence of dynamic instabilities in a PEMFC. Oscillations are characterized by the presence of very high oscillation amplitude, ca. 0.8 V, which is almost twice that observed in a PEMFC with a Pt-Ru/C anode under similar conditions. The effects of the H 2/CO flow rate and cell current density on the oscillatory dynamics were investigated and the mechanism rationalized in terms of the CO oxidation and adsorption processes. We also discuss the fundamental aspects concerning the operation of a PEMFC under oscillatory regime in terms of the benefit resulting from the higher average power output.

  8. Spray Forming of NiTi and NiTiPd Shape-Memory Alloys

    Science.gov (United States)

    Mabe, James; Ruggeri, Robert; Noebe, Ronald

    2008-01-01

    In the work to be presented, vacuum plasma spray forming has been used as a process to deposit and consolidate prealloyed NiTi and NiTiPd powders into near net shape actuators. Testing showed that excellent shape memory behavior could be developed in the deposited materials and the investigation proved that VPS forming could be a means to directly form a wide range of shape memory alloy components. The results of DSC characterization and actual actuation test results will be presented demonstrating the behavior of a Nitinol 55 alloy and a higher transition temperature NiTiPd alloy in the form of torque tube actuators that could be used in aircraft and aerospace controls.

  9. Spray Forming of NiTi and NiTiPd Shape-Memory Alloys

    Science.gov (United States)

    Mabe, James; Ruggeri, Robert; Noebe, Ronald

    2008-01-01

    In the work to be presented, vacuum plasma spray forming has been used as a process to deposit and consolidate prealloyed NiTi and NiTiPd powders into near net shape actuators. Testing showed that excellent shape memory behavior could be developed in the deposited materials and the investigation proved that VPS forming could be a means to directly form a wide range of shape memory alloy components. The results of DSC characterization and actual actuation test results will be presented demonstrating the behavior of a Nitinol 55 alloy and a higher transition temperature NiTiPd alloy in the form of torque tube actuators that could be used in aircraft and aerospace controls.

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

    Science.gov (United States)

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

    2012-04-01

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

  11. NiO spacer mediated magnetic anisotropy in L 10-FePt /NiO /A 1 -FePt trilayer structures

    Science.gov (United States)

    Gao, Tenghua; Harumoto, Takashi; Zhang, Song; Tu, Rong; Zhang, Lianmeng; Nakamura, Yoshio; Shi, Ji

    2017-04-01

    L 10-FePt /NiO /A 1 -FePt trilayers have been grown on MgO(001) substrate, in which the top FePt layer is of A 1 structure, and the bottom FePt layer is of L 10 structure with 001 preferred orientation and strong perpendicular anisotropy. This structure gives rise to a 90∘ spin alignment configuration of the two ferromagnetic layers across the NiO spacer. To further manipulate the spin configurations of the trilayer structure, we performed an in-plane field cooling (FC). The subsequent hysteresis measurements for the top FePt layer show unambiguous angular dependence of remanent magnetization relative to the direction of the field during FC; i.e., in-plane anisotropy is induced. Taking into account the spin-flop configuration predicted in previous theoretical study, the coupling at the lower interface makes the Ni spins cant out of the (1 ¯1 ¯1 ) easy plane, and difficult to rotate around the axis perpendicular to the film plane. Correspondingly, the induced anisotropy after FC is considered to result from the realignment of Ni spins and enhancement of the coupling at the upper interface. The magnetic domain imaging results for the bottom perpendicular magnetized FePt layer strongly support this consideration; some of the stripe domains tend to be along the direction of the applied field during FC with reduced stripe width.

  12. Molecular Dynamics Simulation of Solidification of Pd-Ni Clusters with Different Nickel Content

    Directory of Open Access Journals (Sweden)

    Chen Gang

    2014-01-01

    Full Text Available Molecular dynamics simulation has been performed for investigating the glass transition of Pd-Ni alloy nanoparticles in the solidification process. The results showed that the Pd-Ni nanoparticles with composition far from pure metal should form amorphous structure more easily, which is in accordance with the results of the thermodynamic calculation. There are some regular and distorted fivefold symmetry in the amorphous Pd-Ni alloy nanoparticles. The nanoclusters with bigger difference value between formation enthalpies of solutions and glasses will transform to glass more easily than the other Pd-Ni alloy nanoclusters.

  13. Oxygen reduction reaction on a highly-alloyed Pt-Ni supported carbon electrocatalyst in acid solution

    CSIR Research Space (South Africa)

    Zheng, H

    2010-08-31

    Full Text Available Alloyed electrocatalysts such as PtNi/C[1-2], PtCo/C[3], PtCr/C[4], PtFe/C [5-6], and non-alloyed Pt-TiO2/C were reportedly investigated for methanol tolerance during Oxygen reduction reaction (ORR). The high methanol tolerance...

  14. Evaluation of the behavior of PtPd/MWCNT electrocatalysts as ethylene glycol-tolerant electrodes for oxygen oxidation reaction (ORR); Evaluacion del comportamiento de electrocatalizadores tipo PtPd/MWCNT como electrodos para la reaccion de oxidacion del oxigeno (ORR) tolerantes al etilenglicol

    Energy Technology Data Exchange (ETDEWEB)

    Morales-Acosta, D.; Arriaga, L.G. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Pedro Escobedo, Queretaro (Mexico)]. E-mail: dmorales@cideteq.mx; Alvarez-Contreras, L. [Centro de Investigacion en Materiales Avanzados S. C., Chihuahua, Chihuahua (Mexico); Fraire Luna, S.; Rodriguez Varela, F.J. [Cinvestav, Unidad Saltillo, Ramos Arizpe, Coahuila, (Mexico)

    2009-09-15

    Pt-Pd/MWCNTs (atomic ratio Pt:Pd 43:57) and Pt/MWCNTs electrocatalysts were synthesized and evaluated as cathodes for oxygen reduction reaction (ORR) with the application of direct ethylene glycol fuel cells (DEGFC). A commercial PtC material was also evaluated as a reference. It was found that Pt-Pd/MWCNT has a capability for high tolerance to ethylene glycol (EG) and higher selectivity for ORR compared to a single Pt- cathode. As a result, the change in onset potential of the ORR, Eonset, in Pt-Pd/MWCNTs was considerably less than the change in Pt/MWCNTs or Pt/C. The average particle size (XRD) was 3.5nm and 4nm for Pt/MWCNTs and Pt-Pd/MWCNTs, respectively. A moderate degree of alloying was determined for the material. The application of Pt-Pd electrocatalysts in DEGFCs should be advantageous. [Spanish] Electrocatalizadores Pt-Pd/MWCNTs (relacion atomic Pt:Pd 43:57) y Pt/MWCNTs fueron sintetizados y evaluados como catodos para la reaccion de reduccion del oxigeno (ORR) con aplicacion del celdas de consumo directo de etilenglicol (Direct Ethylene Glycol Fuel Cells, o DEGFC). Como referencia, un material comercial tipo Pt/C fue tambien evaluado. Se encontro que Pt-Pd/MWCNTs tiene una alta capacidad de tolerancia al etilenglicol (EG) y una selectividad mayor hacia la ORR comparado con el catodo basado en Pt-solo. Como resultado, el cambio en potencial de inicio de la ORR, Eonset, en Pt-Pd/MWCNTs fue considerablemente menor que el cambio en Pt/MWCNTs o Pt/C. La talla de particula promedio (de XRD) fue 3.5 nm y 4 nm para Pt/MWCNTs y Pt-Pd/MWCNTs, respectivamente. Un moderado grado de aleacion fue determinado para el material. Una aplicacion ventajosa para electrocatalizadores tipo Pt-Pd debe ser en DEGFCs.

  15. Pt单层修饰Pd/C氧还原催化剂%Pt monolayer on Pd/C as electrocatalyst for oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    章欢; 戴煜; 胡晓宏; 陈胜利; 陈经广

    2011-01-01

    Carbon supported Pd nanoparticle catalysts (Pd/C) for oxygen reduction reaction (ORR) were synthesized by using the liquid-phase pyrolysis method and the impregnation method respectively. Although the Pd/C catalysts produced in liquid phase method possessed larger particle sizes, they exhibited higher activity for ORR and much better durability as compared with Pd/C prepared by the impregnation-reduction method. By galvanic displacement of the monolayer Cu formed on Pd nanoparticle surface through under potential deposition, Pt monolayer decorated Pd/C catalysts (PtML/Pd/C) were fabricated. The thus prepared Pt monolayer catalysts exhibited ORR activity close and durability superior to the state-of-the-art commercial Pt/C. The Pt mass activity of the PtML/Pd/C catalyst for ORR was more than 4 times higher than that given by the Pt/C, showing a great perspective of the Pt monolayer electrocatalysts in fuel cells applications.%分别利用液相热解法和浸渍还原法制备了碳载钯纳米催化剂(Pd/C),并研究了其对氧还原反应的电催化活性.与浸渍还原法相比,液相热解法得到的Pd/C催化剂虽然粒径较大,但表现出较好的氧还原反应(ORR)活性和稳定性在所制备的Pd/C催化剂基础上,通过置换欠电势沉积的Cu原子单层,获得了Pt单层修饰的Pd/C催化剂,其ORR活性较Pd/C催化剂有显著提高,且与纯Pt/C催化剂接近,而其耐久性则较纯Pt/C催化剂有显著提升,显示出Pt单层催化剂的潜在优势.

  16. Synthesis of PtNi Alloy Nanoparticles on Graphene-Based Polymer Nanohybrids for Electrocatalytic Oxidation of Methanol

    Directory of Open Access Journals (Sweden)

    Tung-Yuan Yung

    2016-12-01

    Full Text Available We have successfully produced bimetallic PtNi alloy nanoparticles on poly(diallyldimethylammonium chloride (PDDA-modified graphene nanosheets (PtNi/PDDA-G by the “one-pot” hydrothermal method. The size of PtNi alloy nanoparticles is approximately 2–5 nm. The PDDA-modified graphene nanosheets (PDDA-G provides an anchored site for metal precursors; hence, the PtNi nanoparticles could be easily bond on the PDDA-G substrate. PtNi alloy nanoparticles (2–5 nm display a homogenous alloy phase embedded on the PDDA-G substrate, evaluated by Raman, X-ray diffractometer (XRD, thermal gravity analysis (TGA, electron surface chemical analysis (ESCA, and electron energy loss spectroscopy (EELS. The Pt/Ni ratio of PtNi alloy nanoparticles is ~1.7, examined by the energy dispersive spectroscopy (EDS spectra of transmitting electron microscopy (EDS/TEM spectra and mapping technique. The methanol electro-oxidation of PtNi/PDDA-G was evaluated by cyclic voltammetry (CV in 0.5 M of H2SO4 and 0.5 M of CH3OH. Compared to Pt on carbon nanoparticles (Pt/C and Pt on Graphene (Pt/G, the PtNi/PDDA-G exhibits the optimal electrochemical surface area (ECSA, methanol oxidation reaction (MOR activity, and durability by chrono amperometry (CA test, which can be a candidate for MOR in the electro-catalysis of direct methanol fuel cells (DMFC.

  17. Characterization of Ternary NiTiPt High-Temperature Shape Memory Alloys

    Science.gov (United States)

    Rios, Orlando; Noebe, Ronald; Biles, Tiffany; Garg, Anita; Palczer, Anna; Scheiman, Daniel; Seifert, Hans Jurgen; Kaufman, Michael

    2005-01-01

    Pt additions substituted for Ni in NiTi alloys are known to increase the transformation temperature of the alloy but only at fairly high Pt levels. However, until now only ternary compositions with a very specific stoichiometry, Ni50-xPtxTi50, have been investigated and then only to very limited extent. In order to learn about this potential high-temperature shape memory alloy system, a series of over twenty alloys along and on either side of a line of constant stoichiometry between NiTi and TiPt were arc melted, homogenized, and characterized in terms of their microstructure, transformation temperatures, and hardness. The resulting microstructures were examined by scanning electron microscopy and the phase compositions quantified by energy dispersive spectroscopy."Stoichiometric" compositions along a line of constant stoichiometry between NiTi to TiPt were essentially single phase but by any deviations from a stoichiometry of (Ni,Pt)50Ti50 resulted in the presence of at least two different intermetallic phases, depending on the overall composition of the alloy. Essentially all alloys, whether single or two-phase, still under went a martensitic transformation. It was found that the transformation temperatures were depressed with initial Pt additions but at levels greater than 10 at.% the transformation temperature increased linearly with Pt content. Also, the transformation temperatures were relatively insensitive to alloy stoichiometry within the range of alloys examined. Finally, the dependence of hardness on Pt content for a series of Ni50-xPtxTi50 alloys showed solution softening at low Pt levels, while hardening was observed in ternary alloys containing more than about 10 at.% Pt. On either side of these "stoichiometric" compositions, hardness was also found to increase significantly.

  18. The pilot test of Pt-Pd and Pt-Rh feeds extracted and separated with a new sulfoxide extractant

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Platinum, palladium and rhodium of the raw feeds extracted and separated with a new sulfoxide extractant (MSO)were studied in the paper. The pilot test results showed that the percentage extractions are more than 99% for platinum and palladium in Pt-Pd feed, and the percentage strippings are 100% and 99.2% with HCl and ammonia, respectively. The ratio of palladium to platinum is 0.0016 in stripping platinum solution, and the ratio of platinum to palladium is 0.0020 in stripping palladium solution. The percentage extraction of platinum is 99% in Pt-Rh feed, and the percentage stripping is 100%.The ratio of rhodium to platinum is 0.0002 in stripping platinum solution. Therefore, platinum, palladium, and rhodium feeds are separated effectively with MSO.

  19. High-activity PtRuPd/C catalyst for direct dimethyl ether fuel cells.

    Science.gov (United States)

    Li, Qing; Wen, Xiaodong; Wu, Gang; Chung, Hoon T; Gao, Rui; Zelenay, Piotr

    2015-06-22

    Dimethyl ether (DME) has been considered as a promising alternative fuel for direct-feed fuel cells but lack of an efficient DME oxidation electrocatalyst has remained the challenge for the commercialization of the direct DME fuel cell. The commonly studied binary PtRu catalyst shows much lower activity in DME than methanol oxidation. In this work, guided by density functional theory (DFT) calculation, a ternary carbon-supported PtRuPd catalyst was designed and synthesized for DME electrooxidation. DFT calculations indicated that Pd in the ternary PtRuPd catalyst is capable of significantly decreasing the activation energy of the CO and CH bond scission during the oxidation process. As evidenced by both electrochemical measurements in an aqueous electrolyte and polymer-electrolyte fuel cell testing, the ternary catalyst shows much higher activity (two-fold enhancement at 0.5 V in fuel cells) than the state-of-the-art binary Pt50 Ru50 /C catalyst (HiSPEC 12100).

  20. Efficiency of bimetallic PtPd on polydopamine modified on various carbon supports for alcohol oxidations

    Science.gov (United States)

    Pinithchaisakula, A.; Ounnunkad, K.; Themsirimongkon, S.; Promsawan, N.; Waenkaew, P.; Saipanya, S.

    2017-02-01

    In this work, the preparation, characterization, and electrocatalytic analysis of the catalysts on various carbon substrates for direct alcohol fuel cells were studied. Selected carbons were modified with/without polydopamine (labelled as PDA-C and C) and further metal electrodeposited incorporated onto the glassy carbon (labelled as 5Pt1Pd/PDA-C and 5Pt1Pd/C). Four various carbon materials were used e.g. graphite (G), carbon nanotube (CNT), graphene (GP) and graphene oxide (GO) and the carbons were modified with PDA denoted as PDA-G, PDA-CNT, PDA-GP and PDA-GO, respectively. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) experimental observation showed narrow size distribution of metal anchored on the PDA-C and C materials. Chemical compositions and oxidation states of the catalysts were determined by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX). The catalytic performances for small organic electro-oxidation (e.g. methanol and ethanol) were measured by cyclic voltammetry (CV). Among different PDA-C and C catalysts, monometallic Pt showed less activity than the bimetallic catalysts. Among catalysts with PDA, the 5Pt1Pd/PDA-GO catalyst facilitated methanol and ethanol oxidations with high oxidation currents and If/Ib value and stability with low potentials while among catalysts without PDA, the 5Pt1Pd/CNT provides highest activity and stability. It was found that the catalysts with PDA provided high activity and stability than the catalysts without PDA. The improved catalytic performance of the prepared catalysts could be related to the higher active surface area from polymer modification and bimetallic catalyst system in the catalyst composites.

  1. NiPt hollow nanocatalyst:Green synthesis, size control and electrocatalysis

    Institute of Scientific and Technical Information of China (English)

    Aixian Shan; Ming Cheng; Hongsheng Fan; Zhichao Chen; Rongming Wang; Chinping Chen

    2014-01-01

    Nearly monodispersed hollow nanospheres of bimetallic NiPt have been synthesized by a one-pot wet chemical method at room temperature with a precursor Ni nanocompound as a sacrificial template. The size control is carried out via the sacrificial template, from about 35 nm to nearly 100 nm in diameter. The shell thickness of the NiPt hollow sphere reaches down to as thin as 2-3 nm slightly larger than a single layer of alloyed NiPt nanocrystallites. The product with the citric acid as surfactant exhibits enhanced oxygen reduction activities compared to a commercial Pt/C catalyst and the hollow nanospheres coated with PVP. It has potential applications in fuel cells, biotechnology and environmental chemistry with the facile synthesis, low cost and excellent electrocatalytic activity.

  2. High Work Output Ni-Ti-Pt High Temperature Shape Memory Alloys and Associated Processing Methods

    Science.gov (United States)

    Noebe, Ronald D. (Inventor); Draper, Susan L. (Inventor); Nathal, Michael V. (Inventor); Garg, Anita (Inventor)

    2009-01-01

    According to the invention, compositions of Ni-Ti-Pt high temperature, high force, shape memory alloys are disclosed that have transition temperatures above 100 C.; have narrow hysteresis; and produce a high specific work output.

  3. NiPt hollow nanocatalyst: Green synthesis, size control and electrocatalysis

    Directory of Open Access Journals (Sweden)

    Aixian Shan

    2014-04-01

    Full Text Available Nearly monodispersed hollow nanospheres of bimetallic NiPt have been synthesized by a one-pot wet chemical method at room temperature with a precursor Ni nanocompound as a sacrificial template. The size control is carried out via the sacrificial template, from about 35 nm to nearly 100 nm in diameter. The shell thickness of the NiPt hollow sphere reaches down to as thin as 2–3 nm slightly larger than a single layer of alloyed NiPt nanocrystallites. The product with the citric acid as surfactant exhibits enhanced oxygen reduction activities compared to a commercial Pt/C catalyst and the hollow nanospheres coated with PVP. It has potential applications in fuel cells, biotechnology and environmental chemistry with the facile synthesis, low cost and excellent electrocatalytic activity.

  4. The effect of stress and magnetostriction on the anisotropy of CoNi/Pt multilayers

    NARCIS (Netherlands)

    van Drent, W.P.; van Drent, W.P.; Bijker, M.D.; Lodder, J.C.

    1996-01-01

    An attempt is made to correlate the effective magnetic anisotropy of sputtered CoNi/Pt multilayers to the average stress in the thin film. It was found that compressive film stress decreases the perpendicular magnetic anisotropy.

  5. The effect of stress and magnetostriction on the anisotropy of CoNi/Pt multilayers

    NARCIS (Netherlands)

    Drent, van W.P.; Bijker, M.D.; Lodder, J.C.

    1996-01-01

    An attempt is made to correlate the effective magnetic anisotropy of sputtered CoNi/Pt multilayers to the average stress in the thin film. It was found that compressive film stress decreases the perpendicular magnetic anisotropy.

  6. Bimetallic Pt-Ni catalysts supported on usy zeolite for n-hexane isomerization

    OpenAIRE

    F. V. Barsi; Cardoso,D.

    2009-01-01

    Isomerization of linear alkanes has had considerable importance for the refining industry because the isomers formed in this reaction have high octane number. Most works reported in the literature studied the use of bifunctional catalysts, i.e., ones that have acid sites and metallic sites. In this study, bifunctional monometallic (Ni or Pt) and bimetallic catalysts (Pt-Ni), using HUSY zeolite as the support, were prepared in order to verify the role of the metal content and composition on th...

  7. Electronic and structural influence of Ni by Pd substitution on the hydrogenation properties of TiNi

    Energy Technology Data Exchange (ETDEWEB)

    Emami, Hoda; Souques, Raphaeel [Chimie Metallurgique des Terres Rares, Institut de Chimie et des Materiaux Paris-Est, CNRS, Universite Paris-Est, UMR 7182, 2-8 rue Henri Dunant, F-94320 Thiais (France); Crivello, Jean-Claude, E-mail: crivello@icmpe.cnrs.fr [Chimie Metallurgique des Terres Rares, Institut de Chimie et des Materiaux Paris-Est, CNRS, Universite Paris-Est, UMR 7182, 2-8 rue Henri Dunant, F-94320 Thiais (France); Cuevas, Fermin [Chimie Metallurgique des Terres Rares, Institut de Chimie et des Materiaux Paris-Est, CNRS, Universite Paris-Est, UMR 7182, 2-8 rue Henri Dunant, F-94320 Thiais (France)

    2013-02-15

    In Ti (Ni,Pd) compounds, the hydrogen capacity and the stability of their hydrides decreases when Ni is partially substituted by larger in size Pd atoms. To understand this peculiar behaviour, the crystal structure of TiNi{sub 1-x}Pd{sub x}D{sub y} (x=0.1, 0.3 and 0.5) deuterides and the stability of TiNi{sub 1-x}Pd{sub x} (0{<=}x{<=}0.5) intermetallics and their hydrides have been investigated by both neutron diffraction experiments and Density Functional Theory (DFT) calculations. Neutron diffraction shows that at x=0.1 and 0.3, deuterium absorption induces tetragonal distortion in intermetallics sublattice whereas at x=0.5 the cubic symmetry is preserved. The structural properties and the heat of formation of TiNi{sub 1-x}Pd{sub x} (0{<=}x{<=}0.5) intermetallics and their hydrides have been determined by DFT. These results show that Pd substitution increases the stability of the intermetallics and decreases the stability of the hydrides, which confirms the rule of reverse stability. - Graphical abstract: Crystal structure of Ti(Ni,Pd)Hy hydrides in the I4/mmm space group. Highlights: Black-Right-Pointing-Pointer Neutron Diffraction and DFT calculations have been done on TiNi{sub 1-x}Pd{sub x}H{sub y} compounds. Black-Right-Pointing-Pointer Electronic effect of Pd substitution governs the hydrogenation properties in TiNi. Black-Right-Pointing-Pointer The rule of reverse stability in intermetallics/hydrides is observed with Pd substitution. Black-Right-Pointing-Pointer The hydrogen atoms in the I4/mmm structure prefer to occupy the 16n site.

  8. Activated carbon fibers impregnated with Pd and Pt catalysts for toluene removal.

    Science.gov (United States)

    Liu, Zhen-Shu; Chen, Jian-Yuan; Peng, Yu-Hui

    2013-07-15

    Few studies have investigated the use of activated carbon fibers (ACFs) impregnated with noble metals for the catalytic oxidation of volatile organic compounds (VOCs). This study determined the removal efficiency of toluene as a function of time over ACF-supported metal catalysts. Two catalysts (Pt and Pd), five reaction temperatures (120, 150, 200, 250, and 300°C), and three oxygen contents (6%, 10%, and 21%) were investigated to determine the removal of toluene. To study the effects of the characteristics of the catalysts on toluene removal, the composition and morphology of the ACFs were analyzed using the BET, XPS, ICP, and FE-SEM. The results showed that the 0.42%Pd/ACFs showed greater activity for toluene removal than did 2.68%Pt/ACFs at a reaction temperature of 200°C and an oxygen content of 10%. The main removal mechanism of toluene over the 2.68%Pt/ACFs at reaction temperatures less than 200°C was adsorption. The long-term catalytic activity of the 2.68%Pt/ACFs for toluene removal at a reaction temperature of 250°C and an oxygen content of 10% could be obtained. Furthermore, toluene removal over the 2.68%Pt/ACFs at 200°C could be enhanced with increasing oxygen content.

  9. Correlation between bias fields and magnetoresistance in CoPt biased FeNi/Ta/FeNi GMR heterosystems

    Science.gov (United States)

    Wang, Yi; Sahoo, S.; Echtenkamp, W.; Binek, Ch.

    2009-03-01

    Exchange coupled magnetic hard layer (HL)/ soft layer (SL) thin films show SL biasing in close analogy to conventional exchange bias systems with antiferromagnetic pinning.^1 Here we study CoPt(35nm)/FeNi450nm/Ta(d)/FeNi450nm heterostructures with d between 0.7 and 5nm. The CoPt films have in-plane magnetic anisotropy and pin the adjacent FeNi SL films. The latter are exchange coupled from top via Ta spacer layers with FeNi in a GMR-type architecture. We use AGFM and SQUID magnetometry to study the FeNi magnetization reversal with (CoPt) and without (vacuum) pinning layer proximity. The two minor FeNi hysteresis loops of the GMR trilayer reveal different biasing effects due to the distinct exchange interaction at the respective interfaces. The FeNi/CoPt coupling is systematically tuned via a series of set fields which allow partial demagnetization of the pinning layer. Moreover we study the correlation between the overall and minor magnetization reversals and the corresponding magnetoresistance effects for various temperature between T=20 and 400K. ^1Ch. Binek, S. Polisetty, Xi He and A. Berger, Phys. Rev. Lett. 96, 067201 (2006). Financial support by NSF through Career DMR-0547887, MRSEC DMR-0820521 and the NRI.

  10. Fast response and recovery of hydrogen sensing in Pd-Pt nanoparticle-graphene composite layers

    Science.gov (United States)

    Kumar, Rakesh; Varandani, Deepak; Mehta, B. R.; Singh, V. N.; Wen, Zhenhai; Feng, Xinliang; Müllen, Klaus

    2011-07-01

    This study reports the fast response and recovery of hydrogen sensing in nanoparticle-graphene composite layers fabricated using chemical methods and comprising of isolated Pd alloy nanoparticles dispersed onto graphene layers. For 2% hydrogen at 40 °C and 1 atm pressure, a response time of Pd-Pt nanoparticle-graphene composite material are important for understanding the effect of gas adsorption on electronic conduction in graphene layers and for developing a new type of gas sensor based on changes in the electronic properties of the interface.

  11. Electrochemical reduction of O2 and NO on Ni, Pt and Au

    DEFF Research Database (Denmark)

    Kammer Hansen, Kent

    2008-01-01

    The electrochemical reduction of oxygen and nitric oxide was studied using cyclic voltammetry on point electrodes of Ni, Pt and Au in the temperature range 400-600 degrees C. All the materials were more active towards the reduction of oxygen than towards the reduction of nitric oxide, except Pt...

  12. Use of Hydrogen Chemisorption and Ethylene Hydrogenation as Predictors for Aqueous Phase Reforming of Lactose over Ni@Pt and Co@Pt Bimetallic Overlayer Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lai, Qinghua; Skoglund, Michael D.; Zhang, Chen; Morris, Allen R.; Holles, Joseph H.

    2016-10-20

    Overlayer Pt on Ni (Ni@Pt) or Co (Co@Pt) were synthesized and tested for H2 generation from APR of lactose. H2 chemisorption descriptor showed that Ni@Pt and Co@Pt overlayer catalysts had reduced H2 adsorption strength compared to a Pt only catalyst, which agree with computational predictions. The overlayer catalysts also demonstrated lower activity for ethylene hydrogenation than the Pt only catalyst, which likely resulted from decreased H2 binding strength decreasing the surface coverage of H2. XAS results showed that overlayer catalysts exhibited higher white line intensity than the Pt catalyst, which indicates a negative d-band shift for the Pt overlayer, further providing evidence for overlayer formation. Lactose APR studies showed that lactose can be used as feedstock to produce H2 and CO under desirable reaction conditions. The Pt active sites of Ni@Pt and Co@Pt overlayer catalysts showed significantly enhanced H2 production selectivity and activity when compared with that of a Pt only catalyst. The single deposition overlayer with the largest d-band shift showed the highest H2 activity. The results suggest that overlayer formation using directed deposition technique could modify the behavior of the surface metal and ultimately modify the APR activity.

  13. Predictions of the Pt(8)Ti phase in unexpected systems.

    Science.gov (United States)

    Taylor, Richard H; Curtarolo, Stefano; Hart, Gus L W

    2010-05-19

    The binary A(8)B phase (prototype Pt(8)Ti) has been experimentally observed in 11 systems. A high-throughput search over all the binary transition intermetallics, however, reveals 59 occurrences of the A(8)B phase: Au(8)Zn(dagger), Cd(8)Sc(dagger), Cu(8)Ni(dagger), Cu(8)Zn(dagger), Hg(8)La, Ir(8)Os(dagger), Ir(8)Re, Ir(8)Ru(dagger), Ir(8)Tc, Ir(8)W(dagger), Nb(8)Os(dagger), Nb(8)Rh(dagger), Nb(8)Ru(dagger), Nb(8)Ta(dagger), Ni(8)Fe, Ni(8)Mo(dagger)*, Ni(8)Nb(dagger)*, Ni(8)Ta*, Ni(8)V*, Ni(8)W, Pd(8)Al(dagger), Pd(8)Fe, Pd(8)Hf, Pd(8)Mn, Pd(8)Mo*, Pd(8)Nb, Pd(8)Sc, Pd(8)Ta, Pd(8)Ti, Pd(8)V*, Pd(8)W*, Pd(8)Zn, Pd(8)Zr, Pt(8)Al(dagger), Pt(8)Cr*, Pt(8)Hf, Pt(8)Mn, Pt(8)Mo, Pt(8)Nb, Pt(8)Rh(dagger), Pt(8)Sc, Pt(8)Ta, Pt(8)Ti*, Pt(8)V*, Pt(8)W, Pt(8)Zr*, Rh(8)Mo, Rh(8)W, Ta(8)Pd, Ta(8)Pt, Ta(8)Rh, V(8)Cr(dagger), V(8)Fe(dagger), V(8)Ir(dagger), V(8)Ni(dagger), V(8)Pd, V(8)Pt, V(8)Rh, and V(8)Ru(dagger) ((dagger) = metastable, * = experimentally observed). This is surprising for the wealth of new occurrences that are predicted, especially in well-characterized systems (e.g., Cu-Zn). By verifying all experimental results while offering additional predictions, our study serves as a striking demonstration of the power of the high-throughput approach. The practicality of the method is demonstrated in the Rh-W system. A cluster-expansion-based Monte Carlo model reveals a relatively high order-disorder transition temperature.

  14. Synthesis of Pd-Pt bimetallic nanocrystals with a concave structure through a bromide-induced galvanic replacement reaction.

    Science.gov (United States)

    Zhang, Hui; Jin, Mingshang; Wang, Jinguo; Li, Weiyang; Camargo, Pedro H C; Kim, Moon J; Yang, Deren; Xie, Zhaoxiong; Xia, Younan

    2011-04-20

    This article describes a systematic study of the galvanic replacement reaction between PtCl(6)(2-) ions and Pd nanocrystals with different shapes, including cubes, cuboctahedrons, and octahedrons. It was found that Br(-) ions played an important role in initiating, facilitating, and directing the replacement reaction. The presence of Br(-) ions led to the selective initiation of galvanic replacement from the {100} facets of Pd nanocrystals, likely due to the preferential adsorption of Br(-) ions on this crystallographic plane. The site-selective galvanic replacement resulted in the formation of Pd-Pt bimetallic nanocrystals with a concave structure owing to simultaneous dissolution of Pd atoms from the {100} facets and deposition of the resultant Pt atoms on the {111} facets. The Pd-Pt concave nanocubes with different weight percentages of Pt at 3.4, 10.4, 19.9, and 34.4 were also evaluated as electrocatalysts for the oxygen reduction reaction (ORR). Significantly, the sample with a 3.4 wt.% of Pt exhibited the largest specific electrochemical surface area and was found to be four times as active as the commercial Pt/C catalyst for the ORR in terms of equivalent Pt mass.

  15. Low Pt content direct methanol fuel cell anode catalyst: nanophase PtRuNiZr

    Science.gov (United States)

    Narayanan, Sekharipuram R. (Inventor); Whitacre, Jay F. (Inventor)

    2010-01-01

    A method for the preparation of a metallic material having catalytic activity that includes synthesizing a material composition comprising a metal content with a lower Pt content than a binary alloy containing Pt but that displays at least a comparable catalytic activity on a per mole Pt basis as the binary alloy containing Pt; and evaluating a representative sample of the material composition to ensure that the material composition displays a property of at least a comparable catalytic activity on a per mole Pt basis as a representative binary alloy containing Pt. Furthermore, metallic compositions are disclosed that possess substantial resistance to corrosive acids.

  16. Characterization and reactivity of Pd Pt bimetallic supported catalysts obtained by laser vaporization of bulk alloy

    Science.gov (United States)

    Rousset, J. L.; Cadete Santos Aires, F. J.; Bornette, F.; Cattenot, M.; Pellarin, M.; Stievano, L.; Renouprez, A. J.

    2000-09-01

    Bimetallic Pd-Pt clusters produced by laser vaporization of bulk alloy have been deposited on high surface alumina. Energy dispersive X-ray (EDX) analysis and transmission electron microscopy (TEM) show that they have a perfectly well-defined stoichiometry and a narrow range of size. Therefore, they constitute ideal systems to investigate alloying effects towards reactivity. Pd-Pt alloys are already known for their applications in the hydrogenation of unsaturated hydrocarbons, especially aromatics, because this system is highly resistant to sulfur and nitrogen poisoning. In this context, the catalytic properties of this system have been investigated in the hydrogenation of tetralin in the presence of hydrogen sulfide. Preliminary results show that this model catalyst is more sulfur-resistant than each of the pure supported metals prepared by chemical methods.

  17. Sintering of oxide-supported Pt and Pd nanoparticles in air studied by in situ TEM

    DEFF Research Database (Denmark)

    Simonsen, Søren Bredmose

    at elevated temperatures. The time-resolved TEM images are presented and these offer direct insight into the fundamental dynamics of the sintering process at the nano-scale. For Pt, Pd and bimetallic Pt-Pd nanoparticles it is shown that the sintering process is governed by the Ostwald ripening mechanism...... correlations between neighbouring nanoparticles in the atom-exchange process. The sintering process was also presented statistically by particle size distributions extracted from the TEM images. The statistical data agreed only partly with the mean-field kinetic models for ripening, but the deviations could......This thesis presents a fundamental study of the sintering of supported nanoparticles in relation to diesel oxidation catalysts. The sintering of supported nanoparticles is an important challenge in relation to this catalyst, as well as many other catalyst systems, and a fundamental understanding...

  18. ADSORPTION BEHAVIORS OF Pt(IV) AND Pd(II) ON POLYMERIC ESTER THIOUREA RESIN

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Polymeric ester thiourea resin (PDTU-I) is a new kind of chelating resin with functional atoms S, N and O, so it is an excellent adsorbent for noble metal ions. In batch testes, the adsorption capacities of PDTU-I for Pt(IV) and Pd(II) increase with the increase of contact time, temperature and initial concentration of metal ions. The adsorption data fit Boyd’s diffusion equation of liquid film, Langmuir adsorption isotherm and Freundlich adsorption isotherm. The maximum adsorption capacities calculated by Langmuir equation are 2.54mmol/g for Pt(IV) and 4.88mmol/g for Pd(II). According to FTIR and XPS results, functional groups of PDTU-I coordinate with noble metal ions in the adsorption process.

  19. Ternary Pd2/PtFe networks supported by 3D graphene for efficient and durable electrooxidation of formic acid.

    Science.gov (United States)

    Hu, Chuangang; Zhao, Yang; Cheng, Huhu; Hu, Yue; Shi, Gaoquan; Dai, Liming; Qu, Liangti

    2012-12-18

    A newly-designed network of ternary Pd(2)/PtFe nanowires on a three-dimensional graphene framework has been fabricated via a dual solvothermal approach, which presents superior electrocatalytic activity towards the oxidation of formic acid.

  20. Abnormal infrared effects of nanometer scale thin film material of PtPd alloy in CO adsorption

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Nanometer scale thin film material of PtPd alloy supported on glassy carbon (nm-PtPd/GC) was prepared by the electrochemical codeposition method under cyclic voltammetric conditions. STM patterns demonstrated that the prepared thin films are composed of layered crystallites in elliptic form. Electrochemical in situ FTIRS studies explored the abnormal infrared effects (AIREs) of nmPtPd/GC for CO adsorption, which are ( i ) the remarkable enhancement of IR absorption, (ii) the inversion of COad band direction, and (iii) notable increase in the full width at half maximum (FWHM) of COad bands. The results demonstrated also that the enhancement factor of IR absorption varies with the thickness of PtPd alloy film and has reached a maximum value of 38.3 under the experimental conditions.

  1. Multilevel programming in Cu/NiO y /NiO x /Pt unipolar resistive switching devices

    Science.gov (United States)

    Sarkar, P. K.; Bhattacharjee, S.; Barman, A.; Kanjilal, A.; Roy, A.

    2016-10-01

    The application of a NiO y /NiO x bilayer in resistive switching (RS) devices with x > y was studied for its ability to achieve reliable multilevel cell (MLC) characteristics. A sharp change in resistance brought about by sweeping the voltage, along with an improved on/off ratio (>103) and endurance (104) were achieved in the bilayer structure as compared to the single NiO x layer devices. Moreover, it was found that nonvolatile and stable resistance levels, especially the multiple low-resistance states of Cu/NiO y /NiO x /Pt memory devices, could be controlled by varying the compliance current. All the multilevel resistance states of the Cu/NiO y /NiO x /Pt bilayer devices were stable for up to 500 consecutive dc switching cycles, as compared to the Cu/NiO x /Pt single layer devices. The temperature-dependent variation of the high and low resistance states of both the bilayer and single layer devices was further investigated to elucidate the charge conduction mechanism. Finally, based on a detailed analysis of the experimental results, comparisons of the possible models for RS in bilayer and single layer memory devices have also been discussed.

  2. Supergene neoformation of Pt-Ir-Fe-Ni alloys: multistage grains explain nugget formation in Ni-laterites

    Science.gov (United States)

    Aiglsperger, Thomas; Proenza, Joaquín A.; Font-Bardia, Mercè; Baurier-Aymat, Sandra; Galí, Salvador; Lewis, John F.; Longo, Francisco

    2016-11-01

    Ni-laterites from the Dominican Republic host rare but extremely platinum-group element (PGE)-rich chromitites (up to 17.5 ppm) without economic significance. These chromitites occur either included in saprolite (beneath the Mg discontinuity) or as `floating chromitites' within limonite (above the Mg discontinuity). Both chromitite types have similar iridium-group PGE (IPGE)-enriched chondrite normalized patterns; however, chromitites included in limonite show a pronounced positive Pt anomaly. Investigation of heavy mineral concentrates, obtained via hydroseparation techniques, led to the discovery of multistage PGE grains: (i) Os-Ru-Fe-(Ir) grains of porous appearance are overgrown by (ii) Ni-Fe-Ir and Ir-Fe-Ni-(Pt) phases which are overgrown by (iii) Pt-Ir-Fe-Ni mineral phases. Whereas Ir-dominated overgrowths prevail in chromitites from the saprolite, Pt-dominated overgrowths are observed within floating chromitites. The following formation model for multistage PGE grains is discussed: (i) hypogene platinum-group minerals (PGM) (e.g. laurite) are transformed to secondary PGM by desulphurization during serpentinization; (ii) at the stages of serpentinization and/or at the early stages of lateritization, Ir is mobilized and recrystallizes on porous surfaces of secondary PGM (serving as a natural catalyst) and (iii) at the late stages of lateritization, biogenic mediated neoformation (and accumulation) of Pt-Ir-Fe-Ni nanoparticles occurs. The evidence presented in this work demonstrates that in situ growth of Pt-Ir-Fe-Ni alloy nuggets of isometric symmetry is possible within Ni-laterites from the Dominican Republic.

  3. Size dependence of thermoelectric power of Au, Pd, Pt nanoclusters deposited onto HOPG surface

    OpenAIRE

    Borisyuk, P. V.; V. I. Troyan; Lebedinskii, Yu Yu; Vasilyev, O S

    2016-01-01

    The paper presents the study of tunnel current-voltage characteristics of Au, Pd and Pt nanoclusters deposited onto the highly oriented pyrolytic graphite (HOPG) surface by pulsed laser deposition. The analysis of tunnel current-voltage characteristics obtained by scanning tunneling spectroscopy (STS) allowed to recover the thermoelectric power value of nanoclusters. It was found that the value of thermoelectric power of pulsed laser deposited nanoclusters depends on nanocluster material and ...

  4. Role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Ham, Hyung Chul, E-mail: hchahm@kist.re.kr [Department of Chemical Engineering, The University of Texas at Austin, Austin, TX 78712 (United States); Fuel Cell Research Center, Korea Institute of Science and Technology, Seoul (Korea, Republic of); Manogaran, Dhivya [Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, TX 78712 (United States); Hwang, Gyeong S., E-mail: gshwang@che.utexas.edu [Department of Chemical Engineering, The University of Texas at Austin, Austin, TX 78712 (United States); Han, Jonghee; Kim, Hyoung-Juhn; Nam, Suk Woo; Lim, Tae Hoon [Fuel Cell Research Center, Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2015-03-30

    Graphical abstract: - Highlights: • Pd ensembles greatly reduce CO adsorption energy as compared to Pt ensembles. • The steeper potential energy surface of CO adsorption in Pd(1 1 1) than in Pt(1 1 1). • Switch of binding site preference in ensembles is key to determining CO adsorption. • Opposite electronic (ligand) effect in Pd and Pt ensemble. - Abstract: Using spin-polarized density functional calculations, we investigate the role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys through a study of the energetics, charge transfer, geometric and electronic structures of CO on various Pd/Pt ensembles (monomer/dimer/trimer/tetramer). We find that the effect of Pd ensembles on the reduction of CO chemisorption energy is much larger than the Pt ensemble case. In particular, small-sized Pd ensembles like monomer show a substantial reduction of CO chemisorption energy compared to the pure Pd (1 1 1) surface, while there are no significant size and shape effects of Pt ensembles on CO chemisorption energy. This is related to two factors: (1) the steeper potential energy surface (PES) of CO in Pd (1 1 1) than in Pt (1 1 1), indicating that the effect of switch of binding site preference on CO chemisorption energy is much larger in Pd ensembles than in Pt ensembles, and (2) down-shift of d-band in Pd ensembles/up-shift of d-band in Pt ensembles as compared to the corresponding pure Pd (1 1 1)/Pt (1 1 1) surfaces, suggesting more reduced activity of Pd ensembles toward CO adsorption than the Pt ensemble case. We also present the different bonding mechanism of CO on Pd/Pt ensembles by the analysis of orbital resolved density of state.

  5. The effects of Ni and Mg{sub 2}Ni interlayer on hydrogenation properties of Pd sandwiched Mg films

    Energy Technology Data Exchange (ETDEWEB)

    Jain, Pragya, E-mail: pragya.2604@gmail.com [Centre for Non-Conventional Energy Resources, University of Rajasthan, Jaipur 302055 (India); Jain, Ankur; Vyas, Devendra; Verma, Reena [Centre for Non-Conventional Energy Resources, University of Rajasthan, Jaipur 302055 (India); Khan, S.A. [Inter University Accelerator Centre, New Delhi 110 067 (India); Jain, I.P., E-mail: ipjain46@gmail.com [Centre for Non-Conventional Energy Resources, University of Rajasthan, Jaipur 302055 (India)

    2011-02-03

    Research highlights: > Hydrogen storage in solid state media has been centre of attraction due to several merits over other methods i.e. liquid and gaseous storage of hydrogen. > Particular attention has been focused on Mg based materials because high capacity storage can be achieved in these materials. However, problems regarding high thermodynamic stability and slow kinetics must be addressed before these hydrides can be used for transportation applications. > Thin films are a good approach to understand the mechanism of hydrogen sorption processes in Mg based materials, but on the other hand it is very difficult to measure hydrogen content in thin films using conventional Sievert type method due to low amount of available hydrogen in thin films. > ERDA technique has been proven as a useful tool for depth profiling and content measurement of hydrogen in thin films. > The present research is an attempt to measure hydrogen content in Pd sandwiched Mg thin films using ERDA. Additionally the effect of Ni and Mg2Ni layer on these systems has also been observed and discussed. - Abstract: The scope of present study is to investigate and compare the areal hydrogen concentration of Pd/Mg/Ni/Pd and Pd/Mg/Mg{sub 2}Ni/Pd films with the Pd/Mg/Pd base system using Elastic Recoil Detection Analysis (ERDA) technique. Metals were deposited on Si substrate by thermal evaporation and electron gun evaporation technique followed by hydrogenation for 2 h at 150 deg. C and 2 bar hydrogen pressure. ERDA study reveals that Pd/Mg/Ni/Pd and Pd/Mg/Mg{sub 2}Ni/Pd films absorb 7.08 x 10{sup 17} and 1.68 x 10{sup 18} hydrogen atoms/cm{sup 2}, respectively, in comparison to 4 x 10{sup 17} atoms/cm{sup 2} absorbed by base system. The influence of Ni and Mg{sub 2}Ni interlayer on the hydrogen storage properties of base system were investigated by changes in structural and surface topographical properties using XRD and AFM techniques, respectively. These results strongly supports the ERDA findings

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

    Directory of Open Access Journals (Sweden)

    Hamdi Baccar

    2015-04-01

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

  7. Formic Acid Oxidation over Hierarchical Porous Carbon Containing PtPd Catalysts

    Directory of Open Access Journals (Sweden)

    Elena Pastor

    2013-10-01

    Full Text Available The use of high surface monolithic carbon as support for catalysts offers important advantage, such as elimination of the ohmic drop originated in the interparticle contact and improved mass transport by ad-hoc pore design. Moreover, the approach discussed here has the advantage that it allows the synthesis of materials having a multimodal porous size distribution, with each pore size contributing to the desired properties. On the other hand, the monolithic nature of the porous support also imposes new challenges for metal loading. In this work, the use of Hierarchical Porous Carbon (HPC as support for PtPd nanoparticles was explored. Three hierarchical porous carbon samples (denoted as HPC-300, HPC-400 and HPC-500 with main pore size around 300, 400 and 500 nm respectively, are used as porous support. PtPd nanoparticles were loaded by impregnation and subsequent chemical reduction with NaBH4. The resulting material was characterized by EDX, XRD and conventional electrochemical techniques. The catalytic activity toward formic acid and methanol electrooxidation was evaluated by electrochemical methods, and the results compared with commercial carbon supported PtPd. The Hierarchical Porous Carbon support discussed here seems to be promising for use in DFAFC anodes.

  8. Pt-Pd bimetallic nanoparticles on MWCNTs: catalyst for hydrogen peroxide electrosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Felix-Navarro, R. M., E-mail: moi6salazar@hotmail.com; Beltran-Gastelum, M.; Salazar-Gastelum, M. I.; Silva-Carrillo, C.; Reynoso-Soto, E. A.; Perez-Sicairos, S.; Lin, S. W. [Centro de Graduados e Investigacion, Instituto Tecnologico de Tijuana (Mexico); Paraguay-Delgado, F. [Centro de Investigacion en Materiales Avanzados (Mexico); Alonso-Nunez, G. [Centro de Nanociencias y Nanotecnologia (Mexico)

    2013-08-15

    Bimetallic nanoparticles of Pt-Pd were deposited by the microemulsion method on a multiwall carbon nanotube (MWCNTs) to obtain a Pt-Pd/MWCNTs for electrocatalytic reduction of O{sub 2} to H{sub 2}O{sub 2}. The activity and selectivity of the catalyst was determined qualitatively by the rotating disk electrode method in acidic medium. The catalyst was spray-coated onto a reticulated vitreous carbon substrate and quantitatively was tested in bulk electrolysis for 20 min under potentiostatic conditions (0.5 V vs Ag/AgCl) in a 0.5 M H{sub 2}SO{sub 4} electrolyte using dissolved O{sub 2}. The bulk electrolysis experiments show that the Pt-Pd/MWCNTs catalyst is more efficient for H{sub 2}O{sub 2} electrogeneration than a MWCNTs catalyst. Nitrobenzene degradation by electrogenerated H{sub 2}O{sub 2} alone and Electro-Fenton process were also tested. Our results show that both processes decompose nitrobenzene, but the Electro-Fenton process does it more efficiently. The prepared nanoparticulated catalyst shows a great potential in environmental applications.

  9. Characterization of Pt-Pd/C Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    S. S. Mahapatra

    2011-01-01

    Full Text Available The Pt-Pd/C electrocatalyst was synthesized on graphite substrate by the electrochemical codeposition technique. The physicochemical characterization of the catalyst was done by SEM, XRD, and EDX. The electrochemical characterization of the Pt-Pd/C catalyst for methanol electro-oxidation was studied over a range of NaOH and methanol concentrations using cyclic voltammetry, quasisteady-state polarization, chronoamperometry, and electrochemical impedance spectroscopy. The activity of methanol oxidation increased with pH due to better OH species coverage on the electrode surface. At methanol concentration (>1.0 M, there is no change in the oxidation peak current density because of excess methanol at the electrode surface and/or depletion of OH− at the electrode surface. The Pt-Pd/C catalyst shows good stability and the low value of Tafel slope and charge transfer resistance. The enhanced electrocatalytic activity of the electrodes is ascribed to the synergistic effect of higher electrochemical surface area, preferred OH− adsorption, and ad-atom contribution on the alloyed surface.

  10. The effect of reducing agents on the electronic, magnetic and electrocatalytic properties of thiol-capped Pt/Co and Pt/Ni nanoparticles

    CSIR Research Space (South Africa)

    Mathe, NR

    2015-05-01

    Full Text Available The electronic, magnetic and electrocatalytic properties of bimetallic thiol-capped Pt/Co and Pt/Ni nanoparticles were synthesised using two reducing agents, NaBH(sub4) and N(sub2)H(sub4). X-ray diffraction analysis of the nanoparticles showed Pt...

  11. Efficient photodegradation of methyl violet dye using TiO2/Pt and TiO2/Pd photocatalysts

    Science.gov (United States)

    Saeed, Khalid; Khan, Idrees; Gul, Tamanna; Sadiq, Mohammad

    2017-02-01

    Titanium oxide supported palladium (TiO2/Pd) and titanium oxide supported platinum (TiO2/Pt) nanoparticles were prepared from their precursors through the incipient wetness method. The TiO2/Pd and TiO2/Pt nanoparticles were characterized by scanning electron microscopy (SEM), and energy dispersive X-rays (EDX), while the photodegradation study of methyl violet was performed by UV/VIS spectrophotometry. The morphological study shows that the Pd and Pt were well deposited on the surface of TiO2, which was confirmed by EDX. Both TiO2/Pd and TiO2/Pt nanoparticles were used as photocatalysts for the photodegradation of methyl violet in aqueous media under UV-light irradiation. The photodegradation study revealed that the TiO2/Pd and TiO2/Pt nanoparticles degraded about 95 and 78% of dye within 20 min, respectively. The effect of various parameters such as catalyst dosage, concentration of dye, and medium on the photocatalytic degradation was examined. The activity of recovered TiO2/Pd and TiO2/Pt nanoparticles was studied.

  12. Direct methanol fuel cells: Pt-Ni/C binary electrocatalysts; Celulas a combutivel de metanol direto: eletrocatalisadores binarios de Pt-Ni/C

    Energy Technology Data Exchange (ETDEWEB)

    Salgado, Jose Ricardo Cezar; Antolini, Ermete; Santos, Ana Maria dos; Gonzalez, Ernesto Rafael [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Inst. de Quimica], e-mail: salgado@iqsc.usp.br

    2004-07-01

    Direct methanol fuel cells use platinum alloys as more efficient catalysts than platinum. In the case of binary alloys, the second metal affects several properties of platinum, like the interatomic distance, the electronic density and the capacity of forming oxygenated species at lower potentials. In this work, Pt-Ni catalysts supported on high surface area carbon (Pt-Ni/C) were prepared and characterized, and tested as catalysts in the anode and the cathode in direct methanol fuel cells. In both cases the performance of the material was better than that of Pt/C, and comparing the two situations it was better when the material was used in the cathode. The improved performance in the cathode was attributed to the nickel that forms a true alloy with platinum, while the better performance in the anode was attributed to the presence of nickel oxides. (author)

  13. Large spin-orbit torques in Pt/Co-Ni/W heterostructures

    Science.gov (United States)

    Yu, Jiawei; Qiu, Xuepeng; Legrand, William; Yang, Hyunsoo

    2016-07-01

    The spin orbit torques (SOTs) in perpendicularly magnetized Co-Ni multilayers sandwiched between two heavy metals (HM) have been studied. By exploring various HM materials, we show an efficient enhancement or cancellation of the total SOT, depending on the combination of the two HM materials. The maximum SOT effective field is obtained in Pt/Co-Ni/W heterostructures. We also model our double HM system and show that the effective spin Hall angle has a peak value at certain HM thicknesses. Measuring the SOT in Pt/Co-Ni/W for various W thicknesses confirms an effective spin Hall angle up to 0.45 in our double HM system.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-12-12

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

  15. Temperature dependent two-phase behaviour of magnetisation and spin polarisation in NiPt

    Energy Technology Data Exchange (ETDEWEB)

    Schaefers, Markus; Thomas, Andy; Reiss, Guenter [Bielefeld University, Universitaetsstrasse 25, D-33615 Bielefeld (Germany)

    2007-07-01

    We investigated the temperature dependent behaviour of magnetisation and spin polarisation in NiCu and NiPt alloys. The advantage of these alloys is the reduced Curie temperature compared with pure Nickel. The whole range of magnetisation is accessible in experiment for these alloys. Magnetic tunnel junctions with these alloys as free electrode were prepared by dc-magnetron sputtering in an UHV system with a base pressure of 1 . 10{sup -7} mbar and argon ion beam etching. TMR ratio was measured temperature dependent with a dc 2-point method. Spin polarisation was calculated by Julliere's formula. Magnetisation was measured with a SQUID for different temperatures. The NiPt alloy showed a maximum for in-plane magnetisation and spin polarisation at about 190 K. There are indications for a perpendicular magnetic anisotropy at low temperatures in the NiPt alloy.

  16. Ferromagnetic resonance measurements of (Co/Ni/Co/Pt) multilayers with perpendicular magnetic anisotropy

    Science.gov (United States)

    Sbiaa, R.; Shaw, J. M.; Nembach, H. T.; Bahri, M. Al; Ranjbar, M.; Åkerman, J.; Piramanayagam, S. N.

    2016-10-01

    Multilayers of [Co/Ni(t)/Co/Pt]×8 with varying Ni thickness were investigated for possible use as a free layer in magnetic tunnel junctions and spintronics devices. The thickness t of the Ni sub-layer was varied from 0.3 nm to 0.9 nm and the resulting magnetic properties were compared with (Co/Ni) and (Co/Pt) multilayers. As determined from magnetic force microscopy, magnetometry and ferromagnetic resonance measurements, all multilayers exhibited perpendicular magnetic anisotropy. Compared with (Co/Pt) multilayers, the sample with t of 0.9 nm showed almost the same anisotropy field of μ 0 H k   =  1.15 T but the damping constant was 40% lower. These characteristics make these multilayers attractive for spin torque based magnetoresistive devices with perpendicular anisotropy.

  17. Direct evidence for active site-dependent formic acid electro-oxidation by topmost-surface atomic redistribution in a ternary PtPdCu electrocatalyst.

    Science.gov (United States)

    Cui, Chun-Hua; Li, Hui-Hui; Cong, Huai-Ping; Yu, Shu-Hong; Tao, Franklin Feng

    2012-12-25

    The active site-dependent electrochemical formic acid oxidation was evidenced by the increased coverage of Pt in the topmost mixed PtPd alloy layer of ternary PtPdCu upon potential cycling, which demonstrated two catalytic pathways only in one catalyst owing to surface atomic redistribution in an acidic electrolyte environment.

  18. Enhanced gas sensing performance of electrospun Pt-functionalized NiO nanotubes with chemical and electronic sensitization.

    Science.gov (United States)

    Fu, Jiecai; Zhao, Changhui; Zhang, Junli; Peng, Yong; Xie, Erqing

    2013-08-14

    Pt-functionalized NiO composite nanotubes were synthesized by a simple electrospinning method, and their morphology, chemistry, and crystal structure have been characterized at the nanoscale. It was found that the Pt nanoparticles were dispersed uniformly in the NiO nanotubes, and the Pt-functionalized NiO composite nanotubes showed some dendritic structure in the body of nanotubes just like thorns growing in the nanotubes. Compared with the pristine NiO nanotube based gas sensor and other NiO-based gas sensors reported previously, the Pt-functionalized NiO composite nanotube based gas sensor showed substantially enhanced electrical responses to target gas (methane, hydrogen, acetone, and ethanol), especially ethanol. The NiO-Pt 0.7% composite nanotube based gas sensor displayed a response value of 20.85 at 100 ppm at ethanol and 200 °C, whereas the pristine NiO nanotube based gas sensor only showed a response of 2.06 under the same conditions. Moreover, the Pt-functionalized NiO composite nanotube based gas sensor demonstrated outstanding gas selectivity for ethanol against methane, hydrogen, and acetone. The reason for which the Pt-functionalized NiO composite nanotube based gas sensor obviously enhanced the gas sensing performance is attributed to the role of Pt on the chemical sensitization (catalytic oxidation) of target gases and the electronic sensitization (Fermi-level shifting) of NiO.

  19. Tuning Surface Structure and Strain in Pd-Pt Core-Shell Nanocrystals for Enhanced Electrocatalytic Oxygen Reduction.

    Science.gov (United States)

    Xiong, Yalin; Shan, Hao; Zhou, Zhengnan; Yan, Yucong; Chen, Wenlong; Yang, Yaxiong; Liu, Yongfeng; Tian, He; Wu, Jianbo; Zhang, Hui; Yang, Deren

    2017-02-01

    Icosahedral, octahedral, and cubic Pd@Pt core-shell nanocrystals with two atomic Pt layers are epitaxially generated under thermodynamic control. Such icosahedra exhibit remarkably enhanced catalytic properties for oxygen reduction reaction compared to the octahedra and cubes as well as commercial Pt/C, which can be attributed to ligand and geometry effects, especially twin-induced strain effect that is revealed by geometrical phase analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. 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.

  1. In Situ Generation of Pd-Pt Core-Shell Nanoparticles on Reduced Graphene Oxide (Pd@Pt/rGO) Using Microwaves: Applications in Dehalogenation Reactions and Reduction of Olefins.

    Science.gov (United States)

    Goswami, Anandarup; Rathi, Anuj K; Aparicio, Claudia; Tomanec, Ondrej; Petr, Martin; Pocklanova, Radka; Gawande, Manoj B; Varma, Rajender S; Zboril, Radek

    2017-01-25

    Core-shell nanocatalysts are a distinctive class of nanomaterials with varied potential applications in view of their unique structure, composition-dependent physicochemical properties, and promising synergism among the individual components. A one-pot microwave (MW)-assisted approach is described to prepare the reduced graphene oxide (rGO)-supported Pd-Pt core-shell nanoparticles, (Pd@Pt/rGO); spherical core-shell nanomaterials (∼95 nm) with Pd core (∼80 nm) and 15 nm Pt shell were nicely distributed on the rGO matrix in view of the choice of reductant and reaction conditions. The well-characterized composite nanomaterials, endowed with synergism among its components and rGO support, served as catalysts in aromatic dehalogenation reactions and for the reduction of olefins with high yield (>98%), excellent selectivity (>98%) and recyclability (up to 5 times); both Pt/rGO and Pd/rGO and even their physical mixtures showed considerably lower conversions (20 and 57%) in dehalogenation of 3-bromoaniline. Similarly, in the reduction of styrene to ethylbenzene, Pd@Pt core-shell nanoparticles (without rGO support) possess considerably lower conversion (60%) compared to Pd@Pt/rGO. The mechanism of dehalogenation reactions with Pd@Pt/rGO catalyst is discussed with the explicit premise that rGO matrix facilitates the adsorption of the reducing agent, thus enhancing its local concentration and expediting the hydrazine decomposition rate. The versatility of the catalyst has been validated via diverse substrate scope for both reduction and dehalogenation reactions.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-04-21

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

  3. Structure and Thermal Parameters of Ni20Pd80 Alloy

    Institute of Scientific and Technical Information of China (English)

    S. Ahmad; A.B. Ziya; A. Aziz1; Z.I. Zafar

    2009-01-01

    The structure and thermal parameters of Ni20Pd80 alloy were studied by X-ray diffraction(XRD). The diffraction experiments performed in the temperature range of 308-1100 K revealed that the alloy formed a face centered cubic (fcc) Al-type structure. The temperature dependence of the lattice parameters was investigated by using the Bragg line displacement method showing that the lattice parameter increases with the increase of temperature. The mean linear thermal expansion (MLTE(%)), coefficient of thermal expansion (CTE, α), the characteristic Debye temperature (θD) and mean square amplitudes of vibration were determined from XRD data. The value of Debye temperature was found to be 253 K. It was found that temperature factor was independent of the static displacements.

  4. Session 4: Low-temperature CO oxidation on Ni-Pt/SiO{sub 2} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Arenas-Alatorre, J.; Gomez-Cortes, A.; Diaz, G. [Instituto de Fisica UNAM, Mexico, D.F. (Mexico); Avalos Borja, M [Centro de Cciencias de la Materia Condensada, Ensenada, B.C. (Mexico)

    2004-07-01

    In the present study a set of Ni-Pt catalysts supported on silica have been examined as catalysts for the CO oxidation in the presence of hydrogen. The obtained results show that bimetallic Ni{sub 25}Pt{sub 75} catalyst is very active; total conversion of CO is achieved at 70 C and no significant diminution is observed at higher temperatures. Hydrogen concentration in the gas phase did not changed significantly indicating a very good selectivity towards CO oxidation. Bimetallic Ni{sub 50}Pt{sub 50} and Ni{sub 75}Pt{sub 25} catalysts showed also a good activity but the selectivity for CO oxidation decreases in favor of hydrogen oxidation at higher temperatures. It is interesting to note the performance of mono-metallic Ni/SiO{sub 2} since nickel is known to be not very active for oxidation reactions; at 120 C more than 80% of the CO is converted. On the other hand, Pt/SiO{sub 2} performance is not so good in comparison. (authors)

  5. Structures, thermal stability, and melting behaviors of free-standing pentagonal multi-shell Pd-Pt nanowires

    Science.gov (United States)

    Cheng, D.; Hou, M.

    2010-04-01

    Classical molecular dynamics and Metropolis Monte Carlo simulations were carried out to investigate the thermal stability and melting behaviors of free-standing Pd-Pt bimetallic nanowires (NWs) with pentagonal multi-shell-type (PMS-type) structure in the whole composition range. Equilibrium configurations at 100 K are predicted in the semi-grand canonical ensemble. Pd-Pt PMS-type NWs are stable with a multishell structure of alternating Pd and Pt compositions and Pd segregating systematically to the surface. On thermal heating, an interesting composition-dependent structural transformation from the PMS-type to face-centred-cubic (FCC) by overcoming a high energy barrier is observed for Pd-Pt bimetallic NWs before the melting. Consequently, the system energy is decreased. The FCC structure is found more stable than PMS-type over the whole range of composition. The melting of Pd-Pt bimetallic NWs is also studied. It is found to start at the edges, then propagate over the whole surface, and next to the interior. It occurs in a composition-dependent range of temperature.

  6. Pulse electrodeposition to prepare core-shell structured AuPt@Pd/C catalyst for formic acid fuel cell application

    Science.gov (United States)

    Lu, Xueyi; Luo, Fan; Song, Huiyu; Liao, Shijun; Li, Hualing

    2014-01-01

    A novel core-shell structured AuPt@Pd/C catalyst for the electrooxidation of formic acid is synthesized by a pulse electrodeposition process, and the AuPt core nanoparticles are obtained by a NaBH4 reduction method. The catalyst is characterized with X-ray powder diffraction and transmission electron microscopy, thermogravimetric analysis, cyclic voltammetry, CO stripping and X-ray photoelectron spectroscopy. The core-shell structure of the catalyst is revealed by the increase in particle size resulting from a Pd layer covering the AuPt core, and by a negative shift in the CO stripping peaks. The addition of a small amount of Pt improves the dispersion of Au and results in smaller core particles. The catalyst's activity is evaluated by cyclic voltammetry in formic acid solution. The catalyst shows excellent activity towards the anodic oxidation of formic acid, the mass activity reaches 4.4 A mg-1Pd and 0.83 A mg-1metal, which are 8.5 and 1.6 times that of commercial Pd/C. This enhanced electrocatalytic activity could be ascribed to the good dispersion of Au core particles resulting from the addition of Pt, as well as to the interaction between the Pd shell layer and the Au and Pt in the core nanoparticles.

  7. 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....... This is particularly challenging for alloys containing Au due to a high propensity of Au to segregate to the surface. We also show that once Au is on the surface it will diffuse to defect sites, explaining why small amounts of Au retard dissolution of Pt nanoparticles. For the PtPd thin films there is no pronounced...

  8. 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

    active binary thin films are near-surface alloys of Pt with subsurface Pd and certain PdAu and PtAu thin films with surface and/or subsurface Au. The most active ternary thin films are with pure metal Pt or Pd skins with some degree of Au in the surface and/or subsurface layer and the near-surface alloys...... of Au with mixed Pt/Pd skins. The activity of the binary and ternary catalysts is explained through weakening of the OH binding energy caused by solute elements. However, given the low alloy formation energies it may be difficult to tune and retain the composition under operating conditions....... This is particularly challenging for alloys containing Au due to a high propensity of Au to segregate to the surface. We also show that once Au is on the surface it will diffuse to defect sites, explaining why small amounts of Au retard dissolution of Pt nanoparticles. For the PtPd thin films there is no pronounced...

  9. Thermal- and pressure-induced cooperative spin transition in the 2D and 3D coordination polymers {Fe(5-Br-pmd)z[M(CN)x]y} (M=AgI, AuI, NiII, PdII, PtII).

    Science.gov (United States)

    Agustí, Gloria; Gaspar, Ana Belén; Muñoz, M Carmen; Real, José Antonio

    2007-11-12

    A new family of cyanide-based spin-crossover polymers with the general formula {Fe(5-Br-pmd)z[M(CN)x]y} [M=AgI (1), AuI (2), NiII (3), PdII (4), PtII (5); 5-Br-pmd=5-bromopyrimidine; z=1 or 2, x=2 or 4, and y=2 or 1] have been synthesized and characterized using single-crystal X-ray diffraction (XRD), X-ray powder diffraction (XRPD), magnetic susceptibility measurements, and differential scanning calorimetry (DSC). At 293 K, compound 1 presents the monoclinic space group C2/c, whereas at 120 K, it changes to the monoclinic space group P21/c. At 293 K, the crystal structure of 1 displays an uninodal three-dimensional network whose nodes, constituted of FeII, lie at the inversion center of an elongated octahedron. The equatorial bond lengths are defined by the N atoms of four [AgI(CN)2]- groups belonging to two crystallographically nonequivalent AgI atoms, Ag(1) and Ag(2). They are shorter than those of the axial positions occupied by the N atoms of the 5-Br-pmd ligands. The Fe-N average bond length of 2.1657(7) A is consistent with a high-spin (HS) state for the FeII ions. At 120 K, the crystal structure changes refer mainly to the FeII environment. There are two crystallographically independent FeII ions at this temperature, Fe(1) and Fe(2), which adopt the HS and low-spin (LS) states, respectively. The average Fe-N bond length for Fe(1) [2.174(5) A] and Fe(2) [1.955(5) A] agrees well with the reported magnetic data at this temperature. The spin transition of the FeII ions labeled as Fe(1) is found to be centered at Tc downward arrow=149 K and Tc upward arrow=167 K and accompanied by a drastic change of color from orange (HS) to red (LS). Magnetic susceptibility measurements under applied hydrostatic pressure performed on 1 have shown a linear displacement of the transition to higher temperatures while the hysteresis width remains unaltered in the interval of pressures of 105 Pa to 0.34 GPa. A further increase of the pressure induces the spin transition in the Fe(2

  10. Reforming of oxygenates for H2 production: correlating reactivity of ethylene glycol and ethanol on Pt(111) and Ni/Pt(111) with surface d-band center.

    Science.gov (United States)

    Skoplyak, Orest; Barteau, Mark A; Chen, Jingguang G

    2006-02-02

    The dehydrogenation and decarbonylation of ethylene glycol and ethanol were studied using temperature programmed desorption (TPD) on Pt(111) and Ni/Pt(111) bimetallic surfaces, as probe reactions for the reforming of oxygenates for the production of H2 for fuel cells. Ethylene glycol reacted via dehydrogenation to form CO and H2, corresponding to the desired reforming reaction, and via total decomposition to produce C(ad), O(ad), and H2. Ethanol reacted by three reaction pathways, dehydrogenation, decarbonylation, and total decomposition, producing CO, H2, CH4, C(ad), and O(ad). Surfaces prepared by deposition of a monolayer of Ni on Pt(111) at 300 K, designated Ni-Pt-Pt(111), displayed increased reforming activity compared to Pt(111), subsurface monolayer Pt-Ni-Pt(111), and thick Ni/Pt(111). Reforming activity was correlated with the d-band center of the surfaces and displayed a linear trend for both ethylene glycol and ethanol, with activity increasing as the surface d-band center moved closer to the Fermi level. This trend was opposite to that previously observed for hydrogenation reactions, where increased activity occurred on subsurface monolayers as the d-band center shifted away from the Fermi level. Extrapolation of the correlation between activity and the surface d-band center of bimetallic systems may provide useful predictions for the selection and rational design of bimetallic catalysts for the reforming of oxygenates.

  11. Deposition temperature mediated tunable tilt angle magnetization in Co-Pt/Ni81Fe19 exchange springs

    Science.gov (United States)

    Saravanan, P.; Hsu, Jen-Hwa; Tsai, C. L.; Lee, C.-M.

    2015-05-01

    In this study, we investigate the effect of deposition temperature of Co-Pt fixed layer, Td,CoPt (150, 250 and 350 °C) on the tilt angle magnetization (θM) of Ni81Fe19-layer grown at room temperature (RT) and at different thicknesses (tNiFe=0, 1.0, 2.5 and 4.0 nm) in Co-Pt(Td,CoPt)/NiFe(tNiFe) exchange springs. The magnetic studies demonstrated a strong perpendicular magnetic anisotropy (PMA) for the equi-compositional ordered Co-Pt layer grown on glass substrate using the film sequence: Ta(20 nm)/Pt(20 nm)/CoPt(5 nm), regardless of Td,CoPt. The PMA can be retained with the addition of a 4-nm NiFe layer on the top when Td,CoPt≥250 °C. In contrast, relatively a thin layer of Ni-Fe (2.5 nm) can destroy the perpendicular exchange-spring behavior if the Co-Pt layer is deposited at RT. Using 3-D micromagnetic simulation, the interfacial exchange coupling strength (Aij) between the Co-Pt and NiFe-layers was estimated and the Aij value is found to increase rapidly when Td,CoPt is increased from RT to 300 °C. Besides, the magnetization tilted angle (θM) of NiFe can be easily tuned from completely out-of-plane to almost 60° when tNiFe=4.0 nm. Through this study, it is demonstrated that the θM of NiFe-layer can be tuned by not only altering the tNiFe; but also by varying the Td,CoPt.

  12. Nanosized (mu12-Pt)Pd164-xPtx(CO)72(PPh3)20 (x approximately 7) containing Pt-centered four-shell 165-atom Pd-Pt core with unprecedented intershell bridging carbonyl ligands: comparative analysis of icosahedral shell-growth patterns with geometrically related Pd145(CO)x(PEt3)30 (x approximately 60) containing capped three-shell Pd145 core.

    Science.gov (United States)

    Mednikov, Evgueni G; Jewell, Matthew C; Dahl, Lawrence F

    2007-09-19

    Presented herein are the preparation and crystallographic/microanalytical/magnetic/spectroscopic characterization of the Pt-centered four-shell 165-atom Pd-Pt cluster, (mu(12)-Pt)Pd(164-x)Pt(x)(CO)(72)(PPh(3))(20) (x approximately 7), 1, that replaces the geometrically related capped three-shell icosahedral Pd(145) cluster, Pd(145)(CO)(x)(PEt(3))(30) (x approximately 60), 2, as the largest crystallographically determined discrete transition metal cluster with direct metal-metal bonding. A detailed comparison of their shell-growth patterns gives rise to important stereochemical implications concerning completely unexpected structural dissimilarities as well as similarities and provides new insight concerning possible synthetic approaches for generation of multi-shell metal clusters. 1 was reproducibly prepared in small yields (Pd-Pt anatomy of 1 consists of: (a) shell 1 with the centered (mu(12)-Pt) atom encapsulated by the 12-atom icosahedral Pt(x)Pd(12-x) cage, x = 1.2(3); (b) shell 2 with the 42-atom nu(2) icosahedral Pt(x)Pd(42-x) cage, x = 3.5(5); (c) shell 3 with the anti-Mackay 60-atom semi-regular rhombicosidodecahedral Pt(x)Pd(60-x) cage, x = 2.2(6); (d) shell 4 with the 50-atom nu(2) pentagonal dodecahedral Pd(50) cage. The total number of crystallographically estimated Pt atoms, 8 +/- 3, which was obtained from least-squares (Pt(x)/Pd(1-x))-occupancy analysis of the X-ray data that conclusively revealed the central atom to be pure Pt (occupancy factor, x = 1.00(3)), is fortuitously in agreement with that of 7.6(7) found from an X-ray Pt/Pd microanalysis (WDS spectrometer) on three crystals of 1. Our utilization of this site-occupancy (Pt(x)Pd(1-x))-analysis for shells 1-3 originated from the microanalytical results; otherwise, the presumed metal-core composition would have been (mu(12)-Pt)Pd(164). [Alternatively, the (mu(12)-Pt)M(164) core-geometry of 1 may be viewed as a pseudo-Ih Pt-centered six-shell successive nu(1) polyhedral system, each with

  13. Superior hydrogen storage and electrochemical properties of Mg(x)Ni(100-x)/Pd films at room temperature.

    Science.gov (United States)

    Liu, Tong; Cao, Yurong; Xin, Gongbiao; Li, Xingguo

    2013-10-07

    The Mg(x)Ni(100-x) films of 100 nm have been prepared by magnetron co-sputtering Mg and Ni targets, and a Pd layer of 10 nm was deposited on these films by magnetron sputtering a Pd target. Mg2Ni and MgNi2 are directly generated during the co-sputtering process in the Mg84Ni16/Pd and Mg48Ni52/Pd films. The hydrogen storage properties of the films under 0.1 MPa H2 at 298 K were investigated. The hydrogenation of the Mg84Ni16/Pd film saturates within 45 s and exhibits the faster absorption kinetics compared with Mg94Ni6/Pd and Mg48Ni52/Pd films. The electrochemical properties of the Mg(x)Ni(100-x)/Pd films were investigated in 6 M KOH with a three-electrode cell. The Mg84Ni16/Pd film can be activated just at the first cycle. The maximum discharge capacity of the Mg84Ni16/Pd film is 482.7 mAh g(-1), the highest among these films.

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

    Energy Technology Data Exchange (ETDEWEB)

    Vidal-Iglesias, F.J.; Solla-Gullon, J.; Montiel, V.; Feliu, J.M.; Aldaz, A. [Instituto de Electroquimica, Universidad de Alicante, Apartado 99, 03080 Alicante (Spain)

    2007-09-27

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

  15. C-O Reductive Elimination from High Valent Pt and Pd Centers

    Science.gov (United States)

    Vedernikov, Andrei N.

    Reactions of high valent platinum and palladium complexes leading to the formation of C(sp 2)-O and C(sp 3)-O bonds are involved in various catalytic applications such as oxidative functionalization of hydrocarbons, which are especially rich in the case of palladium chemistry. This Chapter emphasizes on the mechanisms of C-O reductive elimination from octahedral d 6 Pt(IV) and, in part, from Pd(IV) complexes. The nature of the leaving groups, the metal center, the presence of soft/hard spectator ligands, the number of hydrocarbyl ligands at the metal, and some other factors affecting the reactivity of such complexes are considered. As shown here, there are still uncharted territories in the area of high valent organoplatinum and organopalladium chemistry: C(sp 2)-O reductive elimination from PtIV, reactivity and reaction mechanisms of PtIII and PdIII organometallic derivatives, synthesis and reactivity of monoalkyl and monoaryl palladium(IV) complexes stabilized by O-donor ligands, and others. The rapid progress observed in this field of chemistry suggests that some of these areas will soon be explored.

  16. NiO增强Pt/C催化剂催化氧化甲醇活性的研究%Studies of electro-oxidation of methanol in acidic solution on NiO-enhanced Pt/C catalysts

    Institute of Scientific and Technical Information of China (English)

    白庆星; 陈金伟; 杨鑫; 陆超; 胥诚成; 顾佳林; 姜春萍; 王瑞林

    2012-01-01

    本文基于NiO作为Pt催化甲醇助催化剂的思路,通过Pt纳米颗粒担载在NiO修饰的碳材料载体上制备了Pt/NiO-C催化剂,系统地研究了不同的NiO/C热处理温度对Pt粒径的影响,并重点探讨了Pt对NiO的质量比对催化氧化甲醇的影响.X射线衍射分析结果显示NiO和Pt均为立方晶系,且NiO的加入有利于主催化剂Pt形成较小的粒径,且经400℃热处理NiO修饰的C材料作为载体有利于Pt的有效分散.所获得的Pt/NiO-C催化剂的电化学活性在甲醇酸性溶液中通过循环伏安法(CV)和计时电流法(CA)进行性能测试.CV测试结果显示以Pt/NiO重量比为4∶1的催化剂其电氧化甲醇活性最大,其峰值氧化电流密度达806 mA/mgPt,是Pt/C催化剂的1.64倍.CA测试结果显示Pt/NiO-C比Pt/C具有更好的抗CO中毒性能和稳定性.%In an attempt to utilize NiO as a co-catalyst with Pt for methanol electro-oxidation,Pt/NiO-C were prepared by attaching Pt nanoparticles on NiO coated Vulcan XC-72R carbon blacks in this study. Heat treatment of NiO at different temperatures on the influences of Pt particle size was investigated,and the weight ratio of Pt to NiO on the catalytic oxidation of methanol was also studied. X-ray diffraction results indicated that both NiO and Pt belong to cubic structure and Pt nano-particles on NiO/C supports had smaller particle size than those on Vulcan XC-72R without NiO. NiO/C heat treatment at 400℃ is good for Pt effective dispersion. The methanol electro-oxidation was studied in acid medium by cyclic voltammetry and chronoamperometry. The catalytic activity of Pt for methanol oxidation can be significantly enhanced by introducing NiO. The composition with ratio of Pt to NiO(4:l)exhibited the highest mass activity(806 mA/mgp,)in the as-prepared version,which was 1. 64 times higher that that on the Pt/C catalyst. Pt/NiO-C catalysts showed better stability and CO tolerant capability than Pt/C catalysts from chronoamperometry

  17. Robust electric-field tunable opto-electrical behavior in Pt-NiO-Pt planar structures.

    Science.gov (United States)

    Rebello, A; Adeyeye, A O

    2016-06-13

    Capacitor-like metal-NiO-metal structures have attracted large interest in non-volatile memory applications based on electric field control of resistance, known as resistive switching (RS). Formation of conducting nanofilaments by the application of an electric field (electroformation) is considered an important pre-requisite for RS. Besides RS, due to the wide band gap and p-type semiconducting nature, NiO has been used to fabricate heterojunctions for photodetector applications. However, very little is known about the electrical and opto-electrical properties of NiO films in planar structure. Here, we demonstrate intriguing photoresponse and electrical behavior in electroformed Pt-NiO-Pt planar structures. While the pristine devices show ohmic electrical behavior and negligible photoresponse, the electroformed devices exhibit a nonlinear rectification behavior and a remarkable photoresponse at low voltage biases. More interestingly, the devices show a dramatic change of sign of rectification under light illumination at higher voltage biases. A polarity dependent and robust gain phenomenon is demonstrated in these devices. The large sensitivity, fast response, simple design and ease of preparation of these planar structures make them attractive for integration with current circuit technologies and various novel opto-electrical applications.

  18. Robust electric-field tunable opto-electrical behavior in Pt-NiO-Pt planar structures

    Science.gov (United States)

    Rebello, A.; Adeyeye, A. O.

    2016-01-01

    Capacitor-like metal-NiO-metal structures have attracted large interest in non-volatile memory applications based on electric field control of resistance, known as resistive switching (RS). Formation of conducting nanofilaments by the application of an electric field (electroformation) is considered an important pre-requisite for RS. Besides RS, due to the wide band gap and p-type semiconducting nature, NiO has been used to fabricate heterojunctions for photodetector applications. However, very little is known about the electrical and opto-electrical properties of NiO films in planar structure. Here, we demonstrate intriguing photoresponse and electrical behavior in electroformed Pt-NiO-Pt planar structures. While the pristine devices show ohmic electrical behavior and negligible photoresponse, the electroformed devices exhibit a nonlinear rectification behavior and a remarkable photoresponse at low voltage biases. More interestingly, the devices show a dramatic change of sign of rectification under light illumination at higher voltage biases. A polarity dependent and robust gain phenomenon is demonstrated in these devices. The large sensitivity, fast response, simple design and ease of preparation of these planar structures make them attractive for integration with current circuit technologies and various novel opto-electrical applications. PMID:27294614

  19. Effect of Pd loading in Pd-Pt bimetallic catalysts doped into hollow core mesoporous shell carbon on performance of proton exchange membrane fuel cells

    Science.gov (United States)

    Fıçıcılar, Berker; Bayrakçeken, Ayşe; Eroğlu, İnci

    A significantly active Pd-Pt/carbon electrocatalyst for polymer electrolyte membrane fuel cells was synthesized by microwave irradiation using a hollow core mesoporous shell (HCMS) carbon as catalyst support that was prepared by template replication of core/shell spherical silica particles and two different carbon precursors. Pt/Pd percent weight ratios on carbon support were varied as 20/0, 15/5, 10/10, 5/15 to 0/20. As the average pore diameter of the carbon support was increased from 3.02 nm to 3.90 nm by changing the type of the carbon precursor, fuel cell performances of the HCMS carbon based Pd-Pt bimetallic catalysts were improved significantly.

  20. Direct decomposition of methane over Pd promoted Ni/SBA-15 catalysts

    Science.gov (United States)

    Pudukudy, Manoj; Yaakob, Zahira; Akmal, Zubair Shamsul

    2015-10-01

    The catalytic performance of Ni/SBA-15 catalysts promoted with different loadings of Pd is investigated for the thermocatalytic decomposition of methane into COx-free hydrogen and nanocarbon. The catalysts are characterized in terms of their structural, textural and redox properties. The results showed that the Pd deposition increased the crystallinity of NiO and allowed the fine dispersion of NiO on the SBA-15 support. The decreased surface area of SBA-15 after Ni loading, due to pore blocking, increased after the Pd deposition. Moreover, it reduced the reduction temperatures of NiO interacting with the SBA-15 due to the spillover effect of hydrogen. Furthermore, the addition of Pd increased the catalytic efficiency of the catalysts. A maximum hydrogen yield of 59% is observed over the 0.4% Pd catalyst within 30 min of time on stream. No deactivation is observed until 420 min of streaming for all of the catalysts, indicating a high catalytic stability of the Ni/SBA-15 catalysts for methane decomposition. A new set of multi-walled carbon nanotubes with open tips were deposited over the catalysts, irrespective of the role of Pd and its loading. Moreover, a high graphitization degree and oxidation stability are observed for the nanotubes deposited over the 0.4% Pd catalyst.

  1. Modification of the hydrogenation properties of LaNi{sub 5} upon Ni substitution by Rh, Ir, Pt or Au

    Energy Technology Data Exchange (ETDEWEB)

    Prigent, J. [Chimie Metallurgique des Terres Rares, Institut de Chimie et des Materiaux Paris-Est, CNRS, Universite Paris-Est, 2-8 rue H. Dunant, 94320 Thiais Cedex (France); Laboratoire de Thermodynamique et Physico-Chimie des Hydrures et Oxydes, Universite Paris-Sud Orsay, Bat 410, 91405 Orsay (France); Joubert, J.-M., E-mail: jean-marc.joubert@icmpe.cnrs.fr [Chimie Metallurgique des Terres Rares, Institut de Chimie et des Materiaux Paris-Est, CNRS, Universite Paris-Est, 2-8 rue H. Dunant, 94320 Thiais Cedex (France); Gupta, M. [Laboratoire de Thermodynamique et Physico-Chimie des Hydrures et Oxydes, Universite Paris-Sud Orsay, Bat 410, 91405 Orsay (France)

    2012-01-15

    Highlights: > Hydrogen absorption properties of LaNi{sub 5-x}M{sub x} intermetallic compounds (M = Rh, Ir, Au). > Stability of LaNi{sub 5-x}M{sub x} (M = Rh, Pt) intermetallics and hydrides using ab initio calculations. > Influence of the substituting elements (geometric, thermodynamic and electronic) on the hydride stability. - Abstract: The hydrogenation properties of the LaNi{sub 5-x}M{sub x} (M = Rh, Ir, Au) compounds have been studied. The Ni substitution has several consequences: pressure plateau splitting and increase of plateau pressure. This latter observation disagrees with the general rule that a cell volume increase of the alloy should result in a plateau pressure lowering. In order to elucidate the origin of this anomalous behaviour, DFT calculations have been performed on both LaNi{sub 5-x}Rh{sub x} and LaNi{sub 5-x}Pt{sub x} intermetallic compounds, which, according to the present and previous experimental work, present a similar anomaly. We discuss our results in light of the models proposed in the literature. We conclude that, in the case of a Ni substitution by 4d or 5d elements, the size effect alone fails in predicting the hydrogen absorption properties while the rule of reverse stability is obeyed.

  2. Bimetallic Pt-Ni catalysts supported on usy zeolite for n-hexane isomerization

    Directory of Open Access Journals (Sweden)

    F. V. Barsi

    2009-06-01

    Full Text Available Isomerization of linear alkanes has had considerable importance for the refining industry because the isomers formed in this reaction have high octane number. Most works reported in the literature studied the use of bifunctional catalysts, i.e., ones that have acid sites and metallic sites. In this study, bifunctional monometallic (Ni or Pt and bimetallic catalysts (Pt-Ni, using HUSY zeolite as the support, were prepared in order to verify the role of the metal content and composition on the catalytic properties for n-hexane isomerization. The method used for metal dispersion in the zeolite was competitive ion exchange using ammine complexes [Ni(NH36]Cl2 and [Pt(NH34]Cl2 as precursors. Four series of catalysts with constant atomic metal content had total metal amounts between 130 and 280 µmol M/g cat. Catalysts were characterized by temperature programmed reduction (TPR and subjected to catalytic evaluation for n-hexane isomerization at 250 ºC and 1 atm using H2/C6 = 9 molar ratio. TPR results show an easier reducibility of Ni+2 cations in the presence of Pt, which was evidenced by the displacement of the reduction peak of those cations towards lower temperatures in bimetallic catalysts. The bimetallic catalysts presented a higher activity in the isomerization of n-hexane when compared to the monometallic ones, as well better stability as the Pt content in the solid increases. The results of the activity as a function of the Pt content in the bimetallic catalysts show a maximum value around 50% of Pt. An addition of Pt above this critical value leads to a small decrease of the catalytic activity.

  3. L1{sub 0} phase formation in ternary FePdNi alloys

    Energy Technology Data Exchange (ETDEWEB)

    Montes-Arango, A.M. [Department of Mechanical and Industrial Engineering, Northeastern University, Boston, MA 02115 (United States); Bordeaux, N.C. [Department of Chemical Engineering, Northeastern University, Boston, MA 02115 (United States); Liu, J.; Barmak, K. [Department of Applied Physics and Applied Mathematics, Columbia University, New York, NY 10027 (United States); Lewis, L.H., E-mail: lhlewis@neu.edu [Department of Mechanical and Industrial Engineering, Northeastern University, Boston, MA 02115 (United States); Department of Chemical Engineering, Northeastern University, Boston, MA 02115 (United States)

    2015-11-05

    Metallurgical routes to highly metastable phases are required to access new materials with new functionalities. To this end, the stability of the tetragonal chemically ordered L1{sub 0} phase in the ternary Fe–Pd–Ni system is quantified to provide enabling information concerning synthesis of L1{sub 0}-type FeNi, a highly attractive yet highly elusive advanced permanent magnet candidate. Fe{sub 50}Pd{sub 50−x}Ni{sub x} (x = 0–7 at%) samples were arc-melted and annealed at 773 K (500 °C) for 100 h to induce formation of the chemically ordered L1{sub 0} phase. Coupled calorimetry, structural and magnetic investigations allow determination of an isothermal section of the ternary Fe–Pd–Ni phase diagram featuring a single phase L1{sub 0} region near the FePd boundary for x < 6 at%. It is demonstrated that increased Ni content in Fe{sub 50}Pd{sub 50−x}Ni{sub x} alloys systematically decreases the order-disorder transition temperature, resulting in a lower thermodynamic driving force for the ordering phase transformation. The Fe{sub 50}Pd{sub 50−x}Ni{sub x} L1{sub 0} → fcc disordering transformation is determined to occur via a two-step process, with compositionally-dependent enthalpies and transition temperatures. These results highlight the need to investigate ternary alloys with higher Ni content to determine the stability range of the L1{sub 0} phase near the FeNi boundary, thereby facilitating kinetic access to the important L1{sub 0} FeNi ferromagnetic phase. - Highlights: • Chemical ordering in FePdNi enhances intrinsic and extrinsic magnetic properties. • 773 K annealed FePdNi alloys studied show a stable L1{sub 0} phase for Ni ≤ 5.2 at%. • Chemical disordering in FePdNi occurs by a previously unreported two-step process. • Ni additions to FePd dramatically decrease the chemical order-disorder temperature. • The chemical-ordering transformation kinetics are greatly affected by Ni content.

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

    Science.gov (United States)

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

    2016-06-15

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

  5. Etching approach to hybrid structures of PtPd nanocages and graphene for efficient oxygen reduction reaction catalysts

    Institute of Scientific and Technical Information of China (English)

    Song Bai[1; Chengming Wang[1; Wenya Jiang[1; Nana Du[1; Jing Li[1; Junteng Du[1; Ran Long[1; Zhengquan Li[2; Yujie Xiong[1

    2015-01-01

    Cathodic oxygen reduction reaction (ORR) is a highly important electrochemical reaction in renewable-energy technologies. In general, the surface area, exposed facets and electrical conductivity of catalysts all play important roles in determining their electrocatalytic activities, while their performance durability can be improved by integration with supporting materials. In this work we have developed a method to synthesize hybrid structures between PtPd bimetallic nanocages and graphene by employing selective epitaxial growth of single-crystal Pt shells on Pd nanocubes supported on reduced graphene oxide (rGO), followed by Pd etching. The hollow nature, {100} surface facets and bimetallic composition of PtPd nanocages, together with the good conductivity and stability of graphene, enable high electrocatalytic performance in ORR. The obtained PtPd nanocage-rGO structures exhibit mass activity (0.534 A.m-1) and which are 4.4 times and 3.9 times greater than the specific activity (0.482 mA-cm-2) corresponding values for Pt/C.

  6. A theoretical study of the lowest-energy PtPd co-doped silicon clusters: Chirality and fluxional transformation

    Science.gov (United States)

    Lv, Peng; Lu, Zhansheng; Yang, Feng; Zhang, Yi; Yang, Xinwei; Xu, Guoliang; Yang, Zongxian

    2017-03-01

    The lowest-energy structures of PtPdSiqn (n = 1- 7; q = 0 , ± 1) clusters are searched based on the PSO algorithm implemented in the CALYPSO code and the first-principle DFT-D computations implemented in DMol3 code. Interestingly, the chirality has been found for the lowest-energy structures of the neutral and charged PtPdSi4, neutral and anionic PtPdSi5, and cationic PtPdSi7 clusters. The first principles molecular dynamics (MD) simulations show that the fluxional transformation between the chiral configurations for neutral PtPdSi4 cluster can take place at 400 K, which is also confirmed by the rather small transformation barrier. The equivalent atoms involved in the bond breaking and formation, as well as the other atoms (modulator), may facilitate the dynamical behavior. The current finding is thus beyond imagination. It is noticeable that the current study provides a potential way to create interesting cluster with chirality and transformation, based on silicon.

  7. Deposition temperature mediated tunable tilt angle magnetization in Co–Pt/Ni{sub 81}Fe{sub 19} exchange springs

    Energy Technology Data Exchange (ETDEWEB)

    Saravanan, P. [Department of Physics, National Taiwan University, Taipei 106, Taiwan (China); Defence Metallurgical Research Laboratory, Hyderabad 500058 (India); Hsu, Jen-Hwa, E-mail: jhhsu@phys.ntu.edu.tw [Department of Physics, National Taiwan University, Taipei 106, Taiwan (China); Tsai, C.L. [Department of Physics, National Taiwan University, Taipei 106, Taiwan (China); Lee, C.-M. [Graduate School of Materials Science, National Yunlin University of Science and Technology, Douliou 64002, Taiwan (China)

    2015-05-01

    In this study, we investigate the effect of deposition temperature of Co–Pt fixed layer, T{sub d,CoPt} (150, 250 and 350 °C) on the tilt angle magnetization (θ{sub M}) of Ni{sub 81}Fe{sub 19}-layer grown at room temperature (RT) and at different thicknesses (t{sub NiFe}=0, 1.0, 2.5 and 4.0 nm) in Co–Pt(T{sub d,CoPt})/NiFe(t{sub NiFe}) exchange springs. The magnetic studies demonstrated a strong perpendicular magnetic anisotropy (PMA) for the equi-compositional ordered Co–Pt layer grown on glass substrate using the film sequence: Ta(20 nm)/Pt(20 nm)/CoPt(5 nm), regardless of T{sub d,CoPt}. The PMA can be retained with the addition of a 4-nm NiFe layer on the top when T{sub d,CoPt}≥250 °C. In contrast, relatively a thin layer of Ni–Fe (2.5 nm) can destroy the perpendicular exchange-spring behavior if the Co–Pt layer is deposited at RT. Using 3-D micromagnetic simulation, the interfacial exchange coupling strength (A{sub ij}) between the Co–Pt and NiFe-layers was estimated and the A{sub ij} value is found to increase rapidly when T{sub d,CoPt} is increased from RT to 300 °C. Besides, the magnetization tilted angle (θ{sub M}) of NiFe can be easily tuned from completely out-of-plane to almost 60° when t{sub NiFe}=4.0 nm. Through this study, it is demonstrated that the θ{sub M} of NiFe-layer can be tuned by not only altering the t{sub NiFe}; but also by varying the T{sub d,CoPt}. - Highlights: • Equi-compositional ordered 5-nm thick Co–Pt with strong PMA was grown on glass. • The ordered Co–Pt and Ni{sub 81}Fe{sub 19} layers were utilized for OOP and IP-anisotropies. • Tunable tilt angle magnetization was investigated by varying T{sub d,CoPt}. • Using micromagnetic simulation, interfacial exchange coupling strength was deduced. • Deposition temperature mediated θ{sub M} in Co–Pt/NiFe provides a new scope for STO.

  8. Pt-Ni/Nafion材料的制备及电致动性能研究%Preparation and Electro-actuating Characteristic of Pt-Ni/Nafion

    Institute of Scientific and Technical Information of China (English)

    郭文莎; 罗欣; 金建新

    2012-01-01

    IPMC intelligent materials can generate large deformation and tensile force at low voltage, and hence they could serve as actuators. To reduce the production cost, the chemical reduction method was used to synthesize Pt-Ni/Nafion double-metallic-layer ionomer composite, and a complete set of fabrication procedures were determined. The actuating properties of Pt-Ni/Nafion under different driving voltages were also studied. The result snowed that the deformation of IPMC membrane increases with increasing DC voltage, and the maximum deflection angle can reach up to 47°;deformatin of IPMC membrane is proportional to the amplitude but inversely proportional to the frequency of the AC driving voltage%IPMC智能材料具有在低电压下产生较大形变和张力的特点,可作为新型的致动器.为了降低制备成本,采用渗透还原法制备了Pt-Ni/Nafion双金属层离子聚合物复合材料,确定了一套完整的制备工艺,测试了Pt-Ni/Nafion材料在不同驱动电压下的致动特性.结果表明,IPMC膜的形变随着直流电压的增大而增大,与初始位置的最大偏转角为47°;IPMC膜在正弦交流电压驱动下,形变随着电压幅值增大而增大,随着电压频率的增大而减小,并且电压输入与位移输出具有线性关系.

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

    Science.gov (United States)

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

    2016-01-01

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

  10. Atomic-Scale Snapshots of the Formation and Growth of Hollow PtNi/C Nanocatalysts.

    Science.gov (United States)

    Chattot, Raphaël; Asset, Tristan; Drnec, Jakub; Bordet, Pierre; Nelayah, Jaysen; Dubau, Laetitia; Maillard, Frédéric

    2017-03-30

    Determining the formation and growth mechanism of bimetallic nanoparticles (NPs) with atomic detail is fundamental to synthesize efficient "catalysts by design". However, an understanding of the elementary steps which take place during their synthesis remains elusive. Herein, we have exploited scanning transmission electron microscopy coupled to energy-dispersive X-ray spectroscopy, operando wide angle and small-angle X-ray scattering, and electrochemistry to unveil the formation and growth mechanism of hollow PtNi/C NPs. Such NPs, composed of a PtNi shell surrounding a nanoscale void, catalyze efficiently and sustainably the oxygen reduction reaction (ORR) in an acidic electrolyte. Our step-by-step study reveals that (i) Ni-rich/C NPs form first, before being embedded in a NixByOz shell, (ii) the combined action of galvanic displacement and the nanoscale Kirkendall effect then results in the sequential formation of Ni-rich core@Pt-rich/C shell and ultimately hollow PtNi/C NPs. The electrocatalytic properties for the ORR and the stability of the different synthesis intermediates were tested and structure-activity-stability relationships established both in acidic and alkaline electrolytes. Beyond its interest for the ORR electrocatalysis, this study also presents a methodology that is capable to unravel the formation and growth mechanism of various nanomaterials including preferentially shaped metal NPs, core@shell NPs, onion-like NPs, Janus NPs, or a combination of several of these structures.

  11. Improving electromechanical output of IPMC by high surface area Pd-Pt electrodes and tailored ionomer membrane thickness

    Directory of Open Access Journals (Sweden)

    Viljar Palmre

    2014-04-01

    Full Text Available In this study, we attempt to improve the electromechanical performance of ionic polymer–metal composites (IPMCs by developing high surface area Pd-Pt electrodes and tailoring the ionomer membrane thickness. With proper electroless plating techniques, a high dispersion of palladium particles is achieved deep in the ionomer membrane, thereby increasing notably the interfacial surface area of electrodes. The membrane thickness is increased using 0.5 and 1 mm thick ionomer films. For comparison, IPMCs with the same ionomer membranes, but conventional Pt electrodes, are also prepared and studied. The electromechanical, mechanoelectrical, electrochemical and mechanical properties of different IPMCs are characterized and discussed. Scanning electron microscopy-energy dispersive X-ray (SEM-EDS is used to investigate the distribution of deposited electrode metals in the cross section of Pd-Pt IPMCs. Our experiments demonstrate that IPMCs assembled with millimeter thick ionomer membranes and newly developed Pd-Pt electrodes are superior in mechanoelectrical transduction, and show significantly higher blocking force compared to conventional type of IPMCs. The blocking forces of more than 0.3 N were measured at 4V DC input, exceeding the force output of typical Nafion® 117-based Pt IPMCs more than two orders of magnitude. The newly designed Pd-Pt IPMCs can be useful in more demanding applications, e.g., in biomimetic underwater robotics, where high stress and drag forces are encountered.

  12. 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.

  13. Direct ethanol fuel cell, CO and ethanol oxidation on core-shell C/Ni-Au-[Pt and (Pt- Ir)] catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, C.A.D.; Tremiliosi-Filho, G. [Universidade de Sao Paulo (IQSC/USP), Sao Carlos, SP (Brazil). Inst. de Quimica], Email: cesaraug@sc.usp.br; Kokoh, K.B.; Coutanceau, C.; Baranton, S. [Universite de Poitiers (France). Lab. de Catalyse en Chimie Organique (LACCO). Equipe Electrocatalyse

    2010-07-01

    In this paper presents to study of the Pt and Pt-Ir monolayer that were deposited on core-shell Ni-Au nanoparticles supported on carbon. Catalysts with the following molar ratios were prepared: Pt and Pt{sub 65}Ir{sub 35}, Pt{sub 75}Ir{sub 2}5, Pt{sub 80}Ir{sub 20} and Pt{sub 85}Ir{sub 15}. The means particle sizes were in the range of 2 - 6 nm for all catalysts. The electrochemical properties examined in the ethanol and CO oxidation by cyclic voltammetry, and In situ IR spectroscopy measurements (SPAIRS) enabled to determine intermediates and reaction products as a function of the metallic compositions of catalysts. All of the catalysts were tested as anodes of a single direct ethanol fuel cell (DEFC) tests in 1.0 M ethanol solution. As a result, higher power densities were obtained with the core-shell particles in comparison to those issued from the commercial catalyst (Pt-ETEK). Thus, the maximum power densities at 90 deg C for the different systems are: (i) commercial C/Pt catalyst (E-TEK): ca. 0.010 W cm{sup -2}, C/Ni-Au-(Pt{sub 85}Ir{sub 15}): ca. 0.013 W cm{sup -2} and C/Ni-Au-Pt: ca. 0.018 W cm{sup -2} (all core-shell systems were normalization by Pt load). As a result, the performance of the core-shell nanoparticles is much better than that produced for the commercial catalyst and the C/Ni-Au-Pt system showed the best performance. (author)

  14. Preparation and Electro-catalytic Activity of Pd@Pt/C Catalyst%低铂催化剂Pd@Pt/C的制备及其电催化活性的研究

    Institute of Scientific and Technical Information of China (English)

    陈容; 黄琦杰

    2016-01-01

    The kinetics of the oxygen reduction reaction in fuel cell cathodes is sluggish that needs using large amounts of Pt to compensate, which mainly leads to the high cost of fuel cell, as well as hider the large scale application of proton exchange membrane fuel cell. In order to overcome these problems, it needs to investigate high performance, low platinum loading, excellent durability electrocatalysts. Core-shell structure catalyst, because of its special structure which can make the Pt dispersion, utilization, and activity be greatly improved as well as reduce Pt loading, has been widely recognized as being among the most promising candidates to achieve the commercialization of proton exchange membrane fuel cell. A novel pulse deposition method was used to prepare a low platinum catalyst Pd@Pt/C. For the cathodic reduction of oxygen, Pd@ Pt/C catalyst demonstrated three times higher mass activity towards the cathodic reduction of oxygen than commercial Pt/C catalyst, exhibiting competitive performance compared with commercial Pt/C catalyst.%燃料电池阴极氧还原动力学缓慢,需要使用大量的铂催化剂,导致电池高昂的成本,制约了质子交换膜燃料电池的大规模产业化。解决这个瓶颈的关键在于研究与制备高性能、低铂载量、耐久性好的燃料电池催化剂。而核壳结构催化剂因其特殊的结构可以使得Pt的分散度、利用率、活性得到很大的提高。本文采用脉冲电流沉积的方法制备了Pd@Pt/C催化剂。电化学测试结果表明, Pd@Pt/C催化剂的氧还原活性可媲美商品的20% Pt/C催化剂, Pd@Pt/C催化剂的Pt质量活性可达JM Pt/C催化剂的3.1倍。

  15. The system Pd-Fe-Ni-S at 900 and 725 degree C

    DEFF Research Database (Denmark)

    Makovicky, E.; Karup-Møller, Sven

    1995-01-01

    /Fe ratio in the melt changes regularly against that in mss with increasing S fugacity and Pd contents in these two phases. (Ni,Fe)(3+/-x)S-2 and Pd4S play important roles at 725 degrees C. The data offer an array of distribution coefficients and solubility values suitable for geological interpretations....

  16. Highly dispersed Pt-Ni nanoparticles on nitrogen-doped carbon nanotubes for application in direct methanol fuel cells.

    Science.gov (United States)

    Jiang, Shujuan; Ma, Yanwen; Tao, Haisheng; Jian, Guoqiang; Wang, Xizhang; Fan, Yining; Zhu, Jianmin; Hu, Zheng

    2010-06-01

    Binary Pt-Ni alloyed nanoparticles supported on nitrogen-doped carbon nanotubes (NCNTs) have been facilely constructed without pre-modification by making use of the active sites in NCNTs due to the N-participation. So-obtained binary Pt-Ni alloyed nanoparticles have been highly dispersed on the outer surface of the support with the size of about 3-4 nm. The electrochemical properties of the catalysts for methanol oxidation have been systematically evaluated. Binary Pt-Ni alloyed composites with molar ratio (Pt:Ni) of 3:2 and 3:1 present enhanced electrocatalytic activities and improved tolerance to CO poisoning as well as the similar stability, in comparison with the commercial Pt/C catalyst and the monometallic Pt/NCNTs catalysts. These results imply that so-constructed nanocomposite catalysts have the potential for applications in direct methanol fuel cells.

  17. Modeling of diffusion mechanism of conductive channel oxidation in a Pt/NiO/Pt memory switching structure

    Science.gov (United States)

    Sysun, V. I.; Bute, I. V.; Boriskov, P. P.

    2016-09-01

    The transition process from the low resistance state into the high resistance state in a Pt/NiO/Pt memory switching structure has been studied by numerical modeling. Detailed analysis shows, that thermally induced diffusion oxidation by nickel vacancies is the key factor for distortion of the channel metallic conductivity. Spatial dynamics of the process of oxidation defines channel narrowing mainly in its central part, and also sets the critical current through the structure sufficient for final rupture of the channel and the transition to high resistance state. The increase in critical current above the limit even by 10% reduces the switching time by an order of magnitude, which is in agreement with experiments. The developed radial diffusion model of conductive channel (or filaments) oxidation may be suitable for the analysis of switching effect a number of other ReRAM oxide structures.

  18. Simultaneous leaching of Pt, Pd and Rh from automotive catalytic converters in chloride-containing solutions

    Science.gov (United States)

    Hasani, M.; Khodadadi, A.; Koleini, S. M. J.; Saeedi, A. H.; Meléndez, A. M.

    2017-01-01

    Dissolution of platinum group metals (PGM; herein Pt, Pd and Rh) in different chloride-based leaching systems from spent auto catalysts was performed. Response surface methodology and a five-level-five-factor central composite design were used to evaluate the effects of 1) temperature, 2) liquid-to-solid ratio, 3) stirring speed, 4) acid concentration and 5) particle size on extraction yield of PGM by aqua regia. Analysis of variance was used to determine the optimum conditions and most significant factors affecting the overall metal extraction. In the optimum conditions, leaching of Pt, Pd and Rh was 91.58%, 93.49% and 60.15%, respectively. The effect of different oxidizing agents on the PGM dissolution in chloride medium was studied comparatively in the following leaching systems: a) aqua regia/sulfuric acid mixture, b) hydrogen peroxide in sulfuric acid (piranha solution), c) sodium hypochlorite and d) copper(II). Dissolution of Rh is increased in both aqua regia and hydrogen peroxide/hydrochloric acid solutions by adding sulfuric acid.

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

    Science.gov (United States)

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

    2016-03-01

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

  20. Hydrogen-Sensing Behaviors of Pd-and Pt-SiC Schottky Diodes

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Chang Kyo; Lee, Joo Hun; Hong, Chin Soo [Soonchunhyang University (Korea); Cho, Nam Ihn [Sunmoon University (Korea)

    2000-07-01

    Hydrogen-sensing behaviors of Pd-and Pt-SiC Schottky diodes, fabricated on the same SiC substrate, have been systematically compared and analyzed as a function of hydrogen concentration and temperature by I-V and {delta}I-t methods under steady-state and transient conditions. The effects of hydrogen adsorption on the device parameters such as the barrier height are investigated. The significant differences in their hydrogen sensing characteristics have been examined in terms of sensitivity limit, linearity of response, response rate, and response time. For the investigated temperature range, Pd-SiC Schottky diode shows better performance for H{sub 2} detection than Pt-SiC Schottky diode under the same testing conditions. The physical and chemical mechanisms responsible for hydrogen detection are discussed. Analysis of the steady-state reaction kinetics using I-V method confirmed that the atomistic hydrogen process is responsible for the barrier height change in the diodes. (author). 16 refs., 10 figs.

  1. Simulating Linear Sweep Voltammetry from First-Principles: Application to Electrochemical Oxidation of Water on Pt(111) and Pt3Ni(111)

    DEFF Research Database (Denmark)

    Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan

    2012-01-01

    Cyclic voltammetry is a fundamental experimental method for characterizing adsorbates on electrochemical surfaces. We present a model for the electrochemical solid–liquid interface, and we simulate the linear sweep voltammogram of the electrochemical oxidation of H2O on Pt(111) and Pt3Ni(111...

  2. Electric field modification of magnetotransport in Ni thin films on (011) PMN-PT piezosubstrates

    Science.gov (United States)

    Tkach, Alexander; Kehlberger, Andreas; Büttner, Felix; Jakob, Gerhard; Eisebitt, Stefan; Kläui, Mathias

    2015-02-01

    This study reports the magnetotransport and magnetic properties of 20 nm-thick polycrystalline Ni films deposited by magnetron sputtering on unpoled piezoelectric (011) [PbMg1/3Nb2/3O3]0.68-[PbTiO3]0.32 (PMN-PT) substrates. The longitudinal magnetoresistance (MR) of the Ni films on (011) PMN-PT, measured at room temperature in the magnetic field range of -0.3 T PMN-PT substrate, which results in a transfer of strain to the Ni film, the MR value decreases by factor of 20 for the current along [100] of PMN-PT and slightly increases for the [ 01 1 ¯ ] current direction. Simultaneously, a strong increase (decrease) in the field value, where the MR saturates, is observed for the [ 01 1 ¯ ] ([100]) current direction. The anisotropic magnetoresistance is also strongly affected by the remanent strain induced by the electric field pulses applied to the PMN-PT in the non-linear regime revealing a large (132 mT) magnetic anisotropy field. Applying a critical electric field of 2.4 kV/cm, the anisotropy field value changes back to the original value, opening a path to voltage-tuned magnetic field sensor or storage devices. This strain mediated voltage control of the MR and its dependence on the crystallographic direction is correlated with the results of magnetization reversal measurements.

  3. Ab initio modelling of magnetic anisotropy in Sr3NiPtO6

    NARCIS (Netherlands)

    Pradipto, A. -M.; Broer, R.; Picozzi, S.

    2016-01-01

    First principles calculations in the framework of Density Functional Theory (DFT) and wavefunction-based correlated methods have been performed to investigate in detail the magnetic anisotropy in Sr3NiPtO6. This material is known for the easy-plane anisotropy with a large anisotropy constant of abou

  4. Synthesis of Pt3Ni Microspheres with High Performance for Rapid Degradation of Organic Dyes

    Science.gov (United States)

    Wang, Min; Yang, Yushi; Long, Jia; Mao, Zhou; Qiu, Tong; Wu, Qingzhi; Chen, Xiaohui

    2015-05-01

    In this study, Pt3Ni microspheres consisted of nanoparticles were synthesized without addition of surfactants via the solvothermal route. The obtained sample was characterized by X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometer (ICP-AES), X-ray photoelectron spectroscopy (XPS), and field-emission scanning electron microscopy (FESEM). Furthermore, the catalytic performance of as-synthesized Pt3Ni microspheres was evaluated on the degradation of different organic dyes (methylene blue, methyl orange, Congo red, and rhodamine B). The results show that different dyes were rapidly decomposed by Pt3Ni microspheres in different pathways. Among different dyes, the formation and further degradation of the intermediates was observed during the degradation of methylene blue and methyl orange, suggesting the indirect degradation process of these dyes. This study provides not only a promising catalyst for the removal of organic contaminants for environment remediation, but also new insights for Pt3Ni alloy as a high-performance catalyst in organic synthesis.

  5. On the causes of compositional order in the Ni sub c Pt sub (1-c) alloys

    Energy Technology Data Exchange (ETDEWEB)

    Gyorffy, B.L. (Bristol Univ. (United Kingdom). H.H. Wills Physics Lab.); Pinski, F.J. (Cincinnati Univ., OH (United States). Dept. of Physics); Ginatempo, B. (Messina Univ. (Italy). Ist. di Fisica Teorica); Johnson, D.D. (Sandia National Labs., Albuquerque, NM (United States)); Staunton, J.B. (Warwick Univ., Coventry (United Kingdom). Dept. of Physics); Shelton, W.A.; Stocks, G.M.; Nicholson, D.M.

    1991-01-01

    We review, briefly, the arguments which gave rise to the current controversy concerning the origin of compositional order in Ni{sub c}Pt{sub 1-c} alloys. We note that strain fluctuations play an important role in determining the state of compositional order in this system and outline a theoretical framework that takes account of them. 29 refs., 4 figs.

  6. Synthesis of Pt3Ni microspheres with high performance for rapid degradation of organic dyes.

    Science.gov (United States)

    Wang, Min; Yang, Yushi; Long, Jia; Mao, Zhou; Qiu, Tong; Wu, Qingzhi; Chen, Xiaohui

    2015-12-01

    In this study, Pt3Ni microspheres consisted of nanoparticles were synthesized without addition of surfactants via the solvothermal route. The obtained sample was characterized by X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometer (ICP-AES), X-ray photoelectron spectroscopy (XPS), and field-emission scanning electron microscopy (FESEM). Furthermore, the catalytic performance of as-synthesized Pt3Ni microspheres was evaluated on the degradation of different organic dyes (methylene blue, methyl orange, Congo red, and rhodamine B). The results show that different dyes were rapidly decomposed by Pt3Ni microspheres in different pathways. Among different dyes, the formation and further degradation of the intermediates was observed during the degradation of methylene blue and methyl orange, suggesting the indirect degradation process of these dyes. This study provides not only a promising catalyst for the removal of organic contaminants for environment remediation, but also new insights for Pt3Ni alloy as a high-performance catalyst in organic synthesis.

  7. Comparison of Clinical Effects of Au-Pt Based and Ni-Cr Based Porcelain Crowns

    Institute of Scientific and Technical Information of China (English)

    Li-chun Wu; Ye Shi; Teng Ma

    2012-01-01

    Objective To compare the long-term clinical effects of two kinds of crowns and bridges made of porcelain fused to Au-Pt alloy and Ni-Cr alloy.Methods A total of 131 teeth (64 patients) were rehabilitated using porcelain-fused-to-metal crowns,among which 59 were rehabilitated with Au-Pt alloy metal ceramic crown and 72 with Ni-Cr alloy metal ceramic crown.The porcelain fracture,shade,marginal adaptation,gingival discoloration,and gingival status after finishing restoration and 36 months of follow-up were evaluated.Results After 36 months of restoration,porcelain fused to Au-Pt alloy crown showed better clinical effects than porcelain fused to Ni-Cr alloy crown in shade,marginal adaptation,gingival discoloration,as well as gingival status (all P<0.05).Conclusion The Au-Pt alloy ceramic crown is superior to Ni-Cr alloy ceramic crown in long-term clinical effects.

  8. Molecular dynamics simulation of temperature and strain rate effects on the elastic properties of bimetallic Pd-Pt nanowires

    Science.gov (United States)

    Sankaranarayanan, Subramanian K. R. S.; Bhethanabotla, Venkat R.; Joseph, Babu

    2007-10-01

    Molecular dynamics simulation is used to investigate the mechanical properties of infinitely long, cylindrical bimetallic Pd-Pt nanowires, with an approximate diameter of 1.4nm and two different compositions (25% and 50% Pt). The nanowires are subjected to uniaxial tensile strain along the [001] axis with varying strain rates of 0.05%ps-1 , and 5.0%ps-1 , at simulation temperatures of 50 and 300K , to study the effects of strain rates and thermal conditions on the deformation characteristics and mechanical properties of the nanowire. The deformation and rupture mechanism of these nanowires is explored in detail. Comparisons to the behavior exhibited by pure Pd and Pt nanowires of similar diameter are also made. The effect of lattice mismatch on the observed deformation modes in bimetallic nanowires is also discussed. Our simulations indicate that Pd-Pt alloy nanowires of various compositions, with little lattice mismatch between Pd and Pt atoms, undergo similar deformation and rupture upon uniaxial stretching. It is found that yielding and fracture mechanisms depend on the applied strain rate as well as atomic arrangement and temperature. At low temperature and strain rate, where crystal order and stability are highly preserved, the calculated stress-strain response of pure Pt and Pd as well as Pd-Pt alloy nanowires showed clear periodic, stepwise dislocation-relaxation behavior. Crystalline to amorphous transformation takes place at high strain rates (5%ps-1) , with amorphous melting detected at 300K . Deformation of nanowires at higher strain rates and low temperature, where the superplasticity characteristic is significantly enhanced, results in the development of a multishell helical structure. Mechanical properties of the alloy nanowires are significantly different from those of bulk phase and are dictated by the applied strain rate, temperature, alloy composition, as well as the structural rearrangement associated with nanowire elongation. We find that Young

  9. Edge-modulated perpendicular magnetic anisotropy in [Co/Pd]n and L10-FePt thin film wires

    Science.gov (United States)

    Zhang, Jinshuo; Ho, Pin; Currivan-Incorvia, Jean Anne; Siddiqui, Saima A.; Baldo, Marc A.; Ross, Caroline A.

    2015-11-01

    Thickness modulation at the edges of nanostructured magnetic thin films is shown to have important effects on their perpendicular magnetic anisotropy. Thin film wires with tapered edges were made from [Co/Pd]20 multilayers or L10-FePt films using liftoff with a double-layer resist. The effect of edge taper on the reversal process was studied using magnetic force microscopy and micromagnetic modeling. In [Co/Pd]20, the anisotropy was lower in the tapered edge regions which switched at a lower reverse field compared to the center of the wire. The L10-FePt wires showed opposite behavior with the tapered regions exhibiting higher anisotropy.

  10. 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.

  11. Radiolytically prepared Ni-Pd sols as catalysts for water photoreduction

    Energy Technology Data Exchange (ETDEWEB)

    Amouyal, E.; Georgopoulos, M.; Delcourt, M.O. (Paris-11 Univ., 91 - Orsay (FR). Lab. de Physico-Chimie des Rayonnements)

    1989-07-01

    Ni-Pd sols containing 10% Pd, prepared via radiolytic reduction, display a catalytic activity notably enhanced, compared to pure nickel sols, towards the water photoreduction to hydrogen. The test system is Ru(bipy){sub 3}{sup 2+}/methylviologen/N-phenylglycine: a favourable pH effect is shown at pH 2.5. Hydrogen evolution rate is not far from the optimal values obtained with platinum sols in acidic medium. These Ni-Pd aggregates are the first example of an aqueous colloid metal catalyst being improved by alloying effect.

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

    Science.gov (United States)

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

    2014-08-13

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

  13. Controlling the alloy composition of PtNi nanocrystals using solid-state dewetting of bilayer films

    Energy Technology Data Exchange (ETDEWEB)

    Seo, Okkyun; Oh, Se An; Lee, Ji Yeon; Ha, Sung Soo; Kim, Jae Myung; Choi, Jung Won; Kim, Jin-Woo [Department of Physics and Photon Science & School of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 61005 (Korea, Republic of); Kang, Hyon Chol [Department of Materials and Science Engineering, Chosun University, Gwangju 61542 (Korea, Republic of); Noh, Do Young, E-mail: dynoh@gist.ac.kr [Department of Physics and Photon Science & School of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 61005 (Korea, Republic of)

    2016-05-15

    We demonstrate that solid-state dewetting of bilayer films is an effective way for obtaining bimetallic alloy nanocrystals of controlled composition. When a Pt–Ni bilayer film were annealed near 700 °C, Pt and Ni atoms inter-diffused to form a PtNi bimetallic alloy film. Upon annealing at higher temperatures, the bilayer films transformed into <111> oriented PtNi alloy nanocrystals in small-rhombicuboctahedron shape through solid-state dewetting process. The Pt content of the nanocrystals and the alloy films, estimated by applying the Vegard's law to the relaxed lattice constant, was closely related to the thickness of each layer in the as-grown bilayer films which can be readily controlled during bilayer deposition. - Highlights: • Composition control of PtNi nanoparticles using solid state dewetting is proposed. • PtNi alloy composition was controlled by thickness ratio of Pt–Ni bilayer films. • PtNi alloy nanocrystals were obtained in small-rhombicuboctahedron shape.

  14. DFT study of difference caused by catalyst supports in Pt and Pd catalysis of oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Based on an experimental phenomenon that catalytic activity of Pt and Pd for oxygen reduction reaction (ORR) changes with catalyst supports from C to TiO2, density function theory (DFT) was used to elucidate the cause behind the difference in catalysis caused by catalyst supports. First, factors closely associated with the first electron transfer of the ORR were assessed in the light of quantum chemistry. Then intermediate (atomic oxygen, O) adsorption strength on the catalyst surface was calculated. The results show that, in terms of minimum energy difference, the best orbital symmetry match, and the maximum orbital overlap, TiO2 does bring about a very positive effect on catalysts Pd/TiO2 for the first electron transfer of the ORR. Especially, TiO2 remarkably expands the space size of Pd/TiO2 HOMO orbital and improves orbital overlap of Pd/TiO2 HOMO and O2 LUMO. The analysis of deformation density and partial density of state shows that the strong interaction between Pt and Ti leads to a strong adsorption of intermediate O on Pt/TiO2, but the strong interaction between Pd and surface O causes positive net charge of Pd and a weak adsorption of intermediate O on Pd/TiO2. Thus, the ORR can proceed more smoothly on Pd/TiO2 than Pt/TiO2 in every respect of maximum orbital overlap and rate delay by intermediate O. The research also discloses that several factors lead to less activity of TiO2-supported Pt and Pd catalysts than the C-supported ones for the ORR. These factors include the poor dispersion of Pt and Pd particles on TiO2, poor electric conduction of TiO2 carrier itself, and bigger energy difference between HOMO of TiO2-carried metallic catalysts and LUMO of O2 molecule due to electrons deeply embedded in the semiconductor TiO2 carrier.

  15. DFT study of difference caused by catalyst supports in Pt and Pd catalysis of oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    LI Li; WEI ZiDong; ZHANG Yi; QI XueQiang; XIA MeiRong; ZHANG Jie; SHAO ZhiGang

    2009-01-01

    Based on an experimental phenomenon that catalytic activity of Pt and Pd for oxygen reduction reac-tion (ORR) changes with catalyst supports from C to TiO2, density function theory (DFT) was used to elucidate the cause behind the difference in catalysis caused by catalyst supports. First, factors closely associated with the first electron transfer of the ORR were assessed in the light of quantum chemistry. Then intermediate (atomic oxygen, O) adsorption strength on the catalyst surface was calculated. The results show that, in terms of minimum energy difference, the best orbital symmetry match, and the maximum orbital overlap, TiO2 does bring about a very positive effect on catalysts Pd/TiO2 for the first electron transfer of the ORR. Especially, TiO2 remarkably expands the space size of Pd/TiO2 HOMO or-bital and improves orbital overlap of Pd/TiO2 HOMO and O2 LUMO. The analysis of deformation density and partial density of state shows that the strong interaction between Pt and Ti leads to a strong ad-sorption of intermediate O on Pt/TiO2, but the strong interaction between Pd and surface O causes positive net charge of Pd and a weak adsorption of intermediate O on Pd/TiO2. Thus, the ORR can proceed more smoothly on Pd/TiO2 than Pt/TiO2 in every respect of maximum orbital overlap and rate delay by intermediate O. The research also discloses that several factors lead to less activity of TiO2-supported Pt and Pd catalysts than the C-supported ones for the ORR. These factors include the poor dispersion of Pt and Pd particles on TiO2, poor electric conduction of TiO2 carrier itself, and bigger energy difference between HOMO of TiO2-carried metallic catalysts and LUMO of O2 molecule due to electrons deeply embedded in the semiconductor TiO2 carrier.

  16. Large enhancement of perpendicular magnetic anisotropy and high annealing stability by Pt insertion layer in (Co/Ni-based multilayers

    Directory of Open Access Journals (Sweden)

    Xi Chen

    2015-09-01

    Full Text Available We have investigated the influence of ultrathin Pt insertion layers on the perpendicular magnetic anisotropy (PMA and annealing stability of Ta/Pt/(Co/Ni×3/Co/Pt/Ta multilayered films. When the Pt layers were inserted at the Co/Ni interfaces, the PMA of the multilayered films decreased monotonically as the thickness of the Pt insertion layer (tPt was increased. However, when the Pt layers were inserted at the Ni/Co interfaces, the PMA increased from 1.39 × 106 to 3.5 × 106 erg/cm3 as tPt increased from 0 to 10 Å. Moreover, the multilayered film containing 6-Å-thick Pt insertion layers that inserted at the Ni/Co interfaces exhibited the highest annealing stability for PMA, which was up to temperature of 480 °C. We hypothesize that the introduced Pt/Co interfaces, due to the Pt insertion layers, are responsible for the enhanced PMA and high annealing stability. This study is particularly important for perpendicularly magnetized spintronic devices that require high PMA and high annealing stability.

  17. Low Pt content on the Pd{sub 45}Pt{sub 5}Sn{sub 50} cathode catalyst for PEM fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Salvador-Pascual, J.J.; Solorza-Feria, O. [Depto. Quimica, Centro de Investigacion y de Estudios Avanzados del IPN, A. Postal 14-740, 07360 Mexico D.F. (Mexico); Collins-Martinez, V.; Lopez-Ortiz, A. [Centro de Investigacion en Materiales Avanzados, Miguel de Cervantes 120, 31109 Chihuahua (Mexico)

    2010-06-01

    Pd{sub 45}Pt{sub 5}Sn{sub 50} electrocatalyst was prepared by a NaBH{sub 4} reduction of PdCl{sub 2}, H{sub 2}PtCl{sub 6} and SnCl{sub 2} in THF at 0 C. This catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS) microanalysis and hydrodynamic electrochemical technique. XRD, SEM and TEM results demonstrate that the borohydrate reduction methodology enable the synthesis of conglomerated particles nanometric in size ranging from 1 to 6 nm. Oxygen reduction reaction (ORR) activity was investigated on carbon dispersed catalyst by rotating disk electrode (RDE) technique in H{sub 2}SO{sub 4} 0.5 M. The effect of temperature on the kinetics was analyzing resulting in an apparent activation energy of 42.54 {+-} 1 kJ mol{sup -1}, value which is less than the obtained for the nanostructured bimetallic PdSn electrocatalyst under the same experimental condition. The Pd{sub 45}Pt{sub 5}Sn{sub 50} electrocatalyst dispersed on a carbon powder was tested as cathode electrocatalyst in a membrane-electrode assembly (MEA) arriving to a power density of 210 mW cm{sup -2} at 0.35 V and 80 C. (author)

  18. Control of the composition of Pt-Ni electrocatalysts in surfactant-free synthesis using neat N-formylpiperidine

    Science.gov (United States)

    Zhang, Na; Tsao, Kai-Chieh; Pan, Yung-Tin; Yang, Hong

    2016-01-01

    This paper describes the facile and surfactant-free synthesis of faceted Pt-Ni alloy nanoparticle electrocatalysts using neat N-formylpiperidine as a new type of solvent. Unlike the widely-used colloidal synthesis based on long-carbon chain surfactants, nanoparticles made in neat N-formylpiperidine possess a directly accessible surface for electrocatalytic reactions, making it a very attractive alternative solvent. The area-specific oxygen reduction reaction (ORR) activity is much higher than the commercial Pt/C catalyst reference and reaches a maximum of 1.12 mA cm-2 for the Pt-Ni alloy nanoparticles. We observed that the freshly formed Pt-Ni alloy could have controllable bulk and near surface compositions under the same initial reaction conditions and precursor ratio. The change in the composition could be attributed to the effect of CO on the formation of uniform nuclei at the initial stage, and a different deposition rate between Pt and Ni metals during the growth. The well-defined Pt-Ni nanoparticle catalysts show strong composition-dependent catalytic behavior in ORR, highlighting the important role of controlling the growth kinetics in the preparation of active Pt-Ni ORR catalysts.This paper describes the facile and surfactant-free synthesis of faceted Pt-Ni alloy nanoparticle electrocatalysts using neat N-formylpiperidine as a new type of solvent. Unlike the widely-used colloidal synthesis based on long-carbon chain surfactants, nanoparticles made in neat N-formylpiperidine possess a directly accessible surface for electrocatalytic reactions, making it a very attractive alternative solvent. The area-specific oxygen reduction reaction (ORR) activity is much higher than the commercial Pt/C catalyst reference and reaches a maximum of 1.12 mA cm-2 for the Pt-Ni alloy nanoparticles. We observed that the freshly formed Pt-Ni alloy could have controllable bulk and near surface compositions under the same initial reaction conditions and precursor ratio. The change

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-11-01

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

  20. Formation of hard magnetic L1{sub 0}-FePt/FePd monolayers from elemental multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Goo, Nam Hoon

    2007-06-18

    In this thesis, ordered L1{sub 0}-FePt and FePd films of different nominal compositions are prepared from Fe/Pt and Fe/Pd multilayers by annealing. In case of the L1{sub 0}-FePt films the composition of the films is modified by changing the individual elemental layer thicknesses in the multilayer precursors. This simple variation of the composition is the great advantage of the multilayer approach compared to sputtering single alloy layer from an alloy target. The formation mechanism of the fct phase from the multilayers and the microstructural properties are investigated. The characteristics of the hysteresis loop (coercivity {mu}{sub 0}H{sub c}, remanence J{sub r}) and of the intrinsic magnetic properties (anisotropy constant K{sub l}, spontaneous polarization J{sub s}, exchange constant A) of the ordered L1{sub 0}-FePt and FePd films are studied. The effects of the composition of the L1{sub 0}-FePt films on the microstructural and magnetic properties are investigated. The microstructure of these ordered L1{sub 0}-FePt films are then correlated to the magnetic properties with microstructural parameters by investigating the temperature dependence of the coercivity. (orig.)

  1. 染料敏化太阳能电池Pt/NiP/ITO对电极的制备和性能%Preparation and Performance of Pt/NiP/ITO Counter Electrode for DSSC

    Institute of Scientific and Technical Information of China (English)

    马换梅; 田建华; 廖文明; 单忠强

    2012-01-01

    NiP alloy film was firstly prepared on the surface of the ITO conductive glass substrate by an electroless plating method,and then,the nanoparticles of platinum were electrodeposited on the NiP–plated layer to obtain Pt/NiP/ITO counter electrode used in DSSC.The parameters of Pt electro-deposition on NiP alloy layer were optimized.The influences of NiP alloy structure and Pt loading on the surface morphology and catalytic activity of Pt/NiP/ITO electrode were investigated.The surface morphology of Pt/NiP/ITO electrode was analyzed by atomic force microscopy.The electrochemical performance of Pt/NiP/ITO electrode was characterized by cyclic voltammetry and electrochemical impedance spectroscopy.The photovoltaic performance was evaluated from photocurrent-voltage curves in a single DSSC.The result shows that the NiP alloy deposited on ITO substrate enhances the conductivity and light reflection performance of the counter electrode,and also improves the distribution of Pt particles on the surface of electrode,resulting in that Jscand η of the DSSC are increased by 4% and 11%,respectively.%在ITO导电玻璃表面化学镀NiP合金薄膜,然后电化学沉积Pt纳米粒子,形成染料敏化太阳能电池Pt/NiP/ITO对电极。优化了化学镀NiP合金的工艺条件;研究了NiP的结构和铂载量对Pt/NiP/ITO电极形貌和催化活性的影响。采用原子力显微镜分析Pt/NiP/ITO电极的表面形貌;采用循环伏安法、电化学交流阻抗法表征其电化学性能;采用单体DSSC的光电流–电压曲线表征其光伏性能。测试结果表明,在ITO基体上化学镀NiP合金,提高了电极的导电性和光反射能力,改善了电极表面Pt粒子的分布,使电池的短路电流密度和光电转化效率分别提高了4%和11%。

  2. Formic acid electro-oxidation on carbon supported Pd{sub x}Pt{sub 1-x} (0 {>=} x {>=} 1) nanoparticles synthesized via modified polyol method

    Energy Technology Data Exchange (ETDEWEB)

    Baranova, Elena A., E-mail: elena.baranova@uottawa.c [Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis-Pasteur St., Ottawa, ON, K1N 6N5 (Canada); Miles, Neil [Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis-Pasteur St., Ottawa, ON, K1N 6N5 (Canada); Mercier, Patrick H.J.; Le Page, Yvon; Patarachao, Bussaraporn [Institute for Chemical Process and Environmental Technology, National Research Council Canada, 1200 Montreal Rd., Ottawa, ON, K1A 0R6 (Canada)

    2010-11-30

    Carbon supported nanoparticle catalysts of Pd{sub x}Pt{sub 1-x} (0 {>=} x {>=} 1) were synthesized using a modified polyol method and poly(N-vinyl-2-pyrrolidone) (PVP) as a stabilizer. Resulting nanoparticles were characterized by X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and chronoamperommetry (CA) study for formic acid electro-oxidation. Surface composition of the synthesized nanoparticles found from XPS revealed the Pt surface segregation even for the Pd-rich compositions. It is suggested that the surface segregation behavior in PdPt nanoparticles supported on carbon may be influenced, in addition to the difference in Pd and Pt surface energies, by particle size and particle interaction with the support. According to CA, the carbon supported Pd nanoparticles show the highest initial activity towards formic acid electro-oxidation at the potential of 0.3 V (RHE), due to the promotion of the direct dehydrogenation mechanism. However its stability is quite poor resulting in the fast deactivation of the Pd surface. Addition of Pt considerably improves the steady-state activity of Pd in 12 h CA experiment. CA measurements show that the most active catalyst is Pd{sub 0.5}Pt{sub 0.5} of 4 nm size, which displays narrow size distribution and Pd to Pt surface atomic ratio of 27-73.

  3. Solid phase metallurgy strategy to sub-5 nm Au-Pd and Ni-Pd bimetallic nanoparticles with controlled redox properties.

    Science.gov (United States)

    Tang, Yu; Xu, Shaodan; Dai, Yihu; Yan, Xiaoqing; Li, Renhong; Xiao, Liping; Fan, Jie

    2014-01-07

    A solid phase metallurgy strategy is applied to synthesize Au-Pd and Ni-Pd bimetallic nanoparticles (BMNPs) with a tight sub-5 nm particle size distribution. The near-surface elemental composition and redox properties of Au-Pd BMNPs can be well tailored, which leads to an optimized catalytic performance in n-hexane combustion.

  4. Electric-field tunable spin diode FMR in patterned PMN-PT/NiFe structures

    Science.gov (United States)

    Zietek, Slawomir; Ogrodnik, Piotr; Skowroński, Witold; Stobiecki, Feliks; van Dijken, Sebastiaan; Barnaś, Józef; Stobiecki, Tomasz

    2016-08-01

    Dynamic properties of NiFe thin films on PMN-PT piezoelectric substrate are investigated using the spin-diode method. Ferromagnetic resonance (FMR) spectra of microstrips with varying width are measured as a function of magnetic field and frequency. The FMR frequency is shown to depend on the electric field applied across the substrate, which induces strain in the NiFe layer. Electric field tunability of up to 100 MHz per 1 kV/cm is achieved. An analytical model based on total energy minimization and the Landau-Lifshitz-Gilbert equation, taking into account the magnetostriction effect, is used to explain the measured dynamics. Based on this model, conditions for optimal electric-field tunable spin diode FMR in patterned NiFe/PMN-PT structures are derived.

  5. Pt, PtCo and PtNi electrocatalysts prepared with mechanical alloying for oxygen reduction reaction in alkaline medium; Electrocatalizadores de Pt, PtCo y PtNi preparados por aleado mecanico para la reaccion de reduccion de oxigeno en medio alcalino

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Contreras, M.A.; Fernandez-Valverde, S.M. [Instituto Nacional de Investigaciones Nucleares, Ocoyoacac, Estado de Mexico (Mexico)]. E-mail: miguel.garcia@inin.gob.mx; Vargas-Garcia, J.R. [ESIQIE-IPN, Mexico D.F. (Mexico

    2009-09-15

    Pt, PtCo and PtNi electrocatalysts were prepared using mechanical alloying and their electrocatalytic activity was investigated for oxygen reduction reaction (ORR) in KOH 0.5 M using cyclic voltametry and rotary disc electrode (RDE) techniques. The electrocatalysts were characterized using x-ray diffraction, sweep electron microscopy, dispersive x-ray transmission and chemical analysis. The physical characterization indicated that all the electrocatalysts are alloys formed by agglomerated particles composed of nanocrystals. The chemical analysis showed the presence of iron in the alloys. For the electrocatalytic evaluation, polarization curves and Koutecky-Levich and Tafel graphs were obtained to determine the kinetic parameters of the electrocatalysts in the study. With the same experimental conditions, the PtCo presented better electrocatalytic performance with a higher exchange current density. [Spanish] Se prepararon electrocatalizadores de Pt, PtCo y PtNi por aleado mecanico y se investigo su actividad electrocatalitica para la reaccion de reduccion de oxigeno (RRO) en KOH 0.5 M utilizando las tecnicas de Voltametria ciclica y Electrodo de Disco Rotatorio. Los electrocatalizadores se caracterizaron por difraccion de rayos X, Microscopia electronica de Barrido, de Transmision y analisis quimico por dispersion de rayos X. La caracterizacion fisica indico que todos los electrocatalizadores son aleaciones formadas de particulas aglomeradas, compuestas de nanocristales. El analisis quimico mostro la presencia de hierro en las aleaciones. Para la evaluacion electrocatalitica se obtuvieron curvas de polarizacion, graficas de Koutecky-Levich y de Tafel para determinar los parametros cineticos de los electrocatalizadores en estudio. En las mismas condiciones experimentales, el PtCo presento el mejor desempeno electrocatalitico con la densidad de corriente de intercambio mas alta.

  6. Effect of NiO growth conditions on the bipolar resistance memory switching of Pt/NiO/SRO structure

    Energy Technology Data Exchange (ETDEWEB)

    Kurnia, F.; Hadiyawarman, H.; Jung, C. U.; Liu, C. L. [Hankuk University of Foreign Studies, Yongin (Korea, Republic of); Lee, S. B.; Yang, S. M.; Park, H. W.; Song, S. J.; Hwang, C. S. [Seoul National University, Seoul (Korea, Republic of)

    2010-12-15

    We deposited NiO thin films with SrRuO{sub 3} bottom electrodes on SrTiO{sub 3} (001) substrates by using pulsed laser deposition. The growth temperature and the oxygen pressure were varied in order to obtain NiO films with different structural and electrical properties. We investigated the I-V characteristics of the Pt/NiO/SRO structures and observed a strong dependence of bipolar resistance switching on the growth conditions of the NiO thin films. Stable bipolar memory resistance switching was observed only in the devices with NiO films deposited at 400 .deg. C and 10 mTorr of O{sub 2}. The off-state I-V curve of bipolar switching showed a linear fitting to the Schottky effect, indicating its origin in the NiO/SRO interface. Our results suggest that the growth conditions of NiO may affect the bipolar switching behavior through the film's resistance, the film's crystallinity, or the status of the grain boundaries.

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

    Science.gov (United States)

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

    2016-01-01

    Herein, a facile ultrasonic-assisted strategy was proposed to fabricate the Pd-Pt alloy/multi-walled carbon nanotubes (Pd-Pt/CNTs) nanocomposites. A good number of Pd-Pt alloy nanoparticles with an average of 3.4 ± 0.5 nm were supported on sidewalls of CNTs with uniform distribution. The composition of the Pd-Pt/CNTs nanocomposites could also be easily controlled, which provided a possible approach for the preparation of other architectures with anticipated properties. The Pd-Pt/CNTs nanocomposites were extensively studied by electron microscopy, induced coupled plasma atomic emission spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, and applied for the ethanol and methanol electro-oxidation reaction in alkaline medium. The electrochemical results indicated that the nanocomposites had better electrocatalytic activities and stabilities, showing promising applications for fuel cells. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Alloying effect via comparative studies of ethanol dehydrogenation on Cu(1 1 1), Cu3Pd(1 1 1), and Cu3Pt(1 1 1)

    Science.gov (United States)

    Wu, Ruitao; Wang, Lichang

    2017-06-01

    Ethanol dehydrogenations on Cu(1 1 1), Cu3Pd(1 1 1), and Cu3Pt(1 1 1) were studied using density functional theory with a PBE functional. The α-C-H and β-C-H scissions are endothermic on all surfaces while the O-H scission is exothermic on Cu(1 1 1) and Cu3Pt(1 1 1) but endothermic on Cu3Pd(1 1 1). The ethanol dehydrogenation occurs on Cu(1 1 1) through both α-C-H and O-H scissions but on Cu3Pd(1 1 1) and Cu3Pt(1 1 1) through only α-C-H scission. Furthermore, alloying Pt or Pd with Cu shows an increase in reaction rate at 493 K by more than 3 orders of magnitude, thus illustrating the promise of alloying Pt or Pd in Cu catalysts for ethanol dehydrogenation.

  9. Gas Phase Fabrication of Pd-Ni Nanoparticle Arrays for Hydrogen Sensor Applications

    Directory of Open Access Journals (Sweden)

    Peng Xing

    2015-01-01

    Full Text Available Pd-Ni nanoparticles have been fabricated by gas aggregation process. The formation of Pd-Ni nano-alloys was confirmed by X-ray photoelectron spectroscopy measurements. By depositing Pd-Ni nanoparticles on the interdigital electrodes, quantum conductance-based hydrogen sensors were fabricated. The Ni content in the nanoparticle showed an obvious effect on the hydrogen response behavior corresponding to the conductance change of the nanoparticle film. Three typical response regions with different conductance-hydrogen pressure correlations were observed. It was found that the α-β phase transition region of palladium hydride moves to significant higher hydrogen pressure with the addition of nickel element, which greatly enhance the hydrogen sensing performance of the nanoparticle film.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Chengzhou; Guo, Shaojun; Dong, Shaojun [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin, 130022 (China)

    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 copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. 3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid

    Directory of Open Access Journals (Sweden)

    Loïc Assaud

    2014-02-01

    Full Text Available Three-dimensionally (3D nanoarchitectured palladium/nickel (Pd/Ni catalysts, which were prepared by atomic layer deposition (ALD on high-aspect-ratio nanoporous alumina templates are investigated with regard to the electrooxidation of formic acid in an acidic medium (0.5 M H2SO4. Both deposition processes, Ni and Pd, with various mass content ratios have been continuously monitored by using a quartz crystal microbalance. The morphology of the Pd/Ni systems has been studied by electron microscopy and shows a homogeneous deposition of granularly structured Pd onto the Ni substrate. X-ray diffraction analysis performed on Ni and NiO substrates revealed an amorphous structure, while the Pd coating crystallized into a fcc lattice with a preferential orientation along the [220]-direction. Surface chemistry analysis by X-ray photoelectron spectroscopy showed both metallic and oxide contributions for the Ni and Pd deposits. Cyclic voltammetry of the Pd/Ni nanocatalysts revealed that the electrooxidation of HCOOH proceeds through the direct dehydrogenation mechanism with the formation of active intermediates. High catalytic activities are measured for low masses of Pd coatings that were generated by a low number of ALD cycles, probably because of the cluster size effect, electronic interactions between Pd and Ni, or diffusion effects.

  12. 3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid.

    Science.gov (United States)

    Assaud, Loïc; Monyoncho, Evans; Pitzschel, Kristina; Allagui, Anis; Petit, Matthieu; Hanbücken, Margrit; Baranova, Elena A; Santinacci, Lionel

    2014-01-01

    Three-dimensionally (3D) nanoarchitectured palladium/nickel (Pd/Ni) catalysts, which were prepared by atomic layer deposition (ALD) on high-aspect-ratio nanoporous alumina templates are investigated with regard to the electrooxidation of formic acid in an acidic medium (0.5 M H2SO4). Both deposition processes, Ni and Pd, with various mass content ratios have been continuously monitored by using a quartz crystal microbalance. The morphology of the Pd/Ni systems has been studied by electron microscopy and shows a homogeneous deposition of granularly structured Pd onto the Ni substrate. X-ray diffraction analysis performed on Ni and NiO substrates revealed an amorphous structure, while the Pd coating crystallized into a fcc lattice with a preferential orientation along the [220]-direction. Surface chemistry analysis by X-ray photoelectron spectroscopy showed both metallic and oxide contributions for the Ni and Pd deposits. Cyclic voltammetry of the Pd/Ni nanocatalysts revealed that the electrooxidation of HCOOH proceeds through the direct dehydrogenation mechanism with the formation of active intermediates. High catalytic activities are measured for low masses of Pd coatings that were generated by a low number of ALD cycles, probably because of the cluster size effect, electronic interactions between Pd and Ni, or diffusion effects.

  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

    2015-12-15

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

  14. Study of the Isothermal Oxidation Process and Phase Transformations in B2-(Ni,PtAl/RENE-N5 System

    Directory of Open Access Journals (Sweden)

    Luis Alberto Cáceres-Díaz

    2016-09-01

    Full Text Available Changes in composition, crystal structure and phase transformations of B2-(Ni,PtAl coatings upon isothermal oxidation experiments (natural and scale free oxidation at 1100 °C, as a function of time beyond their martensitic transformation, are reported. Specifically, the analysis of lattice parameter and composition are performed to identify changes in the B2-(Ni,PtAl phase upon the chemically-driven L10-(Ni,PtAl and L12-(Ni,Pt3Al transformations. The B2-(Ni,PtAl phase was found to disorder and transform the martensite during the heat treatments for both oxidation experiments at approximately 36.3 and 40.9 at. % of Al, 47.7 and 42.9 at. % of Ni, 6.2 and 8.5 at. % of Pt, 4.2 and 2.9 at. % of Cr and 4.4 and 3.8 at. % of Co. The lattice constant and the long-range order parameter of the B2-(Ni,PtAl phase decreased linearly as a function of the elemental content irrespective of the nature of the oxidation experiments.

  15. New insights into the effects of alloying Pt with Ni on oxygen reduction reaction mechanisms in acid medium: a first-principles study.

    Science.gov (United States)

    Ou, Li-Hui

    2015-11-01

    The effects of alloying Pt with transition metal Ni on oxygen reduction reaction (ORR) mechanisms was investigated based on a systematic density functional theory (DFT) calculation explored in the present work. New insights into the ORR mechanisms were reported at the atomic level on Pt-segregated Pt3Ni(111). Only one molecular chemisorption state with the end-on OOH configuration was identified through geometry optimization and minimum energy path (MEP) analysis; top-bridge-top configuration as observed on pure Pt(111) was not identified on Pt-segregated Pt3Ni(111), indicating that alloying Pt with Ni influences the intermediates of ORR, and leads to only the dissociation mechanism of chemisorption state OOH species being involved in acid medium on Pt-segregated Pt3Ni(111). By contrast, the dissociation mechanisms of chemisorbed O2 molecule with top-bridge-top configuration and OOH species both were involved on pure Pt(111). The rds of the entire four-electron ORR was changed after Pt alloying with Ni. The rds of the entire ORR is the proton and electron transfer to O2 to form OOH on Pt-segregated Pt3Ni(111), whereas it is the reaction of O atom protonation to form OH species on pure Pt(111), indicating that sublayer Ni strongly influences the rds of ORR. The comparison of the ORR mechanisms explained that Pt3Ni alloy enhanced the ORR electrocatalytic activity more than pure Pt. The effect of electrode potential on ORR pathway on the pure Pt and Pt3Ni alloy was considered to obtain further insights into the electrochemical reduction of O2. Results showed that the proton and electron transfer becomes difficult at high potential. The ORR can easily proceed when the electrode potential lowers. For pure Pt- and Pt-based alloys, this phenomenon may imply the origin of the overpotential.

  16. Oxidizing behavior of some platinum metal fluorides. [Xe complexes with Pt, Pd fluorides; Chlorine-2 oxidation by transition metal hexafluorides

    Energy Technology Data Exchange (ETDEWEB)

    Graham, L.

    1978-10-01

    The previously known compounds Xe/sub 2/F/sub 3//sup +/PtF/sub 6//sup -/, XeF/sup +/PtF/sub 6//sup -/ and XeF/sub 2/.2PtF/sub 4/(XePt/sub 2/F/sub 10/) were prepared by the interaction of XeF/sub 2/ with PtF/sub 4/. The new compounds XeF/sub 2/.PdF/sub 4/ and XeF/sub 2/.2PdF/sub 4/(XePd/sub 2/F/sub 10/) were produced by interaction of XeF/sub 2/ with either PdF/sub 4/ or Pd/sub 2/F/sub 6/. A weight loss-versus-time curve indicated the presence of 4:1, 3:1 and 2:1 XeF/sub 2//PdF/sub 4/ complexes. The thermal decomposition of XeFPtF/sub 6/ or XePd/sub 2/F/sub 10/ yields highly pure XeF/sub 4/. Thus the interaction of XeF/sub 2/ with platinum fluorides (PtF/sub 4/ or PtF/sub 5/) or palladium fluorides (Pd/sub 2/F/sub 6/ or PdF/sub 4/) provides for the conversion of XeF/sub 2/ to XeF/sub 4/. The compound XePd/sub 2/F/sub 10/ is a close structural relative of XePt/sub 2/F/sub 10/, and spectroscopic evidence suggests that both are salts of XeF/sup +/ and a polymeric (M/sub 2/F/sub 9/)/sub x//sup x-/ ion. A Xe:PtF/sub 6/ material of approximately 1:1 stoichiometry has been prepared and compared with XePdF/sub 6/(XeF/sub 2/.PdF/sub 4/). The interaction of chlorine with the third-series transition metal hexafluorides has been investigated. Gravimetric and tensimetric evidence indicate that the initial product of the Cl/sub 2/ plus IrF/sub 6/ reaction is a solid of composition Cl/sub 2/IrF/sub 6/. Vibrational spectroscopic and other evidence indicates that this solid yields a sequence of products, of which Cl/sub 3//sup +/IrF/sub 6//sup -/, Cl/sub 3//sup +/Ir/sub 2/F/sub 11//sup -/ and Ir/sub 4/F/sub 20/ have been identified, the last being the ultimate solid product of the room temperature decomposition of the adduct. A new chlorine fluoride generated in the room temperature decomposition of Cl/sub 2/IrF/sub 6/ has been tentatively formulated as Cl/sub 3/F from infrared evidence.

  17. Molecular dynamics simulation study of the melting and structural evolution of bimetallic Pd-Pt nanowires

    Science.gov (United States)

    Sankaranarayanan, Subramanian K. R. S.; Bhethanabotla, Venkat R.; Joseph, Babu

    2006-10-01

    Thermal characteristics of Pd-Pt metal nanowires with diameters ranging from 2.3 to 3.5nm and of several compositions were studied by molecular dynamics simulations utilizing the quantum Sutton-Chen potential function. Monte Carlo simulations employing bond order simulation model were used to generate the initial wire configurations that consisted of surface segregated structures. Melting temperatures were estimated based on variations in thermodynamic properties such as potential energy and specific heat capacity. We find that the melting transition temperatures for the nanowires are much lower than those of bulk alloys of the same composition and at least 100-200K higher than those of nanoclusters of the same diameter. Density distributions along the nanowire cross section and axis as well as components of shell-based diffusion coefficients and velocity autocorrelation functions were used to investigate the melting mechanism in these nanowires. Our findings indicate a surface-initiated melting process characterized by predominantly larger cross-sectional movement. This two-dimensional surface melting mechanism in nanowires differs from that in nanoclusters in which atomic movement is more isotropic in all three dimensions. Differences in the surface melting mechanism result in structural transformations from fcc-hcp type and lead to simulated phase boundaries for nanowires that are different from bulk alloys as well as from same-diameter nanoclusters. A composition and temperature dependent fcc-hcp transformation occurs prior to the melting transition in both nanowires and nanoclusters. Hcp phase occurs over a wider temperature range at Pd-rich compositions and a narrower range at low Pd compositions with the fcc-hcp and hcp-liquid transition temperatures showing a minimum at 25% Pt composition. In contrast, the nanoclusters exhibit a near-linear dependence of melting temperature on Pd composition with the hcp phase existing over a much narrower range of

  18. 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

    of Au with mixed Pt/Pd skins. The activity of the binary and ternary catalysts is explained through weakening of the OH binding energy caused by solute elements. However, given the low alloy formation energies it may be difficult to tune and retain the composition under operating conditions...

  19. Facile and Rapid Synthesis of Ultrafine PtPd Bimetallic Nanoparticles and Their High Performance toward Methanol Electrooxidation

    Directory of Open Access Journals (Sweden)

    Tiantian Xia

    2014-01-01

    Full Text Available Uniform and sub-10 nm size bimetallic PtPd nanoparticles (NPs have been synthesized via a simple and facile method without using any surfactants at an ambient temperature. As a green and clean reductive agent, ascorbic acid (AA was employed for the coreduction of K2PtCl4 and K2PdCl4 in aqueous solution. The morphology, composition, and structure of PtPd NPs had been characterized by transmission electron microscopy (TEM, field emission high resolution transmission electron microscopy (FE-HRTEM, energy dispersive spectroscopy (EDS, X-ray diffraction (XRD, and X-ray photoelectron spectroscope (XPS. Comparing with both the monometallic Pt and Pd, the as-prepared alloy nanoparticles show superior electrocatalytic activity and better tolerance against poisoning by intermediates generated during methanol electrooxidation, which makes them a promising electrocatalysts for direct methanol fuel cells (DMFCs. Meanwhile, the green and simple approach could be easily extended to the manufacture of bimetallic or trimetallic alloy nanomaterials.

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

    Science.gov (United States)

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

  1. 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...

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

    Science.gov (United States)

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

  3. Room temperature hydrogen generation from hydrolysis of ammonia-borane over an efficient NiAgPd/C catalyst

    KAUST Repository

    Hu, Lei

    2014-12-01

    NiAgPd nanoparticles are successfully synthesized by in-situ reduction of Ni, Ag and Pd salts on the surface of carbon. Their catalytic activity was examined in ammonia borane (NH3BH3) hydrolysis to generate hydrogen gas. This nanomaterial exhibits a higher catalytic activity than those of monometallic and bimetallic counterparts and a stoichiometric amount of hydrogen was produced at a high generation rate. Hydrogen production rates were investigated in different concentrations of NH3BH3 solutions, including in the borates saturated solution, showing little influence of the concentrations on the reaction rates. The hydrogen production rate can reach 3.6-3.8 mol H2 molcat -1 min-1 at room temperature (21 °C). The activation energy and TOF value are 38.36 kJ/mol and 93.8 mol H2 molcat -1 min-1, respectively, comparable to those of Pt based catalysts. This nanomaterial catalyst also exhibits excellent chemical stability, and no significant morphology change was observed from TEM after the reaction. Using this catalyst for continuously hydrogen generation, the hydrogen production rate can be kept after generating 6.2 L hydrogen with over 10,000 turnovers and a TOF value of 90.3 mol H2 molcat -1 min-1.

  4. A branching NiCuPt alloy counter electrode for high-efficiency dye-sensitized solar cell

    Science.gov (United States)

    Yang, Peizhi; Tang, Qunwei

    2016-01-01

    A rising objective for high-efficiency dye-sensitized solar cells (DSSCs) is to create extraordinary and cost-effective counter electrode (CE) electrocatalysts. We present here a branching NiCuPt alloy CE synthesized by electrodepositing Ni on ZnO microrod templates and subsequently growing branched Cu as well as suffering from a galvanic displacement for Pt uptake. The resultant NiCuPt alloy CE displays a promising electrocatalytic activity toward redox electrolyte having I-/I3- couples. An impressive power conversion efficiency of 9.66% is yielded for the liquid-junction DSSC platform.

  5. In Situ Neutron Diffraction Study of NiTi-21Pt High-Temperature Shape Memory Alloys

    Science.gov (United States)

    Benafan, O.; Gaydosh, D. J.; Noebe, R. D.; Qiu, S.; Vaidyanathan, R.

    2016-12-01

    In situ neutron diffraction was used to investigate the microstructural features of stoichiometric and Ti-rich NiTiPt high-temperature shape memory alloys with target compositions of Ni29Ti50Pt21 and Ni28.5Ti50.5Pt21 (in atomic percent), respectively. The alloys' isothermal and thermomechanical properties (i.e., moduli, thermal expansion, transformation strains, and dimensional stability) were correlated to the lattice strains, volume-averaged elastic moduli, and textures as determined by neutron diffraction. In addition, the unique aspects of this technique when applied to martensitic transformations in shape memory alloys are highlighted throughout the paper.

  6. Exchange coupled composite FePt/TbCo/[Co/Ni]N films with an TbCo interlayer

    Directory of Open Access Journals (Sweden)

    Bin Ma

    2017-05-01

    Full Text Available The exchange coupled composite FePt/TbCo/[Co/Ni]N films have been prepared by DC magnetron sputtering. The net magnetization of ferromagnetic TbCo changes with the temperature variation, and then the magnetic configuration of FePt/TbCo/[Co/Ni]N changes. When a RE-dominated Tb32Co68 is inserted, FePt/Tb32Co68/[Co/Ni]5 has high coercivity at room temperature because of its synthesis ferrimagnetic sandwich structure, but small coercivity is obtained when the temperature is higher than 200 °C because of its graded ECC structure.

  7. Effects of recrystallization annealing on mechanical properties of cold-rolled PdNi5 wires

    Directory of Open Access Journals (Sweden)

    Aleksandra Ivanović

    2016-03-01

    Full Text Available The aim of this investigation was to determine the influence of the recrystallization temperature and recrystallization time on the microstructure and mechanical properties of the PdNi5 alloy subjected to cold deformation in the process of rolling at a constant deformation degree. The samples of PdNi5 alloy were recrystallization annealed within the temperature range of 200-1000ºC and annealing time range of 20-45 min after cold rolling with deformation degree of 97%. The tensile test was carried out using universal material testing machine. The hardness was also measured on the combined device for measuring Vickers and Brinell hardness. Metallographic observations were performed on an optical microscope. The analysis of the results of investigations regarding the microstructural changes and corresponding mechanical properties of cold-rolled PdNi5 strips shows that annealing temperature of 500ºC was sufficient to activate the energy for various recrystallization processes causing a change in the mechanical properties of cold-rolled PdNi5 strips. The annealing time, at constant annealing temperature, almost did not affect a recrystallization temperature and the mechanical properties of the cold-rolled PdNi5 strips.

  8. Negative effect of Ni on PtHY in n-pentane isomerization evidenced by IR and ESR studies

    Institute of Scientific and Technical Information of China (English)

    Muhammad Afif Ab Aziz; Nur Hidayatul Nazirah Kamarudin; Herma Dina Setiabudi; Halimaton Hamdan; Aishah Abdul Jalil; Sugeng Triwahyono

    2012-01-01

    Ni/PtHY with different Ni loadings was prepared by impregnating HY with hexachloroplatinic acid solution and Ni2+/N,N-dimethylformamide solution.An increase in the Ni loading decreased the crystallinity,specific surface area and meso-micropores of the catalysts.Ni interacted with hydroxyl groups to produce IR absorption bands at 3740-3500 cm-1.Increasing Ni loadings resulted in a decrease in the intensities of the broad bands at 3730-3500 cm-1 and the sharp band at 3740 cm-1 with simultaneous development of new absorbance band at 3700 cm-1 that was attributed to (-OH)Ni.The acidity of the samples did not significantly change with Ni loadings up to 1.0 wt%,which indicated that Ni mostly interacts with non-acidic silanol groups (terminal-and structural-defect OH groups).The presence of Ni decreased the activity of PtHY toward the isomerization of n-pentane because of a decrease in the number of active protonic-acid sites that formed from molecular hydrogen.IR and ESR studies confirmed that Pt facilitated the formation of protonic-acid sites from molecular hydrogen,whereas Ni,even when combined with Pt,didn't exhibit such ability.The absence of protonic-acid sites from molecular hydrogen significantly decreased the yield of iso-pentane and markedly increased the cracking products.

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

    Science.gov (United States)

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

    2016-02-01

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

  10. Transformation of Sodium Bicarbonate and CO2 into Sodium Formate over NiPd Nanoparticle Catalyst

    Directory of Open Access Journals (Sweden)

    Mengnan eWang

    2013-09-01

    Full Text Available The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs. Ni NPs and eight NiM (M stands for a second metal NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

  11. Transformation of Sodium Bicarbonate and CO2 into Sodium Formate over NiPd Nanoparticle Catalyst

    Science.gov (United States)

    Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

    2013-09-01

    The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

  12. Spin-orbit interaction tuning of perpendicular magnetic anisotropy in L1{sub 0} FePdPt films

    Energy Technology Data Exchange (ETDEWEB)

    Ma, X.; Lüpke, G., E-mail: gyguo@phys.ntu.edu.tw, E-mail: hbzhao@fudan.edu.cn, E-mail: gxluep@wm.edu [Department of Applied Science, College of William and Mary, 251 Jamestown Road, Williamsburg, Virginia 23187 (United States); He, P.; Ma, L.; Zhou, S. M. [Shanghai Key Laboratory of Special Artificial Microstructure Materials and Technology, School of Physics Science and Engineering, Tongji University, Shanghai 200092 (China); Guo, G. Y., E-mail: gyguo@phys.ntu.edu.tw, E-mail: hbzhao@fudan.edu.cn, E-mail: gxluep@wm.edu [Department of Physics, National Taiwan University, Taipei 10617, Taiwan (China); Zhao, H. B., E-mail: gyguo@phys.ntu.edu.tw, E-mail: hbzhao@fudan.edu.cn, E-mail: gxluep@wm.edu [Department of Optical Science and Engineering, Fudan University, 220 Handan Road, Shanghai 200433 (China)

    2014-05-12

    The dependence of perpendicular magnetic anisotropy K{sub u} on spin-orbit coupling strength ξ is investigated in L1{sub 0} ordered FePd{sub 1−x}Pt{sub x} films by time-resolved magneto-optical Kerr effect measurements and ab initio density functional calculations. Continuous tuning of K{sub u} over a wide range of magnitude is realized by changing the Pt/Pd concentration ratio, which strongly modifies ξ but keeps other leading parameters affecting K{sub u} nearly unchanged. Ab initio calculations predict a nearly quadratic dependence of K{sub u} on ξ, consistent with experimental data. K{sub u} increases with increasing chemical order and decreasing thermal spin fluctuations, which becomes more significant for samples with higher Pt concentration. The results demonstrate an effective method to tune K{sub u} utilizing its sensitivity on ξ, which will help fabricate magnetic systems with desirable magnetic anisotropy.

  13. Physical metallurgy and properties of TiNiSn and PtMnSb

    Energy Technology Data Exchange (ETDEWEB)

    Zhong, Bo [Iowa State Univ., Ames, IA (United States)

    1997-01-10

    The single crystals of TiNiSn and polycrystalline PtMnSb were grown by the flux and melt cooling method. Their lattice parameters and structures were determined by x-ray diffraction. The effect of impurities on the growth of TiNiSn single crystals was investigated. It was found that the concentration of chlorine plays a key role in determining the chemical composition of the phases that are formed. The heat capacity and magnetic susceptibility of TiNiSn was measured in a temperature range from 4.7 K to room temperature. Magnetic measurements show that the TiNiSn is paramagnetic, and that it does not order magnetically.

  14. Mechanical properties of Pt-Ir and Ni-Ir binary alloys for glass-molding dies coating.

    Science.gov (United States)

    Tseng, Shih-Feng; Lee, Chao-Te; Huang, Kuo-Cheng; Chiang, Donyau; Huang, Chien-Yao; Chou, Chang-Pin

    2011-10-01

    In this study, the different compositions of Pt-Ir and Ni-Ir alloys were deposited by utilizing ion source assisted magnetron sputtering system (ISAMSS). The surface roughness and crystallite size of the Pt-Ir and Ni-Ir coatings were analyzed by atomic force microscopy (AFM) and X-ray diffraction (XRD), respectively. In addition, coatings were soaked at 700 degrees and maintained 10 min under N2 atmosphere using a glass-molding machine. The annealed coatings for oxidation test were examined by energy dispersive X-ray spectrometry (EDS) and for microhardness and reduced modulus test were evaluated by nanoindentation instrucment. The cross-sectional structures between the Pt-Ir and Ni-Ir coating layer and substrates were also examined by field emission scanning electron microscope (FESEM). The results show that surface roughness Ra from 1.25 nm to 3.426 nm was observed with increasing the Ni elements. However, the Ra is less than 2 nm measured in Ir-based coatings doped with Pt concentrations under this study. With increasing Pt and Ni doping, the microhardness of both coatings decreased significantly and the values of reduced modulus of Pt-Ir alloys are larger than that of Ni-Ir alloys. After oxidation process, the oxygen concentration of Pt-Ir coatings is less than that of Ni-Ir coatings and the Pt-Ir coatings exhibit superior properties including oxidation resistance, low surface roughness and high reduced modulus over Ni-Ir coatings, especially for the high Pt concentration coatings such as Pt-Ir 2 (55.25 at.% Pt) and Pt-Ir 3 (79.42 at.% Pt) coatings. The surface roughnesses of all specimens annealed at 700 degrees C were slightly larger than as-deposited coatings. Moreover, due to the serious oxidation occurred in Ni-Ir 3 (73.45 at.% Ni) coatings, the value of reduced modulus of this specimen coating is the lowest and the corrsponding Ra value is the largest compared with the rest of Ir-based coatings in the oxidation testing.

  15. Unsupported NiPt alloy metal catalysts prepared by water-in-oil (W/O) microemulsion method for methane cracking

    KAUST Repository

    Zhou, Lu

    2016-05-18

    Unsupported NiPt metal catalyst with Ni/Pt molar ratio of 88/12 is prepared by water-in-oil (W/O) microemulsion method in this study. Compared to monometallic Ni and Pt catalysts, the NiPt catalyst exhibits superior activity and stability for methane cracking. By XRD (X-ray powder diffraction), XPS (X-ray photoelectron spectroscopy) and TEM (Transmission electron microscopy) analyses, the formation of Ni(0)Pt(0) alloy is believed to be the main reason for the reactivity improvement of this catalyst. Carbon nano tube (CNT) with Ni(0)Pt(0) particles anchored on the top of tube are found for the NiPt catalyst. © 2016 Elsevier Ltd.

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

    Science.gov (United States)

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

    2012-01-01

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

  17. Investigation of ordering phenomenon in Me–Pt (Me=Fe,Ni liquid alloys

    Directory of Open Access Journals (Sweden)

    Yisau Adelaja Odusote

    2008-01-01

    Full Text Available The phase diagrams of Fe–Pt and Ni–Pt liquid alloy systems show the existence of FePt and NiPt intermetallic compounds, respectively, in their solid intermediate states, and the associative tendency between unlike atoms in these liquid alloys has been analysed using the self-association model. The concentration dependences of mixing properties such as the free energy of mixing, GM; the concentration fluctuations, Scc(0, in the long-wavelength limits; the chemical short-range order (CSRO parameter, α1; as well as the chemical diffusion, enthalpy and entropy of the mixing of Fe–Pt and Ni–Pt liquid alloys have been investigated to determine the nature of ordering in the liquid alloys. The results show that heterocoordination occurs in the alloys at all concentrations. The effect of CSRO on Scc(0, chemical diffusion, D, and the order parameter, α1, has been considered. The ordering phenomenon in the liquid alloys is also related to the effect of the atomic size mismatch volume on Scc(0.

  18. Study of bimetallic Pd-Pt clusters in both free and supported phases

    Science.gov (United States)

    Rousset, J. L.; Cadrot, A. M.; Cadete Santos Aires, F. J.; Renouprez, A.; Mélinon, P.; Perez, A.; Pellarin, M.; Vialle, J. L.; Broyer, M.

    1995-06-01

    We study PdPt bimetallic clusters in both free and supported phases. These clusters have been produced with a laser vaporization source. Free clusters directly produced by the source are studied by time of flight mass spectrometry and photofragmentation technique. We observed a sequential evaporation of Pd atoms in the mixed clusters consistent with a palladium segregation process. This tendency has been also observed on supported particles from which the structure and the composition are determined by high resolution transmission electron microscopy and energy dispersive x-ray analysis. A main result is that each particle has the composition of the massic rod vaporized in the source. The supported particles are well crystallized and exhibit truncated octahedron shapes. Experimental observations are well explained using a modified tight binding model. Indeed, within this model, we found that the equilibrium shape is strongly related to the variation of the cohesive energy with atomic coordination number. Also, some preliminary results on the specific reactivity of these bimetallic clusters are presented.

  19. Effects of Ni{sub 3}Sn{sub 4} and (Cu,Ni){sub 6}Sn{sub 5} intermetallic layers on cross-interaction between Pd and Ni in solder joints

    Energy Technology Data Exchange (ETDEWEB)

    Baek, Yong-Ho [Department of Materials Science and Engineering, Korea University, Seoul 136-713 (Korea, Republic of); Division of Advanced Circuit Interconnect, Samsung Electro-Mechanics Co., Ltd., Suwon 443-743 (Korea, Republic of); Chung, Bo-Mook [Department of Materials Science and Engineering, Korea University, Seoul 136-713 (Korea, Republic of); Department of Research and Development, KPM TECH, Ansan 425-090 (Korea, Republic of); Choi, Young-Sik [Division of Advanced Circuit Interconnect, Samsung Electro-Mechanics Co., Ltd., Suwon 443-743 (Korea, Republic of); Choi, Jaeho [Department of Advanced Metal and Materials Engineering, Gangneung-Wonju National University, Gangneung 210-702 (Korea, Republic of); Huh, Joo-Youl, E-mail: jyhuh@korea.ac.kr [Department of Materials Science and Engineering, Korea University, Seoul 136-713 (Korea, Republic of)

    2013-12-05

    Highlights: •Ni{sub 3}Sn{sub 4} acts as a source of Ni atoms, leading to a strong cross-interaction with Pd. •(Cu,Ni){sub 6}Sn{sub 5} is an effective Ni diffusion barrier, inhibiting Pd resettlement. •Dissolution kinetics of (Pd,Ni)Sn{sub 4} was interpreted based on the Sn–Ni–Pd isotherm. •Cu addition to solder alleviates the (Pd,Ni)Sn{sub 4}-related risk of reliability deterioration. -- Abstract: We examined the effects of layers of intermetallic compound (IMC) Ni{sub 3}Sn{sub 4} and (Cu,Ni){sub 6}Sn{sub 5} formed at the solder/Ni interface, on the cross-interactions between Pd and Ni during solid-state aging and reflow soldering. Two types of diffusion couples, Pd/Sn/Ni and Pd/Sn–Cu/Ni, were aged at 150 °C to study the solid-state interactions. In contrast to the Pd/Sn/Ni couples in which a Ni{sub 3}Sn{sub 4} layer formed at the Ni interface, the Pd/Sn–Cu/Ni couple where a (Cu,Ni){sub 6}Sn{sub 5} layer formed at the Ni interface exhibited no significant interaction between Pd and Ni. The (Cu,Ni){sub 6}Sn{sub 5} layer acted as an effective barrier against Ni diffusion and thus inhibited the resettlement of (Pd,Ni)Sn{sub 4} onto the Ni interface. For the interaction during reflow, Sn–3.5Ag and Sn–3.0Ag–0.5Cu solder balls were isothermally reflowed on an electroless Ni(P)/electroless Pd/immersion Au (ENEPIG) surface finish at 250 °C, and the dissolution kinetics of the (Pd,Ni)Sn{sub 4} particles converted from the 0.2-μm-thick Pd-finish layer were examined. The spalled (Pd,Ni)Sn{sub 4} particles very quickly dissolved into the molten solder when the IMC layer formed on the Ni substrate was (Cu,Ni){sub 6}Sn{sub 5} rather than Ni{sub 3}Sn{sub 4}. The dependence of the dissolution kinetics of the spalled (Pd,Ni)Sn{sub 4} particles on the IMC layers was rationalized on the basis of a Sn–Ni–Pd isotherm at 250 °C. The present study suggests that the formation of a dense (Cu,Ni){sub 6}Sn{sub 5} layer at the solder/Ni interface can effectively

  20. SÍNTESIS Y CARACTERIZACIÓN DE CATALIZADORES Ni/MCM-22, Pt/MCM-22 Y Pt-Ni/MCM-22

    Directory of Open Access Journals (Sweden)

    Everton R.F. dos Santos

    2012-01-01

    Full Text Available El objetivo de este estudio fue producir la zeolita MCM-22 y, a partir de ésta, desarrollar catalizadores de zeolitas (Ni/MCM-22, Pt/MCM-22 y Pt-Ni/MCM-22. La obtención de estos catalizadores se realizó mediante el proceso de intercambio competitivo de iones. Estos materiales se caracterizaron por Difracción de Rayos X (DRX, Espectrometría de Energía Dispersiva (EDX, Termogravimétrico (TGA, y grado de adsorción de n-butilamina. La difracción de rayos X del precursor MCM-22 (P mostró los picos típicos de la topología MWW (Mobil tWenty tWo. En el patrón de difracción de la muestra calcinada no se observaron picos relacionados con la materia orgánica responsable por la producción de la zeolita MCM-22. Se verificó por termogravimetría, que la pérdida de masa en las muestras del catalizador se encuentra cercana a los 150 °C. La pérdida de masa total de los catalizadores muestra una reducción considerable en la cantidad de n-butilamina fisisorbida para el catalizador bimetálico.

  1. Pt, PtCo and PtNi electrocatalysts prepared by mechanical alloying for the oxygen reduction reaction in 0.5 M H{sub 2}SO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Contreras, M.A. [Instituto Nacional de Investigaciones Nucleares, Depto. de Quimica, Apdo. Postal 18-1027 Col. Escandon, C.P.11801 Mexico D.F. (Mexico); Instituto Politecnico Nacional, Depto. de Ing. Metalurgica, 07300 Mexico D.F. (Mexico); Fernandez-Valverde, S.M. [Instituto Nacional de Investigaciones Nucleares, Depto. de Quimica, Apdo. Postal 18-1027 Col. Escandon, C.P.11801 Mexico D.F. (Mexico); Vargas-Garcia, J.R. [Instituto Politecnico Nacional, Depto. de Ing. Metalurgica, 07300 Mexico D.F. (Mexico); Cortes-Jacome, M.A.; Toledo-Antonio, J.A.; Angeles-Chavez, C. [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas 152, Mexico, D.F.,0 7730 (Mexico)

    2008-11-15

    Electrocatalysts of Pt, PtCo and PtNi powders for the oxygen reduction reaction (ORR) were processed by Mechanical Alloying. Physical characterization was made by X-ray diffraction, scanning electron microscopy and scanning transmission electron microscopy. It was found that milled powders formed agglomerates in the range of 0.2-20 {mu}m formed by nanometric size crystallites. The synthesized powders were alloys of PtFe, PtCoFe and PtNiFe due to iron incorporation during the milling process. The binding energies of Pt in the alloys were determined by XPS. Polarization curves were obtained by Rotating Disk Electrode technique in 0.5 M H{sub 2}SO{sub 4} to determine the electrocatalytic activity of the mechanically alloyed powders. Tafel curves were plotted and kinetic parameters for the ORR were calculated. The PtFe alloy showed the highest electrocatalytic activity for the ORR. However, the lowest overpotential was found for the PtCoFe alloy and it also showed a higher current exchange density. A linear relationship was found between the Pt-binding energy in the alloys and the overpotential at the same current density independent of the Pt alloy composition. (author)

  2. Tuning the interface of Ni@Ni(OH)2/Pd/rGO catalyst to enhance hydrogen evolution activity and stability

    Science.gov (United States)

    Deng, Zihua; Wang, Jun; Nie, Yao; Wei, Zidong

    2017-06-01

    The interface engineering is vital to rational design and synthesis of the heterogeneous catalyst for high-performance electrochemically applications. The smart and elaborate architecture design offers several remarkable advantages, including good dispersion, more exposed active site and good electrical conductivity. We report a trace Pd induced formation of Ni@Ni(OH)2/Pd catalyst on reduced graphene oxides (rGO) by hydrothermal synthesis. We found that the presence of palladium seeds can promote the grain refinement and dispersion of the catalyst. The HRTEM results revealed that most of Ni@Ni(OH)2/Pd with a mean size of ∼10 nm are uniformly dispersed on the rGO sheets, with Pd particles and Ni@Ni(OH)2 balls located side by side. DFT calculations further confirmed a strong interaction existed in the interfaces, which leads to a stable Ni@Ni(OH)2/Pd/rGO morphology. By tailoring Ni@Ni(OH)2-Pd-rGO interfaces of the catalyst, the catalyst gives a current density of 10 mA cm-2 at a small over-potential of 76 mV and exhibits an excellent stability for the hydrogen evolution reaction in an alkaline environments.

  3. Carbon Nanotubes Supported Pt-Ru-Ni as Methanol Electro-Oxidation Catalyst for Direct Methanol Fuel Cells

    Institute of Scientific and Technical Information of China (English)

    Fei Ye; Shengzhou Chen; Xinfa Dong; Weiming Lin

    2007-01-01

    Carbon nanotubes (CNTs) supported Pt-Ru and Pt-Ru-Ni catalysts were prepared by chemical reduction of metal precursors with sodium borohydride at room temperature. The crystallographic properties and composition of the catalysts were characterized by X-ray diffraction (XRD) and energy dispersive X-ray (EDX) analysis, and the catalytic activity and stability for methanol electro-oxidation were measured by electrochemical impedance spectroscopy (EIS), linear sweep voltammetries (LSV), and chronoamperometry (CA). The results show that the catalysts exhibit face-centered cubic (fcc) structure.The particle size of Pt-Ru-Ni/CNTs catalyst is about 4.8 nm. The catalytic activity and stability of the Pt-Ru-Ni/CNTs catalyst are higher than those of Pt-Ru/CNTs catalyst.

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

    Science.gov (United States)

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

    2015-09-15

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

  5. Martensite Aging Effect and Thermal Cyclic Characteristics in Ti-Pd and Ti-Pd-Ni High Temperature Shape Memory Alloys

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The effect of thermal cycling and aging in martensitic state in Ti-Pd-Ni alloys were investigated by DSC and TEM observations. It is shown that the thermal cycling causes the decreases in Ms and Af temperatures in Ti50Pd50-xNix(x=10, 20, 30)alloys, but no obvious thermal cycling effect was observed in Ti50Pd50Pd40Ni10 alloys and the aging effect shows a curious feature, i.e.,the Af temperature does not saturate even after relatively long time aging, which is considered to be due to the occurrence of recovery recrystallization during aging.

  6. Catalytic reduction of 4-nitrophenol over Ni-Pd nanodimers supported on nitrogen-doped reduced graphene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Lijun, E-mail: liulj@wtu.edu.cn [College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, People' s Republic of China (China); Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Chen, Ruifen; Liu, Weikai [College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, People' s Republic of China (China); Wu, Jiamin [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Gao, Di, E-mail: gaod@pitt.edu [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States)

    2016-12-15

    Catalytic reduction of toxic 4-nitrophenol to 4-aminophenol over magnetically recoverable nanocatalysts has attracted much attention. Herein, we report a Ni-Pd/NrGO catalyst through the growth of Ni-Pd nanodimers (NDs) on nitrogen-doped reduced graphene oxide (NrGO). The Ni-Pd NDs show a heterogeneous nanostructure with Ni and Pd subparts contacting with each other, remarkably different from the frequently-observed core/shell nanoparticles (NPs) or nanoalloy. The formation of Ni-Pd NDs follows an initial deposition of Pd NPs on the graphene and in-situ catalytic generation of Ni subparts over the newly-generated Pd NPs. The resulting Ni-Pd/NrGO exhibits a superior catalytic activity towards the reduction of 4-nitrophenol at room temperature with a high rate constant (3400 s{sup -1} g{sup -1}) and a low activated energy (29.1 kJ mol{sup -1}) as compared to unsupported Ni-Pd NDs and supported monometallic catalysts. The conversion rate of 4-NP is calculated to be 99.5% and the percent yield (%) of 4-AP is as high as 99.1%. A synergistic catalysis mechanism is rationally proposed, which is ascribed to the electronic modification of Ni-Pd metals due to the strong metal/support interaction (SMSI) effect as well as the electron transfer between Ni and Pd. The hybrid catalyst shows soft ferromagnetic properties and can be magnetically separated and recycled without obvious loss of activity.

  7. Electrochemical oxidation of ammonia on carbon-supported bi-metallic PtM (M = Ir, Pd, SnO{sub x}) nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Lomocso, Thegy L. [Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis-Pasteur, Ottawa, ON K1N 6N5 (Canada); Baranova, Elena A., E-mail: elena.baranova@uottawa.ca [Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis-Pasteur, Ottawa, ON K1N 6N5 (Canada)

    2011-10-01

    Highlights: > Oxidation of NH{sub 3} is investigated on carbon-supported Pt and PtM (M = Pd, Ir, SnO{sub x}) nanoparticles. > Carbon supported PtPd and PtIr nanoparticles show higher catalytic activity if compared to Pt nanocatalyst. > Pt{sub 7}Ir{sub 3} nanoparticles combine good catalytic activity and enhanced stability for NH{sub 3} oxidation. > Electronic effect between two metals in PtIr is responsible for increase in the catalytic activity. - Abstract: Ammonia electro-oxidation was studied in alkaline solution on carbon-supported Pt and bimetallic Pt{sub y}M{sub 1-y} (M = Pd, Ir, SnO{sub x} and y = 70, 50 at.%) nanoparticles. Catalysts were synthesized using the modified polyol method and deposited on carbon, resulting in 20 wt.% of metal loading. Particle size, structure and surface composition of the particles were investigated using TEM, XRD and XPS. Mean size of PtM bi-metallic nanoparticles varied between 2.0 and 4.7 nm, depending on the second metal (M). XRD revealed the structure of all bi-metallic particles to be face-centered cubic and confirmed alloy formation for Pt{sub y}Pd{sub 1-y} (y = 70, 50 at.%) and Pt{sub 7}Ir{sub 3}nanoparticles, as well as partial alloying between Pt and SnO{sub x}. Electrochemical behaviour of ammonia on Pt and PtM nanoparticles is comparable to that expected for bulk Pt and PtM alloys. Addition of Pd to Pt at the nanoscale decreased the onset potential of ammonia oxidation if compared to pure platinum nanoparticles; however stability of the catalyst was poor. For Pt{sub 7}(SnO{sub x}){sub 3}, current densities were similar to Pt, whereas catalyst stability against deactivation was improved. It is found that carbon supported Pt{sub 7}Ir{sub 3} nanoparticles combine good catalytic activity with enhanced stability for ammonia electro-oxidation. Electronic effect generated between two metals in the bimetallic nanoparticles might be responsible for increase in the catalytic activity of Pd- and Ir-containing catalysts, causing

  8. Improvement in the Mechanical Properties of High Temperature Shape Memory Alloy (Ti50Ni25Pd25) by Copper Addition

    National Research Council Canada - National Science Library

    Rehman, Saif ur; Khan, Mushtaq; Khan, A. Nusair; Jaffery, Syed Husain Imran; Ali, Liaqat; Mubashar, Aamir

    2015-01-01

      High temperature shape memory alloys Ti50Ni25Pd25 and Ti50Ni20Pd25Cu5 were developed, characterized, and tensile tested in both martensite ( [subscript]Mf[/subscript] - 50°C) and austenite ( [subscript]Af[/subscript] + 50°C) phases...

  9. 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...

  10. Nanoporous PdNi Alloy Nanowires As Highly Active Catalysts for the Electro-Oxidation of Formic Acid.

    Science.gov (United States)

    Du, Chunyu; Chen, Meng; Wang, Wengang; Yin, Geping

    2011-02-01

    Highly active and durable catalysts for formic acid oxidation are crucial to the development of direct formic acid fuel cell. In this letter, we report the synthesis, characterization, and electrochemical testing of nanoporous Pd(57)Ni(43) alloy nanowires for use as the electrocatalyst towards formic acid oxidation (FAO). These nanowires are prepared by chemically dealloying of Ni from Ni-rich PdNi alloy nanowires, and have high surface area. X-ray diffraction data show that the Pd(57)Ni(43) nanowires have the face-centered cubic crystalline structure of pure Pd, whereas X-ray photoelectron spectroscopy confirm the modification of electronic structure of Pd by electron transfer from Ni to Pd. Electrocatalytic activity of the nanowires towards FAO exceeds that of the state-of-the-art Pd/C. More importantly, the nanowires are highly resistant to deactivation. It is proposed that the high active surface area and modulated surface properties by Ni are responsible for the improvement of activity and durability. Dealloyed nanoporous Pd(57)Ni(43) alloy nanowires are thus proposed as a promising catalyst towards FAO.

  11. Exploitation Properties of Ni-Pd/Al2O3 Catalyst Supported on Ceramic Foam

    Directory of Open Access Journals (Sweden)

    Vesna Nikolić

    2015-12-01

    Full Text Available The goal of this research was to examine exploitation properties of Ni-Pd/Al2O3 catalyst supported on α-Al2O3 based foam in the dry methane reforming. The catalyst was prepared by using aerosol method. Chloride precursors for Ni and Pd were reduced by hydrogen at low temperature of 533 K, without previous calcination. The reforming experiment was performed for 3 h, with standing time of 1 h for each of the following temperatures: 873, 973 and 1023 K. Conclusions on selectivity, catalytic activity and stability were made on the basis of CO and H2 yields.

  12. 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.

  13. Selective hydrogenation of phenylacetylene on Ni and Ni-Pd catalysts modified with heteropoly compounds of the Keggin type

    Science.gov (United States)

    Navalikhina, M. D.; Kavalerskaya, N. E.; Lokteva, E. S.; Peristyi, A. A.; Golubina, E. V.; Lunin, V. V.

    2012-12-01

    It is established that unmodified Ni catalysts and Ni catalysts modified with Mo- and W-heteropoly compounds (HPC) of the Keggin type (6 wt %) along with catalyst containing 6% K4SiW12O40/Al2O3 appear to be active in the reaction of phenylacetylene (PA) hydrogenation. At low temperatures (100-150°C), the selectivity of the process strongly depends on the nature of the modifier or second active metal (Pd). It is demonstrated that in the presence of 6% Ni-0.015% Pd/Al2O3 modified by HPC K4SiMo6W6O40, the conversion of PA at 100°C was 87% at a styrene: ethylbenzene ratio of 1: 1. The acidity of HPC is found to influence the side reactions of alkylation and condensation. Transmission electron microscopy demonstrates that Ni in modified HPC 6% Ni/Al2O3 is present in the form of the particles below 2 nm in size, and these particles of Ni become larger when affected by the reaction medium during PA hydrogenation.

  14. TiO{sub 2} nanotubes promoted PT-NI/C catalyst with low PT content as anode catalyst for direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Shen, L.; Jiang, Q.Z.; Gan, T.G.; Ma, Z.F. [Shanghai Jiao Tong Univ., Shanghai (China). Dept. of Chemical Engineering; Shen, M. [Oklahoma Univ., Norman, OK (United States). School of Chemical, Biological and Materials Engineering, Sarkeys Energy Center; Rodriguez Varela, F.J. [Cinvestav Unidad Saltillo, Coahuila (Mexico). Grupo de Recursos Naturales y Energeticos; Ocampo, A.L. [Univ. Nacional Autonoma, Mexico City (Mexico). Dept. de Quimica Analitica

    2010-07-15

    Although direct ethanol fuel cells (DEFC) have more energy density than direct methanol fuel cells (DMFC), their widespread use has been hampered by the fact that metallic platinum (Pt) catalysts are readily poisoned by strongly absorbed reaction intermediates such as CO{sub ads} at low operating temperatures. The addition of a second transition metal or a metal oxide component has been considered as a means to improve performance of DEFCs by forming a binary anode based on Pt. In this study, titanium oxide (TiO{sub 2}) nanotubes (TiO{sub 2}NTs) were added into a low-platinum content Pt-Ni/C catalyst to improve its catalytic activity for the ethanol oxidation reaction (EOR). The promotion effect of TiO{sub 2}NTs on Pt-Ni/C catalyst was examined. Cyclic voltametry (CV) and chronoamperometry showed that TiO{sub 2}NTs can improve the catalytic activity of the Pt-Ni/C catalyst considerably. Compared to a commercial Pt-Ru/C catalyst, the Pt-Ni-TiO{sub 2}NT/C catalyst has a larger electrochemical active surface (EAS) and has lower onset potential for the EOR. The elemental composition and electronic structure of the catalyst were characterized by X-ray photoelectron spectroscopy, energy dispersive X-ray spectrometry, inductively coupled plasma-optical emission spectrometry and X-ray diffraction. High resolution transmission electron microscopy was used to characterize the morphological properties of these catalysts. The study showed that onset oxidation potential can be lowered by the presence of TiO{sub 2}NTs because they retain more of the Pt metallic species and provide more hydroxides groups. 35 refs., 2 tabs., 10 figs.

  15. An investigation of the internal temperature dependence of Pd-Pt cluster beam deposition: A molecular dynamics study

    Science.gov (United States)

    Chen, Cha'o.-Kuang; Chang, Shing-Cheng

    2010-02-01

    We investigated the internal temperature dependence of the Pd 1- aPt a cluster beam deposition in the present study via the molecular dynamics simulations of soft-landing. By analysis of the velocity distribution and diffusion coefficient of the bimetallic cluster, Pd atoms with better mobility improved the diffusibility of Pt atoms. The radial composition distribution showed that a Pt-core/Pd-shell structure of the cluster formed at high internal temperatures through migrations of the Pd atoms from inner to surface shells. In the soft-landing process, the diffusing and epitaxial behaviors of the deposited clusters mainly depended on the internal temperature because the incident energy of the cluster was very small. By depositing clusters at high internal temperatures, we obtained a thin film of good epitaxial growth as the energetic cluster impact. Furthermore, nonepitaxial configurations such as scattered nonepitaxial atoms, misoriented particles, and grain boundaries of (1 1 1) planes were produced in the growth of the cluster-assembled film. As the size of the incident cluster increased, the internal temperature of the cluster needed for better interfacial diffusion and contact epitaxy on the substrate also rose.

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

    Science.gov (United States)

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

    2016-03-07

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

  17. Pt@Ag and Pd@Ag core/shell nanoparticles for catalytic degradation of Congo red in aqueous solution.

    Science.gov (United States)

    Salem, Mohamed A; Bakr, Eman A; El-Attar, Heba G

    2018-01-05

    Platinum/silver (Pt@Ag) and palladium/silver (Pd@Ag) core/shell NPs have been synthesized in two steps reaction using the citrate method. The progress of nanoparticle formation was followed by the UV/Vis spectroscopy. Transmission electron microscopy revealed spherical shaped core/shell nanoparticles with average particle diameter 32.17nm for Pt@Ag and 8.8nm for Pd@Ag. The core/shell NPs were further characterized by FT-IR and XRD. Reductive degradation of the Congo red dye was chosen to demonstrate the excellent catalytic activity of these core/shell nanostructures. The nanocatalysts act as electron mediators for the transfer of electrons from the reducing agent (NaBH4) to the dye molecules. Effect of reaction parameters such as nanocatalyst dose, dye and NaBH4 concentrations on the dye degradation was investigated. A comparison between the catalytic activities of both nanocatalysts was made to realize which of them the best in catalytic performance. Pd@Ag was the higher in catalytic activity over Pt@Ag. Such greater activity is originated from the smaller particle size and larger surface area. Pd@Ag nanocatalyst was catalytically stable through four subsequent reaction runs under the utilized reaction conditions. These findings can thus be considered as possible economical alternative for environmental safety against water pollution by dyes. Copyright © 2017. Published by Elsevier B.V.

  18. Estimate of the applicability of Pd-Pt nanoalloy for data recording by the method of phase change

    Science.gov (United States)

    Redel, L. V.; Gafner, Yu. Ya.; Gafner, S. L.; Zamulin, I. S.; Goloven'ko, Zh. V.

    2017-05-01

    Based on the computer simulation, the applicability of using individual nanoclusters of Pt, Pd, and particles of the Pd-Pt nanoalloy as unites of storage of data bits in nonvolatile memory devices, store capability of which is based on the principle of the phase change of the state of the carrier of information, has been estimated. To this end, the temperature and size limits of stability of different internal structures of nanoparticles in the course of the heating (to melting) and subsequent solidification (crystallization) with different rates of heat removal have been established. The results of the computer simulation of the nanoparticles of chemically pure platinum, palladium, and their alloy with different content of Pt atoms have been compared. It has been concluded that the best material for the memory cells the store capability of which is based on the occurrence of phase transitions is the nanoclusters of the Pd-Pt alloy with 10% platinum with a diameter D ≥ 3.5 nm.

  19. Interplay between out-of-plane anisotropic L1{sub 1}-type CoPt and in-plane anisotropic NiFe layers in CoPt/NiFe exchange springs

    Energy Technology Data Exchange (ETDEWEB)

    Saravanan, P. [Department of Physics, National Taiwan University, Taipei 106, Taiwan (China); Defence Metallurgical Research Laboratory, Hyderabad 500058 (India); Hsu, Jen-Hwa, E-mail: jhhsu@phys.ntu.edu.tw; Tsai, C. L. [Department of Physics, National Taiwan University, Taipei 106, Taiwan (China); Tsai, C. Y.; Lin, Y. H. [Graduate Institute of Materials Science and Engineering, National Taiwan University, Taipei 106, Taiwan (China); Kuo, C. Y.; Wu, J.-C. [Department of Physics, National Chang Hua University of Education, Chang Hua 50000, Taiwan (China); Lee, C.-M. [Graduate School of Materials Science, National Yunlin University of Science and Technology, Douliou 64002, Taiwan (China)

    2014-06-28

    Films of L1{sub 1}-type CoPt/NiFe exchange springs were grown with different NiFe (Permalloy) layer thickness (t{sub NiFe} = 0–10 nm). X-ray diffraction analysis reveals that the characteristic peak position of NiFe(111) is not affected by the CoPt-layer—confirming the absence of any inter-diffusion between the CoPt and NiFe layers. Magnetic studies indicate that the magnetization orientation of NiFe layer can be tuned through varying t{sub NiFe} and the perpendicular magnetic anisotropy of L1{sub 1}-type CoPt/NiFe films cannot sustain for t{sub NiFe} larger than 3.0 nm due to the existence of exchange interaction at the interface of L1{sub 1}-CoPt and NiFe layers. Magnetic force microscopy analysis on the as-grown samples shows the changes in morphology from maze-like domains with good contrast to hazy domains when t{sub NiFe} ≥ 3.0 nm. The three-dimensional micro-magnetic simulation results demonstrate that the magnetization orientation in NiFe layer is not uniform, which continuously increases from the interface to the top of NiFe layer. Furthermore, the tilt angle of the topmost NiFe layers can be changed over a very wide range from a small number to about 75° by varying t{sub NiFe} from 1 to 10 nm. It is worth noting that there is an abrupt change in the magnetization direction at the interface, for all the t{sub NiFe} investigated. The results of present study demonstrate that the tunable tilted exchange springs can be realized with L1{sub 1}-type CoPt/NiFe bilayers for future applications in three-axis magnetic sensors or advanced spintronic devices demanding inclined magnetic anisotropy.

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

    DEFF Research Database (Denmark)

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

    2007-01-01

    The glass-transition behavior of Pd40Cu30Ni10P20 bulk metallic glass was investigated by differential scanning calorimetry (DSC) and X-ray powder diffraction (XRD). The effect of pressure on the crystallization behavior of Pd40Cu30Ni10P20 bulk glass was studied by in situ high-pressure and high......-temperature X-ray powder diffraction using synchrotron radiation. Phase analyses show at least six crystalline phases in the crystallized sample, namely, monoclinic, tetragonal Cu3Pd-like, rhombohedral, fcc-Ni2Pd2P, fcc-(Ni, Pd) solid solution, and body-centered tetragonal (bct) Ni3P-like phases. The onset...... crystallization temperature increases with pressure having a slope of I I K/GPa in the range of 0 to 4 GPa. The results are attributed to the competing process between the thermodynamic potential barrier and the diffusion activation energy under pressure....

  1. NiO和(Pt/Co)多层膜的交换耦合作用及对其矫顽力的影响%Exchange Coupling between NiO and (Pt/Co) Multilayer and Control of Multilayer's Coercivity

    Institute of Scientific and Technical Information of China (English)

    刘帅; 俱海浪; 刘洋; 李宝河; 于广华

    2015-01-01

    研究了用磁控溅射法制备的(Pt/Co)多层膜和绝缘体反铁磁材料NiO之间的磁学和晶体学相互作用.室温下,当NiO覆盖在(Pt/Co)多层膜上面且NiO厚度大于25 nm时观察到了交换偏置,偏置场随NiO厚度的增加而增大.但总体上偏置场(HE)很小,对应NiO厚度为120nim时偏置场不到4000 A·m-1.NiO在(Pt/Co)多层膜下面时没有观察到交换偏置,但是对多层膜的矫顽力和垂直磁各向异性产生了很大影响.(Pt/Co)多层膜的矫顽力随NiO厚度的增加呈现非单调衰减趋势,当NiO厚度为1和3 nm时,矫顽力分别出现极小值和极大值,厚度超过3 nm的NiO使矫顽力单调下降,直至减小到接近零.(Pt/Co)多层膜的垂直磁各向异性随底层NiO厚度的增加逐渐变弱,最后垂直方向变为难轴.矫顽力和垂直磁各向异性的这种变化是由超薄NiO和(Pt/Co)多层膜之间可能存在的邻近效应,弱晶化NiO对(Pt/Co)多层膜(111)织构的影响以及NiO与(Pt/Co)多层膜之间的交换耦合共同作用造成的.

  2. Ni-Supported Pd Nanoparticles with Ca Promoter: A New Catalyst for Low-Temperature Ammonia Cracking

    Science.gov (United States)

    Polanski, Jaroslaw; Bartczak, Piotr; Ambrozkiewicz, Weronika; Sitko, Rafal; Siudyga, Tomasz; Mianowski, Andrzej; Szade, Jacek; Balin, Katarzyna; Lelątko, Józef

    2015-01-01

    In this paper we report a new nanometallic, self-activating catalyst, namely, Ni-supported Pd nanoparticles (PdNPs/Ni) for low temperature ammonia cracking, which was prepared using a novel approach involving the transfer of nanoparticles from the intermediate carrier, i.e. nano-spherical SiO2, to the target carrier technical grade Ni (t-Ni) or high purity Ni (p-Ni) grains. The method that was developed allows a uniform nanoparticle size distribution (4,4±0.8 nm) to be obtained. Unexpectedly, the t-Ni-supported Pd NPs, which seemed to have a surface Ca impurity, appeared to be more active than the Ca-free (p-Ni) system. A comparison of the novel PdNPs/Ni catalyst with these reported in the literature clearly indicates the much better hydrogen productivity of the new system, which seems to be a highly efficient, flexible and durable catalyst for gas-phase heterogeneous ammonia cracking in which the TOF reaches a value of 2615 mmolH2/gPd min (10,570 molNH3/molPd(NP) h) at 600°C under a flow of 12 dm3/h (t-Ni). PMID:26308929

  3. Electrochemical Dealloying of PdCu3 Nanoparticles to Achieve Pt-like Activity for the Hydrogen Evolution Reaction.

    Science.gov (United States)

    Jana, Rajkumar; Bhim, Anupam; Bothra, Pallavi; Pati, Swapan K; Peter, Sebastian C

    2016-10-20

    Manipulating the d-band center of the metal surface and hence optimizing the free energy of hydrogen adsorption (ΔGH ) close to the optimal adsorption energy (ΔGH =0) for hydrogen evolution reaction (HER), is an efficient strategy to enhance the activity for HER. Herein, we report a oleylamine-mediated (acting as the solvent, stabilizer, and reducing agent) strategy to synthesize intermetallic PdCu3 nanoparticles (NPs) without using any external reducing agent. Upon electrochemical cycling, PdCu3 transforms into Pd-rich PdCu (ΔGH =0.05 eV), exhibiting remarkably enhanced activity (with a current density of 25 mA cm(-2) at ∼69 mV overpotential) as an alternative to Pt for HER. The first-principle calculation suggests that formation of low coordination number Pd active sites alters the d-band center and hence optimal adsorption of hydrogen, leading to enhanced activity. This finding may provide guidelines towards the design and development of Pt-free highly active and robust electrocatalysts. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The adsorption of 1,3-butadiene on Pd/Ni multilayers: The interplay between spin polarization and chemisorption strength

    Science.gov (United States)

    Gómez, Guillermina; Belelli, Patricia G.; Cabeza, Gabriela F.; Castellani, Norberto J.

    2010-12-01

    The adsorption of 1,3-butadiene (BD) on the Pd/Ni(1 1 1) multilayers has been studied using the VASP method in the framework of the density functional theory (DFT). The adsorption on two different configurations of the Pd n/Ni m(1 1 1) systems were considered. The most stable adsorption sites are dependent on the substrate composition and on the inclusion or not of spin polarization. On Pd 1Ni 3(1 1 1) surface, di-π-cis and 1,2,3,4-tetra-σ adsorption structures are the most stable for non-spin polarized (NSP) and spin polarized (SP) levels of calculation, respectively. Conversely, on Pd 3Ni 1(1 1 1) surface, the 1,2,3,4-tetra-σ adsorption structure is the most stable for both NSP and SP levels, respectively. The magnetization of the Pd atoms strongly modifies the adsorption energy of BD and its most stable adsorption mode. On the other hand, as a consequence of BD adsorption, the Pd magnetization decreases. The smaller adsorption energies of BD and 1-butene on the Pd 1Ni 3(1 1 1) surface than on Pd(1 1 1) can be associated to the strained Pd overlayer deposited on Ni(1 1 1).

  5. Electrooxidation of ethylene glycol and glycerol on Pd-(Ni-Zn)/C anodes in direct alcohol fuel cells.

    Science.gov (United States)

    Marchionni, Andrea; Bevilacqua, Manuela; Bianchini, Claudio; Chen, Yan-Xin; Filippi, Jonathan; Fornasiero, Paolo; Lavacchi, Alessandro; Miller, Hamish; Wang, Lianqin; Vizza, Francesco

    2013-03-01

    The electrooxidation of ethylene glycol (EG) and glycerol (G) has been studied: in alkaline media, in passive as well as active direct ethylene glycol fuel cells (DEGFCs), and in direct glycerol fuel cells (DGFCs) containing Pd-(Ni-Zn)/C as an anode electrocatalyst, that is, Pd nanoparticles supported on a Ni-Zn phase. For comparison, an anode electrocatalyst containing Pd nanoparticles (Pd/C) has been also investigated. The oxidation of EG and G has primarily been investigated in half cells. The results obtained have highlighted the excellent electrocatalytic activity of Pd-(Ni-Zn)/C in terms of peak current density, which is as high as 3300 A g(Pd)(-1) for EG and 2150 A g(Pd)(-1) for G. Membrane-electrode assemblies (MEA) have been fabricated using Pd-(Ni-Zn)/C anodes, proprietary Fe-Co/C cathodes, and Tokuyama A-201 anion-exchange membranes. The MEA performance has been evaluated in either passive or active cells fed with aqueous solutions of 5 wt % EG and 5 wt % G. In view of the peak-power densities obtained in the temperature range from 20 to 80 °C, at Pd loadings as low as 1 mg cm(-2) at the anode, these results show that Pd-(Ni-Zn)/C can be classified amongst the best performing electrocatalysts ever reported for EG and G oxidation.

  6. Pd/RGO modified carbon felt cathode for electro-Fenton removing of EDTA-Ni.

    Science.gov (United States)

    Zhang, Zhen; Zhang, Junya; Ye, Xiaokun; Hu, Yongyou; Chen, Yuancai

    Ethylenediaminetetraacetic acid (EDTA) forms stable complexes with toxic metals such as nickel due to its strong chelation. The electro-Fenton (EF) process using a cathode made from palladium (Pd), reduced graphene oxide (RGO) and carbon felt, fed with air, exhibited high activities and stability for the removal of 10 mg L(-1) EDTA-Ni solution. Pd/RGO catalyst was prepared by one-pot synthesis; the scanning electron microscopy and X-ray diffraction analysis indicated nanoparticles and RGO were well distributed on carbon felt, forming three dimensional architecture with both large macropores and a mesoporous structure. The cyclic voltammetric results showed that the presence of RGO in Pd/RGO/carbon felt significantly increased the current response of two-electron reduction of O2 (0.45 V). The key factors influencing the removal efficiency of EDTA-Ni, such as pH, current and Fe(2+) concentration, were investigated. Under the optimum conditions, the removal efficiency of EDTA-Ni reached 83.8% after 100 min EF treatment. Mechanism analysis indicated that the introduction of RGO in Pd/RGO/carbon felt significantly enhanced the electrocatalytic activities by inducing •OH in the EF process; direct H2O2 oxidation still accounted for a large amount of EDTA-Ni removal efficiency.

  7. Atomic-scale insights into structural and thermodynamic stability of Pd-Ni bimetallic nanoparticles.

    Science.gov (United States)

    Huang, Rao; Wen, Yu-Hua; Zhu, Zi-Zhong; Sun, Shi-Gang

    2016-04-14

    Atomic-scale understanding of structures and thermodynamic stability of core-shell nanoparticles is important for both their synthesis and application. In this study, we systematically investigated the structural stability and thermodynamic evolution of core-shell structured Pd-Ni nanoparticles by molecular dynamics simulations. It has been revealed that dislocations and stacking faults occur in the shell and their amounts are strongly dependent on the core/shell ratio. The presence of these defects lowers the structural and thermal stability of these nanoparticles, resulting in even lower melting points than both Pd and Ni monometallic nanoparticles. Furthermore, different melting behaviors have been disclosed in Pd-core/Ni-shell and Ni-core/Pd-shell nanoparticles. These diverse behaviors cause different relationships between the melting temperature and the amount of stacking faults. Our results display direct evidence for the tunable stability of bimetallic nanoparticles. This study provides a fundamental perspective on core-shell structured nanoparticles and has important implications for further tailoring their structural and thermodynamic stability by core/shell ratio or composition controlling.

  8. First-principles investigations of the structural, electronic, and magnetic properties of Pt{sub 13−n}Ni{sub n} clusters

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Fangfang; Liu, Chuan [Division of Molecule and Materials Simulation, State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Wang, Peng [Research Institute of Petroleum Processing, SINOPEC, Beijing 100083 (China); Huang, Shiping, E-mail: huangsp@mail.buct.edu.cn [Division of Molecule and Materials Simulation, State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Tian, Huiping [Research Institute of Petroleum Processing, SINOPEC, Beijing 100083 (China)

    2013-11-15

    Highlights: •Magnetic properties of Pt{sub 13−n}Ni{sub n} clusters are performed by DFT calculations. •Ni 3d orbitals make mainly contribution to the magnetism of Pt{sub 13−n}Ni{sub n} clusters. •Magnetic moments of Pt{sub 13−n}Ni{sub n} clusters are as a function of Ni concentration. •Binding energies of Pt{sub 13−n}Ni{sub n} clusters decrease with increasing Ni concentration. -- Abstract: First-principles method based on the density functional theory has been utilized to calculate the structural, electronic and magnetic properties of Pt{sub 13−n}Ni{sub n} (n = 0–13) clusters. For Pt{sub 13−n}Ni{sub n} clusters, Ni atoms are mainly found in the cluster core and Pt atoms are segregated to the cluster surface. The calculated binding energies of Pt{sub 13−n}Ni{sub n} clusters decrease with increasing Ni concentration. Through the bader charge and difference charge density analyses, it is observed that the small charge transfer is from Ni to Pt. In the total and partial density of states of Pt{sub 13−n}Ni{sub n} clusters, Pt 5d and Ni 3d orbitals make the main contribution to the electronic states and play an important role in determining the magnetism of Pt{sub 13−n}Ni{sub n} clusters. From n ⩾ 2, the calculated magnetic moments of Pt{sub 13−n}Ni{sub n} clusters increase to the maximum (8.34 μ{sub B}) in Pt{sub 2}Ni{sub 11} cluster as a function of Ni concentration and then decrease slightly. The variation in the magnetic behavior of Pt{sub 13−n}Ni{sub n} clusters can be attributed to the exchange splitting of the energy bands near the Fermi level.

  9. Anticancer Potencies of Pt(II) - and Pd(II)-linked M2L4 Coordination Capsules with Improved Selectivity.

    Science.gov (United States)

    Ahmedova, Anife; Momekova, Denitsa; Yamashina, Masahiro; Shestakova, Pavletta; Momekov, Georgi; Akita, Munetaka; Yoshizawa, Michito

    2016-02-18

    Pt(II) - and Pd(II)-linked M2 L4 coordination capsules, providing a confined cavity encircled by polyaromatic frameworks, exhibit anticancer activities superior to cisplatin against two types of leukemic cells (HL-60 and SKW-3) and pronounced toxicity against cisplatin-resistant cells (HL-60/CDDP). Notably, the cytotoxic selectivities of the Pt(II) and Pd(II) capsules toward cancerous cells are up to 5.3-fold higher than that of cisplatin, as estimated through the non-malignant/malignant-cells toxicity ratio employing normal kidney cells (HEK-293). In addition, the anticancer activity of the coordination capsules can be easily altered upon encapsulation of organic guest molecules.

  10. Mass Spectrometric Studies on Metai-hexafluorobenzene Anionic Comolexes(M=Ag,Au,Pd,Pt,Pb and Bi)

    Institute of Scientific and Technical Information of China (English)

    SUN Zhang; SUN Shu-tao; LIU Hong-tao; ZHU Qi-he; GAO Zhen; TANG Zi-chao

    2009-01-01

    The anionic products from the reactions between metal(M=Ag,Au,Pd,Pt,Pb and Bi) vapour produced by laser ablation and hexafluorobenzene seeded in carrier gas(Ar) were studied by means of a homemade reflectron time-of-flight mass spectrometry(RTOF-MS).Experimental results show that the dominant products were [MmC6F6]-complexes for the reactions of Ag,Au,Pd and Pt with C6F6,while the dominant products were [MmC6Fs]- complexes for the reactions of Pb and Bi with C6F6.The formation mechanisms of the products,including the adsorption of metal cluster anions on hexafluorobenzene and the C-F cleavage induced by metal cluster anions,were discussed.

  11. Nanocrystalline Pd:NiFe2O4 thin films: A selective ethanol gas sensor

    Science.gov (United States)

    Rao, Pratibha; Godbole, R. V.; Bhagwat, Sunita

    2016-10-01

    In this work, Pd:NiFe2O4 thin films were investigated for the detection of reducing gases. These films were fabricated using spray pyrolysis technique and characterized using X-ray diffraction (XRD) to confirm the crystal structure. The surface morphology was studied using scanning electron microscopy (SEM). Magnetization measurements were carried out using SQUID VSM, which shows ferrimagnetic behavior of the samples. These thin film sensors were tested against methanol, ethanol, hydrogen sulfide and liquid petroleum gas, where they were found to be more selective to ethanol. The fabricated thin film sensors exhibited linear response signal for all the gases with concentrations up to 5 w/o Pd. Reduction in optimum operating temperature and enhancement in response was also observed. Pd:NiFe2O4 thin films exhibited faster response and recovery characteristic. These sensors have potential for industrial applications because of their long-term stability, low power requirement and low production cost.

  12. Ultra-small Tetrametallic Pt-Pd-Rh-Ag Nanoframes with Tunable Behavior for Direct Formic Acid/Methanol Oxidation.

    Science.gov (United States)

    Saleem, Faisal; Ni, Bing; Yong, Yang; Gu, Lin; Wang, Xun

    2016-10-01

    Reversible tuning of ultra-small multimetallic Pt-Pd-Rh-Ag nanoframes is achieved. These nanoframes showed tunable and reversible modes for the oxidation of small organic molecules by simply inducing segregation with adsorbates, such as SO4(2-) and OH(-) . This is the first example of reversible segregation under electrocatalytic conditions in atomic-sized electrocatalysts. These nanoframes also showed a controllable activity and good stability for the oxidation of small organic molecules.

  13. Ultrasensitive detection of superoxide anion released from living cells using a porous Pt-Pd decorated enzymatic sensor.

    Science.gov (United States)

    Zhu, Xiang; Liu, Tingting; Zhao, Hongli; Shi, Libo; Li, Xiaoqing; Lan, Minbo

    2016-05-15

    Considering the critical roles of superoxide anion (O2(∙-)) in pathological conditions, it is of great urgency to establish a reliable and durable approach for real-time determination of O2(∙-). In this study, we propose a porous Pt-Pd decorated superoxide dismutase (SOD) sensor for qualitative and quantitative detection O2(∙-). The developed biosensor exhibits a fast, selective and linear amperometric response upon O2(∙-) in the concentration scope of 16 to 1,536 μM (R(2)=0.9941), with a detection limit of 0.13 μM (S/N=3) and a low Michaelis-Menten constant of 1.37 μM which indicating a high enzymatic activity and affinity to O2(∙-). Inspiringly, the proposed sensor possesses an ultrahigh sensitivity of 1270 μA mM(-1)cm(-2). In addition, SOD/porous Pt-Pd sensor exhibits excellent anti-interference property, reproducibility and long-term storage stability. Beyond our expectation, the trace level of O2(∙-) released from living cells has also been successfully captured. These satisfactory results are mainly ascribed to (1) the porous interface with larger surface area and more active sites to provide a biocompatible environment for SOD (2) the specific biocatalysis of SOD towards O2(∙-) and (3) porous Pt-Pd nanomaterials fastening the electron transfer. The superior electrochemical performance makes SOD/porous Pt-Pd sensor a promising candidate for monitoring the dynamic changes of O2(∙-)in vivo.

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

    Science.gov (United States)

    Huang, Liang; Han, Yujie; Dong, Shaojun

    2016-07-05

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

  15. HZSM-5 CATALYST FOR CRACKING PALM OIL TO BIODIESEL: A COMPARATIVE STUDY WITH AND WITHOUT PT AND PD IMPREGNATION

    OpenAIRE

    Agus Budianto; Danawati Hari Prajitno; Achmad Roesyadi; Kusno Budhikarjono

    2014-01-01

    The Needs of healthy environment and green energy poses a great demand for alternative energy. Biofuel is one of the alternative energy products that are environmentally friendly. Biofuel can be made from plant oils, especially palm oil. Cracking of palm oil into biofuel is constrained by the availability of catalysts. Moreover the available catalyst still gives a low yield. This research aims to study the effect of Pt and Pd impregnation into HZSM-5 catalyst on the catalytic properties. Anot...

  16. Tomographic heating holder for in situ TEM: study of Pt/C and PtPd/Al2O3 catalysts as a function of temperature.

    Science.gov (United States)

    Gontard, Lionel C; Dunin-Borkowski, Rafal E; Fernández, Asunción; Ozkaya, Dogan; Kasama, Takeshi

    2014-06-01

    A tomographic heating holder for transmission electron microscopy that can be used to study supported catalysts at temperatures of up to ~1,500°C is described. The specimen is placed in direct thermal contact with a tungsten filament that is oriented perpendicular to the axis of the holder without using a support film, allowing tomographic image acquisition at high specimen tilt angles with minimum optical shadowing. We use the holder to illustrate the evolution of the active phases of Pt nanoparticles on carbon black and PtPd nanoparticles on γ-alumina with temperature. Particle size distributions and changes in active surface area are quantified from tilt series of images acquired after subjecting the specimens to increasing temperatures. The porosity of the alumina support and the sintering mechanisms of the catalysts are shown to depend on distance from the heating filament.

  17. Oxygen Storage Capacity of Pt-, Pd-, Rh/CeO2-Based Oxide Catalyst

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    CZO (CeO2-ZrO2) and CZYO (CeO2-ZrO2-Y2O3) series of mixed oxides were prepared by coprecipitaion, and a part of these oxides were loaded with precious metals (PM). XRD, BET, and oxygen storage capacity (OSC) investigations were performed on samples aged at 750, 900, and 1050 ℃. It was observed that BET surface area and OSC showed a marked decrease in CeO2 aged at high temperature, and the crystallite size showed an obvious increase. The CZO samples consist of cubic- and tetragonal crystal phases, and their crystallite size increase rapidly when aged at high temperature. The CZYO samples consist of single crystal phase when the content of Y exceeds 0.15 mol, and their crystallite size increases slowly during high-temperature aging. It is concluded that additive Y can stabilize the performance of CZYO oxides. In the aged CZO and CZYO mixed-oxide systems, addition of a small amount of precious metals (Pt, Pd, Rh) increased the rate of reduction and led to an obvious improvement in OSC. OSC of CZO and CZYO with precious metals are related to their composition and the type of precious metal.

  18. Shear bond strength of a hot pressed Au-Pd-Pt alloy-porcelain dental composite.

    Science.gov (United States)

    Henriques, B; Soares, D; Silva, F S

    2011-11-01

    The purpose of this study was to evaluate the effect of hot pressing on the shear bond strength of a Au-Pt-Pd alloy-porcelain composite. Several metal-porcelain composites specimens were produced by two different routes: conventional porcelain fused to metal (PFM) and hot pressing. In the latter case, porcelain was hot pressed onto a polished surface (PPPS) as well as a roughened one (PPRS). Bond strength of all metal-porcelain composites were assessed by the means of a shear test performed in a universal test machine (crosshead speed: 0.5 mm/min) until fracture. Interfaces of fractured specimens as well as undestroyed interface specimens were examined with optical microscope, stereomicroscope, Scanning Electron Microscope (SEM) and Energy Dispersive X-Ray Spectroscopy (EDS). The data were analyzed using one-way ANOVA followed by Tuckey's test (p0.05). This study shows that it is possible to significantly improve metal-porcelain bond strength by applying an overpressure during porcelain firing. Copyright © 2011 Elsevier Ltd. All rights reserved.

  19. HZSM-5 CATALYST FOR CRACKING PALM OIL TO BIODIESEL: A COMPARATIVE STUDY WITH AND WITHOUT PT AND PD IMPREGNATION

    Directory of Open Access Journals (Sweden)

    Agus Budianto

    2014-05-01

    Full Text Available The Needs of healthy environment and green energy poses a great demand for alternative energy. Biofuel is one of the alternative energy products that are environmentally friendly. Biofuel can be made from plant oils, especially palm oil. Cracking of palm oil into biofuel is constrained by the availability of catalysts. Moreover the available catalyst still gives a low yield. This research aims to study the effect of Pt and Pd impregnation into HZSM-5 catalyst on the catalytic properties. Another aim is to obtain the operating conditions of the catalytic cracking process of palm oil into biofuel which gives the highest yield and selectivity, especially for biodiesel and biogasoline fractions. Catalytic cracking process was carried out in a micro fixed bed reactor with diameter of 1 cm and length of 16 cm. The reactor was filled with a catalyst. The results of the study successfully prove that Pt and Pd impregnated into HZSM-5 catalyst can increase the yield and selectivity of biodiesel. Pd and Pt are highly recommended to increase the yield and selectivity of biodiesel.

  20. Elastic and electronic properties of antiperovskite-type Pd- and Pt-based ternary carbides from first-principles calculations

    Energy Technology Data Exchange (ETDEWEB)

    Bannikov, V.V.; Ivanovskii, A.L., E-mail: ivanovskii@ihim.uran.ru

    2013-11-15

    Highlights: • 23 Pd- and Pt-based antiperovskite-type ternary carbides are probed from first principles. • Structural, elastic, electronic properties and inter-atomic bonding are evaluated. • A rich variety of mechanical and electronic properties was predicted. -- Abstract: By means of first-principles calculations, the structural, elastic, and electronic properties of a broad series of proposed Pd- and Pt-based antiperovskite-type ternary carbides AC(Pd,Pt){sub 3}, where A are Zn, Ca, Al, Ga, In, Ge, Hg, Sn, Cd, Pb, Ag, Sc, Ti, Y, Nb, Mo, and Ta, have been studied, and their stability, elastic constants, bulk, shear, and Young’s moduli, compressibility, Pugh’s indicator, Poisson’s ratio, indexes of elastic anisotropy, as well as electronic properties have been evaluated. We found that these materials should demonstrate a rich variety of mechanical and electronic properties depending on the type of A sublattices, which can include (unlike the majority of known 3d-metal-based antiperovskites) both sp elements and d atoms. We believe that the presented results will be useful for future synthesis of these phases, as well as for expanding our knowledge of this interesting group of antiperovskite-type materials.

  1. Quantitative Analysis of the Reduction Kinetics Responsible for the One-Pot Synthesis of Pd-Pt Bimetallic Nanocrystals with Different Structures.

    Science.gov (United States)

    Zhou, Ming; Wang, Helan; Vara, Madeline; Hood, Zachary D; Luo, Ming; Yang, Tung-Han; Bao, Shixiong; Chi, Miaofang; Xiao, Peng; Zhang, Yunhuai; Xia, Younan

    2016-09-21

    We report a quantitative understanding of the reduction kinetics responsible for the formation of Pd-Pt bimetallic nanocrystals with two distinctive structures. The syntheses involve the use of KBr to manipulate the reaction kinetics by influencing the redox potentials of metal precursor ions via ligand exchange. In the absence of KBr, the ratio between the initial reduction rates of PdCl4(2-) and PtCl4(2-) was about 10.0, leading to the formation of Pd@Pt octahedra with a core-shell structure. In the presence of 63 mM KBr, the products became Pd-Pt alloy nanocrystals. In this case, the ratio between the initial reduction rates of the two precursors dropped to 2.4 because of ligand exchange and, thus, the formation of PdBr4(2-) and PtBr4(2-). The alloy nanocrystals took a cubic shape owing to the selective capping effect of Br(-) ions toward the {100} facets. Relative to the alloy nanocubes, the Pd@Pt core-shell octahedra showed substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). Specifically, the specific (1.51 mA cm(-2)) and mass (1.05 A mg(-1) Pt) activities of the core-shell octahedra were enhanced by about four- and three-fold relative to the alloy nanocubes (0.39 mA cm(-2) and 0.34 A mg(-1) Pt, respectively). Even after 20000 cycles of accelerated durability test, the core-shell octahedra still exhibited a mass activity of 0.68 A mg(-1) Pt, twice that of a pristine commercial Pt/C catalyst.

  2. Enhanced electrocatalytic performance of processed, ultrathin, supported Pd-Pt core-shell nanowire catalysts for the oxygen reduction reaction.

    Science.gov (United States)

    Koenigsmann, Christopher; Santulli, Alexander C; Gong, Kuanping; Vukmirovic, Miomir B; Zhou, Wei-ping; Sutter, Eli; Wong, Stanislaus S; Adzic, Radoslav R

    2011-06-29

    We report on the synthesis, characterization, and electrochemical performance of novel, ultrathin Pt monolayer shell-Pd nanowire core catalysts. Initially, ultrathin Pd nanowires with diameters of 2.0 ± 0.5 nm were generated, and a method has been developed to achieve highly uniform distributions of these catalysts onto the Vulcan XC-72 carbon support. As-prepared wires are activated by the use of two distinctive treatment protocols followed by selective CO adsorption in order to selectively remove undesirable organic residues. Subsequently, the desired nanowire core-Pt monolayer shell motif was reliably achieved by Cu underpotential deposition followed by galvanic displacement of the Cu adatoms. The surface area and mass activity of the acid and ozone-treated nanowires were assessed, and the ozone-treated nanowires were found to maintain outstanding area and mass specific activities of 0.77 mA/cm(2) and 1.83 A/mg(Pt), respectively, which were significantly enhanced as compared with conventional commercial Pt nanoparticles, core-shell nanoparticles, and acid-treated nanowires. The ozone-treated nanowires also maintained excellent electrochemical durability under accelerated half-cell testing, and it was found that the area-specific activity increased by ~1.5 fold after a simulated catalyst lifetime.

  3. Hydrogenation of tetralin in the presence of dibenzothiophene and quinoline on Pt-Pd/SiO{sub 2}-Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, O.Y.; Yu, Y.; Jentys, A.; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center

    2012-07-01

    Three Pt-Pd catalysts with 0.3 and 0.5 wt.% of Pt and Pd, respectively, were supported on amorphous silica alumina with Al{sub 2}O{sub 3}:SiO{sub 2} wt.% ratios of 20:80, 30:70 and 55:45. The materials were characterized by physisorption of N{sub 2}, TEM, X-ray absorption spectroscopy and adsorption of pyridine and CO followed by IR spectroscopy. The EXAFS fitting and IR characterization showed that bimodal distributions of monometallic Pd and bimetallic Pt-Pd particles. The bimetallic particles in all catalysts have a Pt-rich core and a Pd-rich shell. However, the degree of alloying and proportion of exposed Pt increases with increasing concentration of Lewis acid sites (LAS) in the support, probably because the LAS are good anchoring sites for Pt species. The activity of the catalysts for the hydrogenation of tetralin in the presence of DBT and quinoline, and the corresponding selectivity to cis-decalin increase with the proportion of exposed Pt. Therefore, in the presence of DBT and quinoline the morphology of bimetallic clusters is the parameter determining its hydrogenation performance. (orig.)

  4. Catalytic hydrogenation of CO2 over Pt- and Ni-doped graphene: A comparative DFT study.

    Science.gov (United States)

    Esrafili, Mehdi D; Sharifi, Fahimeh; Dinparast, Leila

    2017-08-28

    Today, the global greenhouse effect of carbon dioxide (CO2) is a serious environmental problem. Therefore, developing efficient methods for CO2 capturing and conversion to valuable chemicals is a great challenge. The aim of the present study is to investigate the catalytic activity of Pt- or Ni-doped graphene for the hydrogenation of CO2 by a hydrogen molecule. To gain a deeper insight into the catalytic mechanism of this reaction, the reliable density functional theory calculations are performed. The adsorption energies, geometric parameters, reaction barriers, and thermodynamic properties are calculated using the M06-2X density functional. Two reaction mechanisms are proposed for the hydrogenation of CO2. In the bimolecular mechanism, the reaction proceeds in two steps, initiating by the co-adsorption of CO2 and H2 molecules over the surface, followed by the formation of a OCOH intermediate by the transfer of H atom of H2 toward O atom of CO2. In the next step, formic acid is produced as a favorable product with the formation of CH bond. In our proposed termolecular mechanism, however, H2 molecule is directly activated by the two pre-adsorbed CO2 molecules. The predicted activation energy for the formation of the OCOH intermediate in the bimolecular mechanism is 20.8 and 47.9kcalmol(-1) over Pt- and Ni-doped graphene, respectively. On the contrary, the formation of the first formic acid in the termolecular mechanism is found as the rate-determining step over these surfaces, with an activation energy of 28.8 and 45.5kcal/mol. Our findings demonstrate that compared to the Ni-doped graphene, the Pt-doped surface has a relatively higher catalytic activity towards the CO2 reduction. These theoretical results could be useful in practical applications for removal and transformation of CO2 to value-added chemical products. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Correlation between bias fields and magnetoresistance in CoPt biased NiFe/Ta/NiFe heterosystems

    Science.gov (United States)

    Wang, Yi; He, Xi; Mukherjee, Tathagata; Sahoo, Sarbeswar; Fitzsimmons, Michael; Binek, Christian

    2011-03-01

    Exchange coupled magnetic hard layer/soft layer (SL) thin films show SL biasing in close analogy to exchange bias systems with antiferromagnetic pinning. Here we study CoPt(35nm)/NiFe(450nm)/Ta(d)/NiFe(450nm) heterostructures with 0.7 < d <5nm. We use alternating gradient force magnetometry to measure the overall magnetization reversal and minor loop behavior. Magnetoresistance (MR) is measured by four-point methodology and modeled using magnetization data thus confirming the assumptions of uniform rotation of the top layer and exchange spring behavior of the pinned NiFe layer. In addition, Polarized Neutron Reflectometry (PNR) provides an independent data set for magnetization depth profiles. We compare and contrast results from our magnetometry and MR technique with PNR results. The objective of this comparison is to show that single-component magnetometry in concert with MR and modeling reveals the full vector and depth profile information of the distinct magnetization reversal mechanisms. Financial support by NSF through Career, MRSEC, DOE-OBES

  6. Numerical Simulation of Pt Overlayers on Ni(111) and Co(0001)

    Science.gov (United States)

    Légaré, P.; Cabeza, G. F.; Castellani, N. J.

    The growth of pseudomorphic Pt layers (from one to four) on Ni(111) and Co(0001) has been investigated by the ECT-BFS method. The behaviors on the two substrates are very similar. The growth of the first layer appears to be highly favorable as the energy of the system is negative. Higher coverages could be stabilized with huge relaxations perpendicularly to the surface. The evolution of the plane-by-plane energies (separated in stress and chemical contributions) and relaxations during the growth is presented and discussed. The always-stabilizing chemical interaction at the interface makes it likely that interdiffusion of metals could be a competing mechanism.

  7. Pd-Cu-Pt/γ-Al2O3催化剂还原水中的硝酸盐%Catalytic Reduction of Nitrate in Water over Pd-Cu-Pt/γ-Al2O3 Catalyst

    Institute of Scientific and Technical Information of China (English)

    高建峰; 徐春彦; 王久芬; 庄源益

    2004-01-01

    以自制的高纯γ-Al2O3为载体,用双浸渍法制备了不同Pd/Cu比的Pd-Cu/γ-Al2O3催化剂,在间歇式反应器中直接处理含硝酸盐废水. 结果表明,利用不同Pd/Cu比的Pd-Cu/γ-Al2O3催化剂及Pd-Cu-Pt/γ-Al2O3催化剂,同时用甲酸为pH调节剂,在适合的条件下,于40 min内就能达到脱除硝酸盐的目的,氮脱除率可达95%. 这有可能发展成为一项有效和实用的水处理技术,特别是在以地下水作为饮用水源的农村地区.

  8. Titania Supported Pt and Pt/Pd Nano-particle Catalysts for the Oxidation of Sulfur Dioxide

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Johannessen, Tue; Eriksen, Kim Michael

    2006-01-01

    Several types of titania (anatase) were used as supports for pure platinum and Pt–Pd bimetallic alloy catalysts. The preparation methods, normal wet impregnation technique and flame aerosol synthesis, obtained metal loadings of 2% by weight. The prepared catalysts were tested for SO2 oxidation...... activity at atmospheric pressure in the temperature range 250–600 °C. The SO2 to SO3 conversion efficiency of the Pt–Pd alloy was significantly higher than that of the individual metals. The effects of the preparation method and the titania type used on the properties and activity of the resulting catalyst...

  9. Local symmetry lowering in the cubic intermetallics YbPdBi and YbNiSb

    Energy Technology Data Exchange (ETDEWEB)

    LeBras, G.; Bonville, P.; Hodges, J.A.; Hammann, J.; Besnus, M.J.; Schmerber, G.; Dhar, S.K.; Aliev, F.G.; Andre, G. [DRECAM/SPEC, CE Saclay, Gif-sur-Yvette (France)

    1995-07-10

    A microscopic investigation of the cubic ternary alloys YbPdBi and YbNiSb, using {sup 170}Yb Mossbauer spectroscopy, reveals that the point symmetry at the site of the Yb{sup 3+} is far from cubic in both compounds. An analysis of the thermal variation of the quadrupolar 4f moment shows that the energy of the first crystal electric field transition is close to 20 K in YbPdBi and to 10 K in YbNiSb. Specific heat measurements are also presented in YbPdBi, and magnetic ordering is detected below 1 K in YbPdBi, with saturated Yb{sup 3+} moments of 1.25 {mu}{sub B}, and below 0.85 K in YbNiSb, with saturated moments of 1 {mu}{sub B}. A tentative explanation of the Yb site symmetry breaking is made in terms of a Jahn-Teller distortion within the {gamma}{sub 8} cubic quartet. (author)

  10. Nano-assemblies consisting of Pd/Pt nanodendrites and poly (diallyldimethylammonium chloride)-coated reduced graphene oxide on glassy carbon electrode for hydrogen peroxide sensors

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yanyan; Zhang, Cong; Zhang, Di; Ma, Min; Wang, Weizhen; Chen, Qiang, E-mail: qiangchen@nankai.edu.cn

    2016-01-01

    Non-enzymatic hydrogen peroxide (H{sub 2}O{sub 2}) sensors were fabricated on the basis of glassy carbon (GC) electrode modified with palladium (Pd) core-platinum (Pt) nanodendrites (Pt-NDs) and poly (diallyldimethylammonium chloride) (PDDA)-coated reduced graphene oxide (rGO). A facile wet-chemical method was developed for preparing Pd core-Pt nanodendrites. In this approach, the growth of Pt NDs was directed by Pd nanocrystal which could be regarded as seed. The PDDA-coated rGO could form uniform film on the surface of GC electrode, which provided a support for Pd core- Pt NDs adsorption by self-assembly. The morphologies of the nanocomposites were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction (spectrum). Electrocatalytic ability of the nanocomposites was evaluated by cyclic voltammetry and chronoamperometric methods. The sensor fabricated by Pd core-Pt NDs/PDDA-rGO/GCE exhibited high sensitivity (672.753 μA mM{sup −1} cm{sup −2}), low detection limit (0.027 μM), wider linear range (0.005–0.5 mM) and rapid response time (within 5 s). Besides, it also exhibited superior reproducibility, excellent anti-interference performance and long-term stability. The present work could afford a viable method and efficient platform for fabricating all kinds of amperometric sensors and biosensors. - Highlights: • A facial wet-chemical method was developed for preparing Pd core-Pt nanodendrites. • The morphologies of graphene and Pd core-Pt nanodendrites were characterized. • A novel H{sub 2}O{sub 2} sensor was fabricated by nano-assembly. • The performance of H{sub 2}O{sub 2} sensor was evaluated by cyclic voltammetry and chronoamperometric methods.

  11. Control of magnetic anisotropy field of (001) oriented L1{sub 0}-Fe(Pd{sub x}Pt{sub 1-x}) films for MRAM application

    Energy Technology Data Exchange (ETDEWEB)

    Yoshimura, Satoru; Omiya, Shogo; Egawa, Genta; Saito, Hitoshi [Center for Geo-environmental Science, Faculty of Engineering and Resource Science, Akita University, Tegatagakuen-machi 1-1, Akita, 010-8502 (Japan); Bai Jianmin, E-mail: syoshi@gipc.akita-u.ac.jp [Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, TianShui Road, S 222, LanZhou, GanSu, 730000 (China)

    2011-01-01

    L1{sub 0}-Fe(Pd,Pt) films which are expected to have tunable perpendicular magnetic anisotropy and lower ordering temperature compared with the L1{sub 0}-FePt films were fabricated and investigated in order to realize high-performance Magnetic Random Access Memory (MRAM) with spin-transfer magnetization switching method and Magnetic Domain-Wall Racetrack Memory with current-driven domain wall motion. The main results are as follows: (1) The long-range chemical order degree S for the L1{sub 0}-Fe(Pd,Pt) films with the optimized thermal treatment temperature fabricated on MgO(001) substrate was about 0.8. (2) The perpendicular coercive force and magnetic anisotropy field for the L1{sub 0}-FePd film with the thermal treatment temperature of 600 {sup 0}C were 300 Oe and 14 kOe respectively, whereas the L1{sub 0}-FePt film with the thermal treatment temperature of 800 {sup 0}C were 2000 Oe and 102 kOe, respectively. (3) The optimized ordering temperature to obtain L1{sub 0} single phase decreased continuously from 800{sup 0}C to 600{sup 0}C with the increasing Pd content for the Fe(Pd,Pt) films. (4) The perpendicular magnetic anisotropy field for the L1{sub 0}-Fe(Pd,Pt) films decreased continuously from 102 kOe to 14 kOe with the increasing Pd content. It is found that the Fe(Pd,Pd) films which have tunable perpendicular magnetic anisotropy field is one of suitable ferromagnetic material for high-performance magnetic recording devices.

  12. Incorporation of metals (Pt-Ni-Ru) in the zeolite ZSM-5 through ion exchange competitive: synthesis and characterization; Incorporacao de metais (Pt-Ni-Ru) na zeolita ZSM-5 atraves da troca ionica competitiva: sintese e caracterizacao

    Energy Technology Data Exchange (ETDEWEB)

    Barbosa, A.S.; Rodrigues, M.G.F., E-mail: antusiasb@hotmail.com [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Departamento de Engenharia Quimica; Grau, J.M. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE/FIQ/UNL-CONICET), Santa Fe (Argentina)

    2012-07-01

    Zeolites are very important materials due to their high specific surface area. Moreover, they are suitable for use as catalyst support. Noble metals supported on zeolites have been widely used as catalysts in the petrochemical industry. This paper was prepared and characterized, a powder aiming its use in heterogeneous catalysis. Support was used as ZSM-5 and the method of incorporation of the metals (Ru-PtNi) was competitive ion exchange. The materials (ZSM-5 and Pt-Ni-Ru/ZSM-5) were characterized by spectrophotometry Energy Dispersive X-ray (EDX), X-Ray Diffraction (XRD) and nitrogen physisorption (BET method). Based on the results of X-ray diffraction, it is possible to demonstrate the preservation of the structure of zeolite ZSM-5 after the competitive ion Exchange with metals (Ru-Pt-Ni) and calcination. The dispersion of metals on ZSM-5 did not change the textural characteristics of the zeolite. (author)

  13. The stages and duration of the Kieveiskoe and Fedorovskoe Pt-Pd deposits formation: U-Pb zircon data (Kola Peninsula)

    Science.gov (United States)

    Nitkina, Elena

    2010-05-01

    The Kola Peninsula is one of the unique geological provinces both in Russia and in the world, where Pt-Pd Kieveiskoe and Fedorovskoe deposits have been discovered (Mitrofanov, 2005). Several deposits within the Northern and Southern belts contain first hundreds of tons of estimated platinum metal resources, allowing us to ascribe the intrusions of the belts to the class of large igneous province (Schissel et al., 2002; Mitrofanov, 2005). The Kieveiskoe and Fedorovskoe deposits belong to the Pt-bearing Fedorovo-Pansky layered intrusion which is situated in the central part of the Kola Peninsula and is one of 14 major Early Proterozoic layered massifs of the Northern belt occurring at the border between Early Proterozoic volcano-sedimentary rift sequences and Archaean basement gneisses (Zagorodny, Radchenko, 1983; Bayanova, 2004). The aim of this report is to summarize all U-Pb data for Kieveiskoe and Fedorovskoe deposits including single grain dating with Pb205 tracer. At present, the following ages have been defined for the different stages of the massif evolution: 2526 - 2516 Ma - pyroxenite and gabbro of the Fedorovskoe deposit magma chamber (Nitkina, 2006), 2515 - 2518 Ma - Pt-bearing gabbro of Federovskoe stratiforme deposit; 2505 - 2496- 2485 Ma (Bayanova, 2004; Nitkina, 2006) - gabbro-norite and gabbro of the main phase of the Kieveiskoe deposit magma chamber and disseminated platinum-metal mineralization and relatively rich Cu-Ni sulphide mineralization in the basal part of the Kieveiskoe and Fedorovskoe non-stratiforme deposits; ca. 2470 Ma (Bayanova, 2004) - pegmatoid gabbro-anothosite and, probably, fluid-associated rich platinum-metal ores of the Lower Layered Horizon (Kieveiskoe deposit); ca. 2447+/-12 Ma (U-Pb zircon and baddeleyte (Bayanova, 2004)) - anorthositic injections and, probably, local lens-like rich Pt-Pd accumulations of the Upper layered Horizon (Kieveiskoe deposit). The U-Pb zircon ages of the massif evolution stages corroborate the

  14. Switching-off toluene formation in the solvent-free oxidation of benzyl alcohol using supported trimetallic Au-Pd-Pt nanoparticles.

    Science.gov (United States)

    He, Qian; Miedziak, Peter J; Kesavan, Lokesh; Dimitratos, Nikolaos; Sankar, Meenakshisundaram; Lopez-Sanchez, Jose Antonio; Forde, Michael M; Edwards, Jennifer K; Knight, David W; Taylor, Stuart H; Kiely, Christopher J; Hutchings, Graham J

    2013-01-01

    Trimetallic Au-Pd-Pt nanoparticles have been supported on activated carbon by the sol-immobilisation method. They are found to be highly active and selective catalysts for the solvent-free aerobic oxidation of benzyl alcohol. The addition of Pt promotes the selectivity to the desired product benzaldehyde at the expense of toluene formation. Detailed aberration corrected STEM-XEDS analysis confirmed that the supported particles are indeed Au-Pd-Pt ternary alloys, but also identified composition fluctuations from particle-to-particle which vary systematically with nanoparticle size.

  15. Failure characteristics and mechanisms of EB-PVD TBCs with Pt-modified NiAl bond coats

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Le; Mukherjee, Sriparna; Huang, Ke; Park, Young Whan; Sohn, Yongho, E-mail: Yongho.Sohn@ucf.edu

    2015-06-18

    Microstructural evolution and failure characteristics/mechanisms were investigated for thermal barrier coatings that consist of electron beam physical vapor deposited ZrO{sub 2}−8 wt% Y{sub 2}O{sub 3} (YSZ) topcoat, Pt-modified nickel aluminide, (Ni,Pt)Al bond coat, and CMSX-4 superalloy substrate with furnace cycling at 1100 °C with 1-h dwell. Photo stimulated luminescence spectroscopy, scanning electron microscopy equipped with X-ray energy dispersive spectroscopy and transmission electron microscopy were employed to examine the residual stress of the thermally grown oxide (TGO) and microstructural changes. For comparison, (Ni,Pt)Al bond coat on CMSX-4 without the YSZ topcoat was also characterized. The TGO grew faster for the YSZ-coated (Ni,Pt)Al bond coat than the (Ni,Pt)Al coating without the YSZ topcoat. Correspondingly, the β-to-γ′/martensite formation in the (Ni,Pt)Al bond coat occurred faster on the YSZ-coated (Ni,Pt)Al bond coat. However the rumpling occurred much faster and with larger amplitude on the (Ni,Pt)Al coating without the YSZ topcoat. Still, the rumpling at the TGO/bond coat interface caused crack initiation as early as 10 thermal cycles, decohesion at the YSZ/TGO interface, and eventual spallation failure primarily through the TGO/bond coat interface. The magnitude of compressive residual stress in the TGO showed an initial increase up to 3−4 GPa followed by a gradual decrease. The rate of stress relaxation was much quicker for the TGO scale without the YSZ topcoat with distinctive relief corresponding to the cracking at the top of geometrical ridges associated with the (Ni,Pt)Al bond coat. The maximum elastic energy for the TGO scale was estimated at 90 J/m{sup 2} at 50% of its lifetime (N{sub f}=545 cycles). The YSZ presence/adhesion to the TGO scale is emphasized to minimize the undulation of the TGO/bond coat interface, i.e., decohesion at the YSZ/TGO scale accelerates the rumpling and crack-coalescence at the TGO/bond coat

  16. The intelligent catalyst having the self-regenerative function of Pd, Rh and Pt for automotive emissions control

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Hirohisa; Uenishi, Mari; Taniguchi, Masashi; Tan, Isao [Materials Research and Development Division, Daihatsu Motor Co. Ltd., Ikeda, Osaka 563-8651 (Japan); Narita, Keiichi; Kimura, Mareo [Research and Development Division, Cataler Corporation, Kakegawa, Shizuoka 437-1492 (Japan); Kaneko, Kimiyoshi [Fine Chemical Research Laboratories, Hokko Chemical Industry Co. Ltd., Atsugi, Kanagawa 243-0023 (Japan); Nishihata, Yasuo; Mizuki, Jun' ichiro [Kansai Photon Science Institute, Japan Atomic Energy Agency, Sayo, Hyogo 679-5148 (Japan)

    2006-09-30

    The self-regenerative function of precious metals in the intelligent catalyst is an epoch-making technology in the history of automotive catalysts after the 1970's. The mechanism of the self-regenerative function is studied by X-ray absorption fine-structure (XAFS) analyses. The function was realized through a cyclic movement of Pd between the outside (as Pd nanoparticles) and the inside (as Pd cations in the lattice) of the perovskite crystal in synchronization with the inherent fluctuations between reductive and oxidative (redox) atmospheres that occur in real automotive exhaust gases. As the result, the growth of Pd particles can be suppressed during the entire lifetime of the vehicle. Moreover, the speed of this function was measured at the time resolution of a 10ms by in situ energy dispersive XAFS, and it is proved that the self-regenerative function occurs at an extremely high speed. Furthermore, the new perovskite catalysts which have the self-regenerative function of Rh and Pt, as well as Pd, are discussed here. This self-regenerative function provides a new and useful tool for designing the future catalyst technology. (author)

  17. Effect of Pt promotion on Ni/Al2O3 for the selective catalytic reduction of NO with hydrogen

    Science.gov (United States)

    Mihet, Maria; Lazar, Mihaela D.; Borodi, G.; Almasan, V.

    2013-11-01

    Ni/Al2O3 (10 wt.% Ni) and Ni-Pt/Al2O3 (10 wt.% Ni, 0.5 wt.% Pt) were comparatively tested in the hydrogen selective catalytic reduction process (H2-SCR), at reaction temperatures below 350°C. Catalytic activity tests consisted in temperature programmed reactions (TPRea) under plug flow conditions from 50 to 350°C, with a temperature rate of 5°C/min, using a feed stream with a reactant ratio NO:H2 = 1:1.3 and a GHSV of 4500 h-1. Promotion with Pt increases the catalytic performances of the Ni based catalyst, in respect to NO conversion, N2 selectivity and N2 yield. The reaction temperatures for NO conversion above 95% decrease significantly due to Pt addition, from 250°C for Ni/Al2O3 to 125°C for Ni-Pt/Al2O3. Characterization of catalysts was performed by: X ray powder diffraction (XRD) for the estimation of Ni crystallite size, temperature programmed reduction (TPR) for the catalyst reducibility, temperature programmed desorption of hydrogen (H2-TPD) for the investigation of active sites and metal dispersion on the support, N2 adsorption-desorption isotherms at -196°C for the determination of total specific surface area and pore size distribution, and H/D isotopic exchange on the catalyst surface. At the request of the Proceedings Editor, and all authors of the paper, an updated version of this article was published on 14 January 2014. Data presented in Table 1 of the original paper contained errors which have been corrected in the updated and re-published article. The Corrigendum attached to the corrected article PDF file explains the errors in more detail.

  18. Obtención y caracterización de MEAs con aleaciones amorfas de base NiNbPtX como catalizadores para celdas de combustibles PEM

    OpenAIRE

    Ruiz Jiménez, Noelia

    2014-01-01

    Tesis doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química Física Aplicada. Fecha de lectura: 23-05-2014 En la presente tesis, se ha realizado un estudio comparativo, en primer lugar, entre dos tipos de monoceldas, de 9 cm2 y de 25 cm2. En ambas se han empleado catalizadores amorfos de composición general Ni59Nb40Pt1-xYx (x= 0 ó 0.4% at.; Y= Ru, Sn, Pd, Rh, Co) como ánodos y como cátodos. Se han soportado en tres tipos de membranas de i...

  19. Atomic-level Pd-Pt alloying and largely enhanced hydrogen-storage capacity in bimetallic nanoparticles reconstructed from core/shell structure by a process of hydrogen absorption/desorption.

    Science.gov (United States)

    Kobayashi, Hirokazu; Yamauchi, Miho; Kitagawa, Hiroshi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki

    2010-04-28

    We have achieved the creation of a solid-solution alloy where Pd and Pt are homogeneously mixed at the atomic level, by a process of hydrogen absorption/desorption as a trigger for core (Pd)/shell (Pt) nanoparticles. The structural change from core/shell to solid solution has been confirmed by in situ powder X-ray diffraction, energy dispersive spectra, solid-state (2)H NMR measurement, and hydrogen pressure-composition isotherms. The successfully obtained Pd-Pt solid-solution nanoparticles with a Pt content of 8-21 atom % had a higher hydrogen-storage capacity than Pd nanoparticles. Moreover, the hydrogen-storage capacity of Pd-Pt solid-solution nanoparticles can be tuned by changing the composition of Pd and Pt.

  20. Preparation and electrochemistry of Pd-Ni/Si nanowire nanocomposite catalytic anode for direct ethanol fuel cell.

    Science.gov (United States)

    Miao, Fengjuan; Tao, Bairui; Chu, Paul K

    2012-04-28

    A new silicon-based anode suitable for direct ethanol fuel cells (DEFCs) is described. Pd-Ni nanoparticles are coated on Si nanowires (SiNWs) by electroless co-plating to form the catalytic materials. The electrocatalytic properties of the SiNWs and ethanol oxidation on the Pd-Ni catalyst (Pd-Ni/SiNWs) are investigated electrochemically. The effects of temperature and working potential limit in the anodic direction on ethanol oxidation are studied by cyclic voltammetry. The Pd-Ni/SiNWs electrode exhibits higher electrocatalytic activity and better long-term stability in an alkaline solution. It also yields a larger current density and negative onset potential thus boding well for its application to fuel cells.

  1. Density functional theory study on the adsorption and decomposition of the formic acid catalyzed by highly active mushroom-like Au@Pd@Pt tri-metallic nanoparticles.

    Science.gov (United States)

    Duan, Sai; Ji, Yong-Fei; Fang, Ping-Ping; Chen, Yan-Xia; Xu, Xin; Luo, Yi; Tian, Zhong-Qun

    2013-04-07

    Local structures and adsorption energies of a formic acid molecule and its decomposed intermediates (H, O, OH, CO, HCOO, and COOH) on highly electrocatalytically active mushroom-like Au-core@Pd-shell@Pt-cluster nanoparticles with two atomic layers of the Pd shell and stoichiometric Pt coverage of around half-monolayer (Au@2 ML Pd@0.5 ML Pt) have been investigated by first principles calculations. The adsorption sites at the center (far away from the Pt cluster) and the edge (close to the Pt cluster) are considered and compared. Significant repulsive interaction between the edge sites and CO is observed. The calculated potential energy surfaces demonstrate that, with respect to the center sites, the CO2 pathway is considerably promoted in the edge area. Our results reveal that the unique edge structure of the Pt cluster is responsible for the experimentally observed high electrocatalytic activity of the Au@Pd@Pt nanoparticles toward formic acid oxidation. Such microscopic understanding should be useful for the design of new electrochemical catalysts.

  2. Towards Highly Performing and Stable PtNi Catalysts in Polymer Electrolyte Fuel Cells for Automotive Application

    Directory of Open Access Journals (Sweden)

    Sabrina C. Zignani

    2017-03-01

    Full Text Available In order to help the introduction on the automotive market of polymer electrolyte fuel cells (PEFCs, it is mandatory to develop highly performing and stable catalysts. The main objective of this work is to investigate PtNi/C catalysts in a PEFC under low relative humidity and pressure conditions, more representative of automotive applications. Carbon supported PtNi nanoparticles were prepared by reduction of metal precursors with formic acid and successive thermal and leaching treatments. The effect of the chemical composition, structure and surface characteristics of the synthesized samples on their electrochemical behavior was investigated. The catalyst characterized by a larger Pt content (Pt3Ni2/C presented the highest catalytic activity (lower potential losses in the activation region among the synthesized bimetallic PtNi catalysts and the commercial Pt/C, used as the reference material, after testing at high temperature (95 °C and low humidification (50% conditions for automotive applications, showing a cell potential (ohmic drop-free of 0.82 V at 500 mA·cm−2. In order to assess the electro-catalysts stability, accelerated degradation tests were carried out by cycling the cell potential between 0.6 V and 1.2 V. By comparing the electrochemical and physico-chemical parameters at the beginning of life (BoL and end of life (EoL, it was demonstrated that the Pt1Ni1/C catalyst was the most stable among the catalyst series, with only a 2% loss of voltage at 200 mA·cm−2 and 12.5% at 950 mA·cm−2. However, further improvements are needed to produce durable catalysts.

  3. Domestic wastewater treatment using Pt,Ni-RE (rare earth electrodes

    Directory of Open Access Journals (Sweden)

    Eurico Moutinho

    2016-11-01

    Full Text Available Electrochemical technologies can be used for the treatment of domestic wastewaters, by eliminating their organic pollutants. They have advantages over conventional methods, such as environmental compatibility, versatility, energy efficiency, safety and cost. The organic compounds degradation process is based on the production of OH radicals, formed during water electrolysis, which oxidize the organic molecules to CO2. At the same time, hydrogen (H2 is produced through reduction of the water in the effluent, which can be later used in a fuel cell. Present study seeks to find effective electrocatalysts to produce H2 by electrolysis, using domestic wastewaters as the hydrogen source, with or without the addition of supporting electrolyte. Herein KOH is used as the supporting electrolyte, as the extra hydroxide can be used to degrade the organic matter. Nine different electrode materials are evaluated as cathodes for the hydrogen evolution reaction (HER in a domestic wastewater. The tested materials include platinum (Pt and platinum-rare earth (Pt-RE binary alloys, and nickel (Ni and Ni-RE alloys, with the REs being cerium (Ce, samarium (Sm, dysprosium (Dy, and holmium (Ho. Linear scan voltammetry measurements are conducted at temperatures ranging from 25 to 85 ºC. Several kinetic parameters are calculated, such as the Tafel slopes, charge transfer coefficients and exchange current densities. The data obtained at the different electrode materials is compared and it is clear that Pt-RE alloys show superior activity for the HER. It is also noticeable that the wastewater effluent containing the supporting electrolyte leads to significantly better HER performances.

  4. Ni2P Makes Application of the PtRu Catalyst Much Stronger in Direct Methanol Fuel Cells.

    Science.gov (United States)

    Chang, Jinfa; Feng, Ligang; Liu, Changpeng; Xing, Wei

    2015-10-12

    PtRu is regarded as the best catalyst for direct methanol fuel cells, but the performance decay resulting from the loss of Ru seriously hinders commercial applications. Herein, we demonstrated that the presence of Ni2 P largely reduces Ru loss, which thus makes the application of PtRu much stronger in direct methanol fuel cells. Outstanding catalytic activity and stability were observed by cyclic voltammetry. Upon integrating the catalyst material into a practical direct methanol fuel cell, the highest maximum power density was achieved on the PtRu-Ni2P/C catalyst among the reference catalysts at different temperatures. A maximum power density of 69.9 mW cm(-2) at 30 °C was obtained on PtRu-Ni2P/C, which is even higher than the power density of the state-of-the-art commercial PtRu catalyst at 70 °C (63.1 mW cm(-2)). Moreover, decay in the performance resulting from Ru loss was greatly reduced owing to the presence of Ni2 P, which is indicative of very promising applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Off-easy-plane antiferromagnetic spin canting in coupled FePt/NiO bilayer structure with perpendicular exchange bias

    Science.gov (United States)

    Gao, Tenghua; Itokawa, Nobuhide; Wang, Jian; Yu, Youxing; Harumoto, Takashi; Nakamura, Yoshio; Shi, Ji

    2016-08-01

    We report on the investigation of perpendicular exchange bias in FePt (001 ) /NiO (1 ¯1 ¯1 ) orthogonal exchange couple with FePt partially L 10 ordered. From initial magnetization curve measurement and magnetic domain imaging, we find that, for the as-grown bilayer structure, the FePt layer experiences a small-angle magnetization rotation when it is magnetized near to saturation in film normal direction. After field cooling, the bilayer structure shows a significant enhancement of perpendicular magnetic anisotropy, indicating the field mediated coupling between the spins across the FePt/NiO interface. According to Koon's theoretical calculation on the basis of lowest energy ferromagnetic/antiferromagnetic coupling configuration for compensated spins at antiferromagnetic side, we consider slightly slanted Ni spins at the interface off the (1 ¯1 ¯1 ) easy plane can stabilize the spin coupling between FePt and NiO and result in the observed exchange bias in this paper. This consideration was further confirmed by stripe domain width calculation.

  6. High Temperature Oxidation Behavior of gamma-Ni+gamma'-Ni3Al Alloys and Coatings Modified with Pt and Reactive Elements

    Energy Technology Data Exchange (ETDEWEB)

    Mu, Nan [Iowa State Univ., Ames, IA (United States)

    2007-12-01

    Materials for high-pressure turbine blades must be able to operate in the high-temperature gases (above 1000 C) emerging from the combustion chamber. Accordingly, the development of nickel-based superalloys has been constantly motivated by the need to have improved engine efficiency, reliability and service lifetime under the harsh conditions imposed by the turbine environment. However, the melting point of nickel (1455 C) provides a natural ceiling for the temperature capability of nickel-based superalloys. Thus, surface-engineered turbine components with modified diffusion coatings and overlay coatings are used. Theses coatings are capable of forming a compact and adherent oxide scale, which greatly impedes the further transport of reactants between the high-temperature gases and the underlying metal and thus reducing attack by the atmosphere. Typically, these coatings contain β-NiAl as a principal constituent phase in order to have sufficient aluminum content to form an Al2O3 scale at elevated temperatures. The drawbacks to the currently-used {beta}-based coatings, such as phase instabilities, associated stresses induced by such phase instabilities, and extensive coating/substrate interdiffusion, are major motivations in this study to seek next-generation coatings. The high-temperature oxidation resistance of novel Pt + Hf-modified γ-Ni + γ-Ni3Al-based alloys and coatings were investigated in this study. Both early-stage and 4-days isothermal oxidation behavior of single-phase γ-Ni and γ'-Ni3Al alloys were assessed by examining the weight changes, oxide-scale structures, and elemental concentration profiles through the scales and subsurface alloy regions. It was found that Pt promotes Al2O3 formation by suppressing the NiO growth on both γ-Ni and γ'Ni3Al single-phase alloys. This effect increases with increasing Pt content. Moreover, Pt exhibits this effect even at

  7. Characterization of sputter-deposited TiPdNi thin films

    Institute of Scientific and Technical Information of China (English)

    田青超; 吴建生

    2002-01-01

    TiPdNi thin films were prepared by magne tron sputtering onto unheated glass and silicon substrate. Atomic force microscope, energy-dispersive X-ray mi croanalyzer, X-ray diffractometer, differential scanning calorimeter and optical microscope were used to characterize the films. It is found that the surface m orphology of the films change during the sputtering process and a shift of about 3%Ti(mole fraction) content from the center to the edge of the substrate occurs. The freestanding as-deposited films undergo crystallization followed by three kinds of cooling conditions. For all these heat-treated films, B2→B19→B19′ two- stage phase transformation takes place. Many Ti2Ni and Ti2Pd type of precipitates are detected in the films. The constraint films on silicon substrate are crystallized at high temperature. After crystallization, the films show a two-way shape memory effect.

  8. Aqueous phase reforming of glycerol over the Pd loaded Ni/Al2O3 catalysts.

    Science.gov (United States)

    Karthikeyan, Dhanapalan; Shin, Gwan Su; Moon, Dong Ju; Kim, Jong Ho; Park, Nam Cook; Kim, Young Chul

    2011-02-01

    Bifunctional catalysts containing (0.5-1.5 wt%) palladium and 15 wt% of Nickel supported on gamma-Al2O3 were prepared via an impregnation technique and catalysts were characterzed by XRD BET surface area and SEM, respectively. The aqueous phase reforming of glycerol (APR) was conducted over alumina-supported catalysts at different reaction conditions for catalytic activity. Finally, we concluded that the 1.0 wt% Pd 15 wt% Ni/gamma-Al2O3 catalyst evidences higher conversion, hydrogen selectivity, lower alkane selectivity and CO production. This indicate that Pd loaded Ni/gamma-Al2O3 could be a potential catalyst for the APR of glycerol.

  9. New system for manipulation of nanoobjects based on composite Ti2NiCu/Pt nanotweezers with shape memory effect

    Science.gov (United States)

    Zhikharev, A. M.; Irzhak, A. V.; Beresin, M. Y.; Lega, P. V.; Koledov, V. V.; Kasyanov, N. N.; Martynov, G. S.

    2016-08-01

    We report the new system for manipulation of nanoobjects based on composite Ti2NiCu/Pt nanotweezers with shape memory effect. The design consists of the bimetallic Ti2NiCu/Pt shape memory nanotweezers placed on a tip of electrochemically etched tungsten needle. The semiconductor diode placed on the tip of the needle plays both role of resistive element of the heater and temperature sensor for feedback control loop closing. The device is compatible with existing positioning systems like OmniProbe®, Kleindiek®, etc. and may find numerous practical applications in various tasks of nanotechnology connected with 3D manipulation.

  10. New structures in Pd-rich ordered alloys

    Science.gov (United States)

    Corbitt, Jacqueline; Gilmartin, Erin; Hart, Gus

    2010-10-01

    An intriguing intermetallic structure with 8:1 stoichiometry was discovered in the 1950s in the Pt-Ti system. Since then a handful of other Pt/Pd/Ni binary systems have been observed to exhibit this curious structure (Pt8Zr, Pd8Mo, Ni8Nb, etc). This ordered structure can significantly increase the hardness of an alloy. For jewelry applications involving Pt and Pd, international hallmarking standards require that the alloys be at least 95% pure by weight. However, Pt- and Pd-rich alloys are often soft when purity is high if the minority atoms are disordered. Because the 8:1 structure maintains a high weight percentage of Pt/Pd, it can satisfy purity standards while increasing performance. Recent calculations and experiments suggest that the 8:1 structure may form in about 20 previously unsuspected Pt/Pd binary systems. Using first-principles calculations and cluster expansion modeling, we have performed a ground state search to find the stable structures in Pd-Nb and Pd-Cu. In collaboration with Candace Lang's group at University of Capetown South Africa, we are working to experimentally validate the predicted ground states.

  11. Low-cost Cr doped Pt3Ni alloy supported on carbon nanofibers composites counter electrode for efficient dye-sensitized solar cells

    Science.gov (United States)

    Xiao, Junying; Cui, Midou; Wang, Mingkun; Sui, Huidong; Yang, Kun; Li, Ling; Zhang, Wenming; Li, Xiaowei; Fu, Guangsheng; Hagfeldt, Anders; Zhang, Yucang

    2016-10-01

    Pt3Ni alloy supported by carbon nanofibers (CNs) composites (Pt3Ni/CNs) synthesized by a simple solvothermal process was introduced into dye-sensitized solar cells (DSCs) as counter electrode (CE) for the first time, and the DSCs based on Pt3Ni/CNs CE obtained a power conversion efficiency (PCE) of 8.34%. To enhance the catalytic activity of Pt3Ni/CNs composites, transition metal chrome (Cr) was doped in Pt3Ni/CNs to synthesize the composites of Cr-Pt3Ni/CNs using the same method. Due to the high electrocatalytic activity and rapid charge transfer ability, the PCE of the DSCs employing Cr-Pt3Ni/CNs as CE increased to 8.76%, which was much higher than that of Pt CE (7.04%) measured in the same condition. The impressive results along with low cost and simple synthesis process demonstrated transition metal doping was a promising method to produce substitutes for Pt to reduce the cost and increase the PCE of DSCs.

  12. Oxidation Kinetics of a NiPtTi High Temperature Shape Memory Alloy

    Science.gov (United States)

    Smialek, James L.; Humphrey, Donald L.; Noebe, Ronald D.

    2007-01-01

    A high temperature shape memory alloy (HTSMA), Ni30Pt50Ti, with an M(sub s) near 600 C, was isothermally oxidized in air for 100 hr over the temperature range of 500 to 900 C. Parabolic kinetics were confirmed by log-log and parabolic plots and showed no indication of fast transient oxidation. The overall behavior could be best described by the Arrhenius relationship: k(sub p) = 1.64 x 10(exp 12)[(-250 kJ/mole)/RT] mg(sup 2)/cm(sup 4)hr. This is about a factor of 4 reduction compared to values measured here for a binary Ni47Ti commercial SMA. The activation energy agreed with most literature values for TiO2 scale growth measured for elemental Ti and other NiTi alloys. Assuming uniform alloy depletion of a 20 mil (0.5 mm) dia. HTSMA wire, approx. 1 percent Ti reduction is predicted after 20,000 hr oxidation at 500 C, but becomes much more serious at higher temperatures.

  13. Synthesis and reactivity of Ph/sub 2/PCH/sub 2/PPh/sub 2/- (dppm-) stabilized Pd-Co and Pd-Pt-Co clusters. Effect of platinum versus palladium on the neighboring palladium center

    Energy Technology Data Exchange (ETDEWEB)

    Braunstein, P.; de Meric de Bellefon, C.; Ries, M.

    1988-04-20

    The quantitative and regioselective synthesis of the mixed-metal cluster (PdPtCo/sub 2/(CO)/sub 7/(dppm)/sub 2/) (1b) was achieved by the reaction of the bimetallic complex (PdPtCl/sub 2/(dppm)/sub 2/) (dppm = /mu/-Ph/sub 2/PCH/sub 2/PPh/sub 2/) with (Co(CO)/sub 4/)/sup /minus//. As a result of phosphorus migration from palladium to cobalt, formal insertion of the Co(CO)/sub 3/ fragment into a metal-phosphorus bond of the precursor exclusively occurs into the more labile P /yields/ Pd bond. The lability of the exocyclic Co(CO)/sub 4/ fragment was evidenced and compared between 1b and (Pd/sub 2/Co/sub 2/(CO)/sub 7/(dppm)/sub 2/) (1a). Although a Pd-Co bond is involved, this lability is very sensitive to the neighboring metal center (Pd or Pt). Transmission of electronic effects from one metal-center to another was evidenced, and a platinum effect was observed in dissociating solvents, where 1a is partly dissociated but 1b is completely dissociated into (PdPtCo(CO)/sub 3/(S)(dppm)/sub 2/)(CO(CO)/sub 4/) (S = solvent). This is a reversible process, as is the equilibrium between 1 and halide anions. Solvento clusters were prepared that possess a labile coordination site on Pd leading to completely regioselective reactions with donor molecules, e.g., phosphines, CO, or C/sub 2/Ph/sub 2/. These ligands are labile (PR/sub 3/ < CO < C/sub 2/Ph/sub 2/ < MeCN < THF), and reversible CO uptake and substitution experiments showed that the Pd-bound CO in 4b is less labile than in 4a, indicating again a platinum effect on the reactive Pd center. The tris(bis(diphenylphosphino)methane) cationic cluster (Pd/sub 2/Co(CO)/sub 2/(dppm)/sub 3/)/sup +/ was isolated, in which all the metal-metal bonds are bridged by dppm ligands. Spectroscopic IR and /sup 1/H, /sup 31/P(/sup 1/H), and /sup 195/Pt(/sup 1/H) NMR data are discussed and confirm that in these reactions the PdMCo(dppm)/sub 2/ (M = Pd, Pt) framework is maintained.

  14. Immobilization of superoxide dismutase on Pt-Pd/MWCNTs hybrid modified electrode surface for superoxide anion detection.

    Science.gov (United States)

    Zhu, Xiang; Niu, Xiangheng; Zhao, Hongli; Tang, Jie; Lan, Minbo

    2015-05-15

    Monitoring of reactive oxygen species like superoxide anion (O2(∙-)) turns to be of increasing significance considering their potential damages to organism. In the present work, we fabricated a novel O2(∙-) electrochemical sensor through immobilizing superoxide dismutase (SOD) onto a Pt-Pd/MWCNTs hybrid modified electrode surface. The Pt-Pd/MWCNTs hybrid was synthesized via a facile one-step alcohol-reduction process, and well characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The immobilization of SOD was accomplished using a simple drop-casting method, and the performance of the assembled enzyme-based sensor for O2(∙-) detection was systematically investigated by several electrochemcial techniques. Thanks to the specific biocatalysis of SOD towards O2(∙-) and the Pt-Pd/MWCNTs - promoted fast electron transfer at the fabricated interface, the developed biosensor exhibits a fast, selective and linear amperometric response upon O2(∙-) in the concentration scope of 40-1550 μM (R(2)=0.9941), with a sensitivity of 0.601 mA cm(-2) mM(-1) and a detection limit of 0.71 μM (S/N=3). In addition, the favorable biocompatibility of this electrode interface endows the prepared biosensor with excellent long-term stability (a sensitivity loss of only 3% over a period of 30 days). It is promising that the proposed sensor will be utilized as an effective tool to quantitatively monitor the dynamic changes of O2(∙-) in biological systems.

  15. Simultaneous electrochemical detection of ascorbic acid, dopamine and uric acid based on graphene anchored with Pd-Pt nanoparticles.

    Science.gov (United States)

    Yan, Jun; Liu, Shi; Zhang, Zhenqin; He, Guangwu; Zhou, Ping; Liang, Haiying; Tian, Lulu; Zhou, Xuemin; Jiang, Huijun

    2013-11-01

    Pd-Pt bimetallic nanoparticles anchored on functionalized reduced graphene oxide (RGO) nanomaterials were synthesized via a one-step in situ reduction process, in which Pt and Pd ions were first attached to poly(diallyldimethylammonium chloride) (PDDA) functionalized graphene oxide (GO) sheets, and then the encased metal ions and GO were subjected to simultaneous reduction by ethylene glycol. The as-prepared Pd3Pt1/PDDA-RGO nanocomposites were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and electrochemical methods. In addition, an electrochemical sensor based on the graphene nanocomposites was fabricated for the simultaneous detection of ascorbic acid (AA), dopamine (DA) and uric acid (UA) in their ternary mixture. Three well-separated voltammetric peaks along with remarkable increasing electro-oxidation currents were obtained in differential pulse voltammetry (DPV) measurements. Under the optimized conditions, there were linear relationships between the peak currents and the concentrations in the range of 40-1200 μM for AA, 4-200 μM for DA and 4-400 μM for UA, with the limit of detection (LOD) (based on S/N=3) of 0.61, 0.04 and 0.10 μM for AA, DA and UA, respectively. This improved electrochemical performance can be attributed to the synergistic effect of metallic nanoparticles and RGO and the combination of the bimetallic nanoparticles. Furthermore, the practical electroanalytical utility of the sensor was demonstrated by the determination of AA, DA and together with UA in human urine and blood serum samples with satisfactory results. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Ab Initio evaluation of electron transport properties of Pt, Rh, Ir, and Pd nanowires for advanced interconnect applications

    Science.gov (United States)

    Lanzillo, Nicholas A.

    2017-05-01

    The electronic and structural properties of nanowires composed of either Pt, Ir, Rh, or Pd are calculated using density functional theory and a non-equilibrium Green's function scattering approach. The results for these nanowires are compared with Cu nanowires of comparable dimensions and evaluated for potential use in interconnect technology applications. The cohesive energies of the Pt, Rh and Ir nanowires are found to be stronger than the corresponding value for bulk Cu, indicating superior structural integrity and resistance to electromigration relative to Cu. Several of the nanowires considered are found to exhibit larger values of ballistic conductance relative to Cu, with maximum conductance occurring along the [110] crystallographic direction. Electron scattering at some representative twin grain boundaries is evaluated and an empirical resistivity model is used to quantitatively estimate the impact of grain size on total resistivity.

  17. Co/Pt and Co/Pd multilayers as a new class of magneto-optical recording materials

    Science.gov (United States)

    Zeper, W. B.; Greidanus, Franciscus J. A. M.; van Kesteren, H. W.; Jacobs, Ben A. J.; Spruit, J. H. M.; Carcia, Peter F.

    1990-08-01

    In this paper we give an overview of the magnetic and magneto-optical properties of Co/Pt and, to a less extent, Co/Pd multilayers as optimized for magneto-optical storage applications. The Co layers should be very thin, i.e. about 4 A , and the Pt layers about 10-20 A to achieve a 100 % remanent layer with perpendicular magnetic anisotropy and high coercivity (80-100 kA/m). Furthermore, the hysteresis loop becomes rectangular for total film thicknesses below about 20 nm. We measured the optical properties as a function of the wavelength of the light and calculated the figure of merit at three wavelengths (820, 633 and 410 nm) for various disk structures. Optimal figures of merit are obtained for film thicknesses below 20 nm, i.e. thicknesses that are optimum for the magnetic properties. The figure of merit at A. = 820 am for Co/Pt is comparable to that of GdTbFe and increases towards shorter wavelengths which favor higher-density recording. We discuss the recording performance using Lorentz images of the written domain patterns. Very regularly shaped domains can be written at normal writing conditions, i.e. at a laser power of 5-10 mW and fields of 25 kA/m. The highest carrier-to-noise ratio measured for Co/Pt is 51 dB (375 kHz carrier, 1.4 m/s, 10 kHz bandwidth). Aging experiments in dry oxygen-nitrogen atmosphere showed that Co/Pt multilayers are chemically stable up to 1 50 °C . Finally, no change in carrier-to-noise ratio is observed for Co/Pt multilayers with a Curie temperature below 300 °C after 2x104 write/read/erase cycles.

  18. Pd-Pt loaded graphene aerogel on nickel foam composite as binder-free anode for a direct glucose fuel cell unit

    Science.gov (United States)

    Tsang, Chi Him A.; Leung, D. Y. C.

    2017-09-01

    Fabrication of electrocatalyst for direct glucose fuel cell (DGFC) operation involves destructive preparation methods with the use of stabilizer like binder, which may cause activity depreciation. Binder-free electrocatalytic electrode becomes a possible solution to the above problem. Binder-free bimetallic Pd-Pt loaded graphene aerogel on nickel foam plates with different Pd/Pt ratios (1:2.32, 1:1.62, and 1:0.98) are successfully fabricated through a green one-step mild reduction process producing a Pd-Pt/GO/nickel form plate (NFP) composite. Anode with the binder-free electrocatalysts exhibit a strong activity in a batch type DGFC unit under room temperature. The effects of glucose and KOH concentrations, and the Pd/Pt ratios of the electrocatalyst on the DGFC performance are also studied. Maximum power density output of 1.25 mW cm-2 is recorded with 0.5 M glucose/3 M KOH as the anodic fuel, and Pd1Pt0.98/GA/NFP as catalyst, which is the highest obtained so far among other types of electrocatalyst.

  19. One-pot, template-free synthesis of Pd-Pt single-crystalline hollow cubes with enhanced catalytic activity.

    Science.gov (United States)

    Sun, Long; Zhang, Zhicheng; Xu, Biao; Wang, Xun

    2013-07-01

    Hollow structures have attracted ever-growing interest owing to their various excellent properties. However, a facile strategy for their fabrication is still desired. Herein, Pd-Pt alloy with three different morphologies, that is, cubes, hollow cubes, and truncated octahedrons, is synthesized by using a one-pot, template-free method. The mechanism and dynamics of this system is also studied in detail. In particular, the hollow cubic structure represents enhanced catalytic activity in both coupling reactions and in the electrochemical oxidation of formic acid. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Optic fiber hydrogen sensor based on high-low reflectivity Bragg gratings and WO3-Pd-Pt multilayer films

    Science.gov (United States)

    Dai, Jixiang; Yang, Minghong; Li, Zhi; Wang, Gaopeng; Huang, Chujia; Qi, Chongjie; Dai, Yutang; Wen, Xiaoyan; Cheng, Cheng; Guo, Huiyong

    2015-09-01

    A novel optic fiber hydrogen sensor is proposed in this paper. Two Bragg gratings with different reflectivity were written in single mode fiber with phase mask method by 248 nm excimer laser. The end-face of singe mode fiber was deposited with WO3-Pd-Pt multilayer films as sensing element. The peak intensity of low reflectivity FBG is employed for hydrogen characterization, while that of high reflectivity FBG is used as reference. The experimental results show the hydrogen sensor still has good repeatability when the optic intensity in the fiber is only 1/3 of its initial value. The hydrogen sensor has great potential in measurement of hydrogen concentration.

  1. Chemical order and selection of the mechanism for strain relaxation in epitaxial FePd(Pt) thin layers

    Science.gov (United States)

    Halley, D.; Marty, A.; Bayle-Guillemaud, P.; Gilles, B.; Attane, J. P.; Samson, Y.

    2004-11-01

    We observed that the relaxation mechanism of the epitaxial strain is dramatically dependent on the chemical ordering within the L10 structure in FePd(Pt) thin films. In disordered or weakly ordered layers, the relaxation takes place though perfect (1)/(2)[101] dislocations, whereas well-ordered films relax through the partial 1/6[112] Shockley dislocations, piled-up within microtwins, with a huge impact on both the morphology and the magnetic properties of the film. We show that the antiphase boundary energy is the key factor preventing the propagation of perfect dislocations in ordered alloys.

  2. Elastic stability and electronic structure of low energy tetragonal and monoclinic PdN2 and PtN2

    Institute of Scientific and Technical Information of China (English)

    Zhao Wen-Jie; Wang Yuan-Xu

    2009-01-01

    This paper studies the elastic and electronic structure properties of two new low-energy structures of PdN2 and PtN2 by first-principles calculations. It finds that tetragonal and monoclinic structures are more stable than a pyrite one. The always positive eigenvalues of the elastic constant matrix confirm that both the tetragonal and monoclinic structures are elastically stable. The origin of the low bulk modulus of the two structures is discussed. The results of the calculated density of states show that both of the two low-energy structures are metallic.

  3. Large enhancement of Blocking temperature by control of interfacial structures in Pt/NiFe/IrMn/MgO/Pt multilayers

    Directory of Open Access Journals (Sweden)

    Xi Chen

    2015-09-01

    Full Text Available The Blocking temperature (TB of Pt/NiFe/IrMn/MgO/Pt multilayers was greatly enhanced from far below room temperature (RT to above RT by inserting 1 nm thick Mg layer at IrMn/MgO interface. Furthermore, the exchange bias field (Heb was increased as well by the control of interfacial structures. The evidence for a significant fraction of Mn-O bonding at IrMn/MgO interface without Mg insertion layer was provided by X-ray photoelectron spectroscopy. The bonding between Mn and O can decrease the antiferromagnetism of IrMn film, leading to lower value of TB in Pt/NiFe/IrMn/MgO/Pt multilayers. Ultrathin Mg film inserted at IrMn/MgO interface acting as an oxygen sinking layer can suppress the oxidation reactions between Mn and O and reduce the formation of Mn-O bonding greatly. The oxidation suppression results in the recovery of the antiferromagnetism of IrMn film, which can enhance TB and Heb. Furthermore, the high resolution transmission electron microscopy demonstrates that the Mg insertion layer can efficiently promote a high-quality MgO (200 texture. This study will enhance the understanding of physics in antiferromagnet-based spintronic devices.

  4. A structural study of effects of NiP seed layer on the magnetic properties of CoCrPt/Ti/NiP perpendicular magnetic films

    CERN Document Server

    Sun, C J; Wang, J P; Soo, E W; Noh, D Y; Je, J H; Hwu, Y K

    2003-01-01

    The CoCrPt/Ti/NiP films for perpendicular magnetic recording were studied using X-ray scattering and anomalous X-ray scattering. When the NiP seed layer was used, the long range order of the texture peak of the magnetic film decreased and less Co was associated with this Bragg order. The structural results were consistent with the observed increased coercivity and decreased magnetization due to the increased magnetic grain isolation caused by the presence of NiP seed layer.

  5. Adsorption and dissociation of H2S on monometallic and monolayer bimetallic Ni/Pd(111) surfaces: A first-principles study

    Science.gov (United States)

    Li, Yi; Huang, Pan; Tao, Dandan; Wu, Juan; Qiu, Mei; Huang, Xin; Ding, Kaining; Chen, Wenkai; Su, Wenyue; Zhang, Yongfan

    2016-11-01

    Periodic density functional theory calculations have been performed to investigate the adsorption structures and dissociative reaction pathways for H2S molecule on Ni(111), Pd(111) and Ni/Pd(111) monolayer bimetallic surfaces with surface monolayer and subsurface monolayer structures. Our results indicate that, for the molecular adsorption mode, the introducing Pd atoms on Ni(111) can enhance the binding strength between H2S and the surface, while an opposite effect is achieved when the Ni monolayer is formed on Pd(111) surface. The decompositions of H2S molecule on all Ni/Pd(111) surfaces are exothermic, especially for the surfaces that the top layer is composed of Ni atoms. According to the predicted minimum energy paths that connect the molecular and dissociative states, two elementary steps are found for all Ni/Pd(111) metal surfaces, and the breaking of the first Hsbnd S bond is the rate-determining step for the H2S dissociation. Our results reveal that in most cases, the decomposition of H2S molecule on the monometallic and Ni/Pd(111) monolayer bimetallic surfaces is easy to happen. However, on the monolayer Ni-Pd(111) surface, there is a competition between the trapping-desorption channel and activated dissociation channel, which implies that depositing one monolayer Ni on a Pd(111) surface may help reducing sulfur poisoning by hindering the dissociation of H2S molecule.

  6. Enhanced H2S Sensing Performance of a p-type Semiconducting PdO-NiO Nanoscale Heteromixture

    Science.gov (United States)

    Balamurugan, C.; Jeong, Y. J.; Lee, D. W.

    2017-10-01

    Semiconducting nanocrystalline nickel oxide (NiO) and PdO-doped NiO heteromixture (2, 5 and 10 wt%) have been synthesized via a metal-citrate complex method. The obtained materials were further characterized using TG/DTA, FT-IR, UV-vis, XRD, XPS, BET/BJH, SEM and TEM analyses to determine their structural and morphological properties. The results indicated that the spherical, uniform PdO nanoparticles were densely deposited on the NiO surface mainly in diameters of 10-15 nm. Moreover, the existence of various defect states was also analyzed with the help of photoluminescence (PL) spectroscopy. The gas response characteristics of synthesized materials were evaluated in the presence and absence of toxic gases such as hydrogen sulfide (H2S), carbon monoxide (CO), liquid petroleum gas (LPG), and ethanol (C2H5OH). The experimental results revealed that the sensitivity and selectivity of the NiO-based sensor material are dependent on the weight% of PdO loading in the NiO nanopowder. Among the investigated compound, the 5 wt% PdO-doped NiO sensor material showed excellent sensitivity and selectivity to 100 ppm H2S wit