WorldWideScience

Sample records for bimetallic mn-co clusters

  1. Mono- and bimetallic manganese-carbonyl complexes and clusters bearing imidazol(in)ium-2-dithiocarboxylate ligands.

    Science.gov (United States)

    Beltrán, Tomás F; Zaragoza, Guillermo; Delaude, Lionel

    2017-02-14

    Five complexes with the generic formula fac-[MnBr(CO)3(S2C·NHC)] were obtained by reacting [MnBr(CO)5] with a set of representative imidazol(in)ium-2-dithiocarboxylate zwitterions. These ligands are the adducts of N-heterocyclic carbenes (NHCs) and carbon disulfide. The mononuclear Mn(i) derivatives were coupled with Na[Mn(CO)5] to afford bimetallic [Mn2(CO)6(S2C·NHC)] clusters. Yet, the most convenient strategy to access these dinuclear Mn(0) products implied a direct carbonyl substitution from the [Mn2(CO)10] dimer. The molecular structures of three monometallic and four bimetallic compounds were elucidated by single crystal X-ray diffraction analysis. In the monometallic complexes, the NHC·CS2 ligands exhibited a bidentate κ(2)-S,S' coordination mode with an S-C-S bite angle of about 116°. In the dinuclear clusters, the CS2(-) unit acted as a chelate toward one manganese center and as a pseudoallylic ligand toward the other one. The S-C-S bite angle was reduced to ca. 104°. Thus, the zwitterions displayed a remarkable flexibility, which also permitted a staggered arrangement of the carbonyl groups in the bimetallic systems. Examination of the [small nu, Greek, macron]CO absorption bands on IR spectroscopy helped identify the presence of fac-Mn(CO)3 or Mn2(CO)6 motifs, while the (13)C NMR chemical shift of the CS2(-) moiety was a reliable indicator for monitoring its hapticity. Whereas the dinuclear clusters were air- and moisture-stable crystalline solids, mononuclear halido derivatives displayed only a limited stability under aerobic conditions. Both types of compounds underwent rather unselective, extensive fragmentations in the gas phase, in sharp contrast with the analogous rhenium derivatives that led to clean sequential decarbonylation processes upon collision-induced dissociation.

  2. Structure and properties of bimetallic titanium and vanadium oxide clusters.

    Science.gov (United States)

    Helmich, Benjamin; Sierka, Marek; Döbler, Jens; Sauer, Joachim

    2014-05-14

    By employing a genetic algorithm together with density functional theory (B3LYP), we investigate the most stable minimum structures of several bimetallic titanium and vanadium oxide clusters that contain four metal atoms. The following compositions are studied: VnTin-4O10(-) (n = 1-4), (TiO2)VOn(-) (n = 1-4), and (TiO2)VOn(+) (n = 1-3). Apart from (TiO2)3VO(-), vanadium oxo groups are always part of the most stable minimum structures when vanadium is present. Anti-ferromagnetic coupling lowers the energy substantially if spin centers are located at neighbored metal atoms rather than at distant oxygen radical sites. Vanadium-rich or oxygen-poor compositions prefer symmetric adamantane-like cage structures, some of which have already been proposed in a previous study. In contrast, vanadium-poor and oxygen-rich compositions show versatile structural motifs that cannot be intuitively derived from the symmetric cage motif. Particularly, for Ti4O10(-) there are several non-symmetric and distorted cages that have an up to 68 kJ mol(-1) lower energy than the symmetric adamantane-like cage structure. Nevertheless, for the adamantane-like cage the simulated infra-red spectrum (within the harmonic approximation) agrees best with the experimental vibrational spectrum. The oxidative power of the (TiO2)3VO3(-) and (TiO2)3VO2(+) clusters as measured by the energy of removing 1/2 O2 (297 and 227 kJ mol(-1), respectively) is less than that of the pure vanadium oxide clusters (V2O5)VO3(-) and (V2O5)VO2(+) (283 and 165 kJ mol(-1), respectively).

  3. 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.

  4. Preparation of Bimetallic PtnPdm Supported Clusters with Well-Defined Stoichiometry

    Science.gov (United States)

    Rousset, J. L.; Cadrot, A. M.; Aires, F. Santos; Renouprez, A.; Mélinon, P.; Perez, A.; Pellarin, M.; Vialle, J. L.; Broyer, M.

    Supported bimetallic Pd-Pt clusters with a well-defined stoichiometry are produced using a laser-vaporization source. Free clusters are also studied by time-of-flight mass spectrometry and photofragmentation. The supported clusters are characterized by energy dispersive x-ray analysis. The low binding energy of palladium atoms compared to that of platinum is clearly demonstrated in both free and supported clusters. The reactivity is briefly discussed.

  5. Platinum-ruthenium bimetallic clusters on graphite: a comparison of vapor deposition and electroless deposition methods.

    Science.gov (United States)

    Galhenage, Randima P; Xie, Kangmin; Diao, Weijian; Tengco, John Meynard M; Seuser, Grant S; Monnier, John R; Chen, Donna A

    2015-11-14

    Bimetallic Pt-Ru clusters have been grown on highly ordered pyrolytic graphite (HOPG) surfaces by vapor deposition and by electroless deposition. These studies help to bridge the material gap between well-characterized vapor deposited clusters and electrolessly deposited clusters, which are better suited for industrial catalyst preparation. In the vapor deposition experiments, bimetallic clusters were formed by the sequential deposition of Pt on Ru or Ru on Pt. Seed clusters of the first metal were grown on HOPG surfaces that were sputtered with Ar(+) to introduce defects, which act as nucleation sites for Pt or Ru. On the unmodified HOPG surface, both Pt and Ru clusters preferentially nucleated at the step edges, whereas on the sputtered surface, clusters with relatively uniform sizes and spatial distributions were formed. Low energy ion scattering experiments showed that the surface compositions of the bimetallic clusters are Pt-rich, regardless of the order of deposition, indicating that the interdiffusion of metals within the clusters is facile at room temperature. Bimetallic clusters on sputtered HOPG were prepared by the electroless deposition of Pt on Ru seed clusters from a Pt(+2) solution using dimethylamine borane as the reducing agent at pH 11 and 40 °C. After exposure to the electroless deposition bath, Pt was selectively deposited on Ru, as demonstrated by the detection of Pt on the surface by XPS, and the increase in the average cluster height without an increase in the number of clusters, indicating that Pt atoms are incorporated into the Ru seed clusters. Electroless deposition of Ru on Pt seed clusters was also achieved, but it should be noted that this deposition method is extremely sensitive to the presence of other metal ions in solution that have a higher reduction potential than the metal ion targeted for deposition.

  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. Preparation and characterization of Ni/Co bimetallic nano-clusters

    Institute of Scientific and Technical Information of China (English)

    Jinzhang Gao; Fei Guan; Yongjun Ma; Jingwan Kang

    2003-01-01

    Ni/Co bimetallic nano-cluters have been prepared from the aqueous solution by reducing their corresponding metal salts under suitable conditions. The experimental conditions including the type and concentration of protective agent, feeding order and the pH of the solution that influence the average particle size have been studied in detail. Transmission electron microscopy (TEM)indicates that the shape of those bimetallic nano-cluster particles is spheroid. The alloy structure has been shown by X-ray powder diffraction (XRD). The X-ray photoelectron spectroscopic (XPS) data have confirmed that the nickel and cobalt in the bimetallic nano-clusters are in the zero-valence state.

  8. Structure and atomic vibrations in bimetallic Ni13 - n Al n clusters

    Science.gov (United States)

    Rusina, G. G.; Borisova, S. D.; Chulkov, E. V.

    2015-04-01

    The binding energy, equilibrium geometry, and vibration frequencies in bimetallic clusters Ni13 - n Al n ( n = 0-13) have been calculated using the embedded atom method potentials. It has been shown that the icosahedral structure is the most stable in monoatomic and bimetallic clusters. A tendency of Al atoms to segregate on the cluster surface has been revealed in agreement with the experimental data. The calculations of the atomic vibrations have shown the nonmonotonic dependence of the minimum and maximum vibration frequencies of cluster atoms on its composition and the coupling of their extreme values with the most stable atomic configuration. The increase in the number of Al atoms leads to the shift of the frequency spectrum and the substantial redistribution of the localization of vibrations on the cluster atoms.

  9. 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.

  10. First principles investigations of small bimetallic PdGa clusters as catalysts for hydrogen dissociation

    Science.gov (United States)

    Kaul, Indu; Ghosh, Prasenjit

    2017-04-01

    Using first principles density functional theory based calculations, we have studied hydrogen dissociation on sub nanometer bimetallic clusters formed from d-block (Pd) and p-block (Ga) elements in gas phase to explore the feasibility of using them as cheap catalysts for hydrogen dissociation. Our calculations show that the dimers, trimers and tetramers of these clusters are thermodynamically more stable than the pure ones for all Ga concentrations. For a given cluster size, we find that the clusters containing equal amount of Pd and Ga are the most stable ones. In contrast to bulk PdGa, the contribution of Pd-d states to the highest occupied molecular orbitals of the bimetallic clusters are either very small or absent. Study of adsorption of hydrogen molecule on these clusters show that hydrogen binds in an activated form only on the Pd rich clusters. From the calculations of hydrogen dissociation barriers on tetramers of pure Pd, 25% Ga (Pd3Ga) and 50% Ga (Pd2Ga2) we find that Pd3Ga is the most efficient catalyst for hydrogen dissociation with barriers even lower than that on the PdGa surfaces.

  11. Photodissociation and spectroscopy of gas phase bimetallic clusters. Progress report for 1990--1991

    Energy Technology Data Exchange (ETDEWEB)

    Duncan, M.A.

    1991-12-31

    The general goals of this research project are (1) to synthesize novel bimetallic clusters in the gas phase; (2) to characterize their geometry, electronic structure, and chemical bonding; and (3) to compare these heterogeneous systems to corresponding pure component clusters. Clusters are synthesized by pulsed laser vaporization of solid metal rods coincident with laser photolysis of volatile metal complexes (e.g., metal carbonyls). Two techniques are used to characterize cluster properties: resonant two-photon ionization spectroscopy (R2PI) of neutral clusters and laser photodissociation spectroscopy of cluster ions. The project focuses on the selected mixtures of iron, chromium, and molybdenum with bismuth, aluminum and silver to probe a variety of heterogeneous effects in transition metal-main group metal mixtures.

  12. 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.

  13. Reactivity control of C-H bond activation over vanadium-silver bimetallic oxide cluster cations.

    Science.gov (United States)

    Li, Xiao-Na; Wu, Xiao-Nan; Ding, Xun-Lei; Xu, Bo; He, Sheng-Gui

    2012-08-27

    Vanadium-silver bimetallic oxide cluster ions (V(x)Ag(y)O(z)(+); x=1-4, y=1-4, z=3-11) are produced by laser ablation and reacted with ethane in a fast-flow reactor. A reflectron time of flight (Re-TOF) mass spectrometer is used to detect the cluster distribution before and after the reactions. Hydrogen atom abstraction (HAA) reactions are identified over VAgO(3)(+), V(2)Ag(2)O(6)(+), V(2)Ag(4)O(7)(+), V(3)AgO(8)(+), V(3)Ag(3)O(9)(+), and V(4)Ag(2)O(11)(+) ions, in which the oxygen-centered radicals terminally bonded on V atoms are active sites for the facile HAA reactions. DFT calculations are performed to study the structures, bonding, and reactivity. The reaction mechanisms of V(2)Ag(2)O(6)(+) +C(2)H(6) are also given. The doped Ag atoms with a valence state of +1 are highly dispersed at the periphery of the V(x)Ag(y)O(z)(+) cluster ions. The reactivity can be well-tuned gradually by controlling the number of Ag atoms. The steric protection due to the peripherally bonded Ag atoms greatly enhances the selectivity of the V-Ag bimetallic oxide clusters with respect to the corresponding pure vanadium oxide systems. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Magnetic properties of Co/Cu and Co/Pt bimetallic clusters

    Science.gov (United States)

    Lu, Q. L.; Zhu, L. Z.; Ma, L.; Wang, G. H.

    2005-05-01

    The ground state structures of Co/Cu and Co/Pt clusters are obtained by empirical genetic algorithm, and further optimized using the density functional theory with generalized gradient approximation. For Co 13, Pt 13 and Cu 13, they show perfect Ih symmetry. The structures of bimetallic clusters are slightly distorted configuration of Co 13. The average magnetic moment of Co 13 is 2.38 μB/atom, and that of Cu 13 and Pt 13 is nonzero. The local moments of the central atom are smaller than that of the surface ones for Co 13 and Cu 13. But the cases are not held for Pt 13. The total magnetic moment of clusters Co/Pt monotonously decreases with increasing the concentration of Pt atoms. But the things are much more complicated for clusters Co/Cu, and the reasons are discussed in detail.

  15. Synthesis and Characterization of Cluster-Derived Supported Bimetallic Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Adams, Richard D; Amiridis, Michael D

    2008-10-10

    New procedures have been developed for synthesizing di- and tri-metallic cluster complexes. The chemical properties of the new complexes have been investigated, particularly toward the activation of molecular hydrogen. These complexes were then converted into bi- and tri-metallic nanoparticles on silica and alumina supports. These nanoparticles were characterized by electron microscopy and were then tested for their ability to produce catalytic hydrogenation of unsaturated hydrocarbons and for the preferential oxidation of CO in the presence of hydrogen. The bi- and tri-metallic nanoparticles exhibited far superior activity and selectivity as hydrogenation catalysts when compared to the individual metallic components. It was found that the addition of tin greatly improved the selectivity of the catalysts for the hydrogenation of polyolefins. The addition of iron improves the catalysts for the selective oxidation of CO by platinum in the presence of hydrogen. The observations should lead to the development of lower cost routes to molecules that can be used to produce polymers and plastics for use by the general public and for procedures to purify hydrogen for use as an alternative energy in the hydrogen economy of the future.

  16. Structural selection and amorphization of small Ni-Ti bimetallic clusters.

    Science.gov (United States)

    Liu, H B; Canizal, G; Schabes-Retchkiman, P S; Ascencio, J A

    2006-06-29

    Classical molecular dynamics simulation is used for structural thermodynamic analysis of Ni-Ti bimetallic clusters. Experimental observation for the nanoclusters synthesized by the bioreduction method is used to consolidate the conclusion. The results demonstrate that Ni-Ti nanoclusters as small as 2-3 nm are not energetically favorable for common ordered geometrical arrangements such as cuboctahedron, decahedron, and icosahedron, though they can be synthesized experimentally. For the elemental distribution, Ni and Ti tend to aggregate separately. In the cases under study, eutectic-like and Ni-core/Ti-shell structures can keep their basic shape and elemental distribution during long periods of relaxation at room temperature. For other cases such as solid solution and Ti-core/Ni-shell, the structures amorphized and the elements tend to distribute uniformly even though they are at temperatures as low as room temperature. Experimental evidence was obtained by the analysis of biosynthesized nanoparticles using transmission electron microscopy techniques. This allowed determination of the partial amorphized structures of small bimetallic particles with cubic and multiple twined-like structures.

  17. Properties of two-dimensional insulators: A DFT study of bimetallic oxide CrW2O9 clusters adsorption on MgO ultrathin films

    Science.gov (United States)

    Zhu, Jia; Zhang, Hui; Zhao, Ling; Xiong, Wei; Huang, Xin; Wang, Bin; Zhang, Yongfan

    2016-08-01

    Periodic density functional theory calculations have been performed to study the electronic properties of bimetallic oxide CrW2O9 clusters adsorbed on MgO/Ag(001) ultrathin films (activities with respect to that of pure W3O9 clusters. As a consequence, present results reveal that the adsorption of bimetallic oxide CrW2O9 clusters on the MgO/Ag(001) ultrathin films provide a new perspective to tune and modify the properties and chemical reactivity of bimetallic oxide adsorbates as a function of the thickness of the oxide films.

  18. Molecular dynamics study of bimetallic nanoparticles: the case of Au xCu y alloy clusters

    Science.gov (United States)

    Rodríguez-López, J. L.; Montejano-Carrizales, J. M.; José-Yacamán, M.

    2003-10-01

    Gold and copper nanoparticles present atomic structures which are either icosahedral (I h), decahedral (D h) or octahedral (O h), depending of the particle size. Some experimental results had previously reported the stabilization of the I h phase in AuCu and AuFe clusters, being this phase predominant at 25% copper concentration in both systems. Another result reports an fcc-like and core/shell structure under similar experimental conditions and/or similar systems. In the present work, we study the possible phase conformations and thermal behavior of AuCu binary clusters using classical molecular dynamics simulations with a Sutton and Chen inter-atomic potential, addressing under which conditions the different phases mentioned above take place. To discern between the structures of bimetallic systems, the following main factors are determinant: the cluster size N, the concentration and nature of the elements in the alloy, and the annealing temperature. We choose the particles in our study closed to the sizes reported experimentally, with the cubo-octahedral symmetry as starting point. We have changed the concentration of copper from 50 to 10%, simulating an annealing process around the temperature of 750 K. We have found optimum stability of the icosahedral phase at concentrations of copper around 75 and 25% in fair agreement with experimental reports, and a trend to adopt a quasi-spherical shape with a core/shell structure at high temperatures in the cluster, just before the melting temperature.

  19. Breakdown of the Hume-Rothery Rules in Sub-Nanometer-Sized Ta-Containing Bimetallic Small Clusters

    Science.gov (United States)

    Miyajima, Ken; Fukushima, Naoya; Himeno, Hidenori; Yamada, Akira; Mafuné, Fumitaka

    2009-11-01

    The Hume-Rothery rules are empirical rules to predict the solid solubility of metals. We examined whether the rules hold for sub-nanometer-sized small particles. We prepared bimetallic cluster ions in the gas phase by a double laser ablation technique. Taking advantage of the magic compositions of the bimetallic cluster ions relating to the distinguished stabilities, the coalescence or the segregation of Ta and another element in the sub-nanometer-sized clusters was discussed. It was found that W, Nb, and Mo readily coalesce with Ta, while Ag, Al, Au, Co, Cu, Fe, Hf, Ni, Pt, Ti, and V are segregated from Ta. On the basis of these results, we concluded that the Hume-Rothery rules do not hold for sub-nanometer-sized particles.

  20. Magnetic properties of bimetallic clusters composed of Gd and transition metals

    Science.gov (United States)

    Mukherjee, Prajna; Gupta, Bikash C.; Jena, Puru

    2016-02-01

    Gadolinium, a rare earth metal, is ferromagnetic, while Mn, a transition metal atom, is antiferromagnetic in the bulk phase. Clusters of these elements, however, share some common properties; both exhibit ferrimagnetic behavior and maintain magnetic moments close to their free atomic value. Using density functional theory and generalized gradient approximation for exchange and correlation, we have studied the magnetic properties of bimetallic clusters composed of Gd and Mn to see if they show unusual behavior. The coupling between Gd and Mn spins is found to be antiferromagnetic, while that between Mn atoms is ferromagnetic. Moreover, the bonding between Gd and Mn atoms is stronger than that between the Gd atoms or Mn atoms, thus enabling the possibility of creating more stable magnetic particles. A systematic study of the magnetic and binding properties of clusters composed of Gd atom and other transition metal atoms such as V, Sc, Ti, Cr, Fe, and Co is also carried out to probe the effect of 3d-orbital occupation on magnetic coupling.

  1. Optical absorption of (Ag-Au133(SCH352 bimetallic monolayer-protected clusters

    Directory of Open Access Journals (Sweden)

    Alessandro Fortunelli

    2016-10-01

    Full Text Available The evolution of the optical absorption spectrum of bimetallic Ag-Au monolayer-protected clusters (MPC obtained by progressively doping Ag into the experimentally known structure of Au133(SR52 was predicted via rigorous time-dependent density-functional theory (TDDFT calculations. In addition to monometallic Au133(SR52 and Ag133(SR52 species, 5 different (Ag-Au133(SR52 homotops were considered with varying Ag content and site positioning, and their electronic structure and optical response were analyzed in terms of Projected Density Of States (PDOS, the induced or transition electron density, and Transition Component Maps (TCM at selected excitation energies. It was found that Ag doping led to the effects rather different from those encountered in bare metal clusters. And it was also observed that Ag doping could produce structured spectral features, especially in the 3–4 eV range but also in the optical region if Ag atoms were located in the sub-staple region, as rationalized by the accompanying electronic analysis. Additionally, Au doping into the staples of Ag-rich MPC also gave rise to a more homogeneous induced electron density. These findings show the great sensitivity of the electronic response of MPC nanoalloy systems to the exact location of the alloying sites.

  2. Effects of bimetallic doping on small cyclic and tubular boron clusters: B7M2 and B14M2 structures with M = Fe, Co.

    Science.gov (United States)

    Pham, Hung Tan; Nguyen, Minh Tho

    2015-07-14

    Using density functional theory with the TPSSh functional and the 6-311+G(d) basis set, we extensively searched for the global minima of two metallic atoms doped boron clusters B6M2, B7M2, B12M2 and B14M2 with transition metal element M being Co and Fe. Structural identifications reveal that B7Co2, B7Fe2 and B7CoFe clusters have global minima in a B-cyclic motif, in which a perfectly planar B7 is coordinated with two metallic atoms placed along the C7 axis. The B6 cluster is too small to form a cycle with the presence of two metals. Similarly, the B12 cluster is not large enough to stabilize the metallic dimer within a double ring 2 × B6 tube. The doped B14M2 clusters including B14Co2, B14Fe2 and B14CoFe have a double ring 2 × B7 tubular shape in which one metal atom is encapsulated by the B14 tube and the other is located at an exposed position. Dissociation energies demonstrate that while bimetallic cyclic cluster B7M2 prefers a fragmentation channel that generates the B7 global minimum plus metallic dimer, the tubular structure B14M2 tends to dissociate giving a bimetallic cyclic structure B7M2 and a B@B6 cluster. The enhanced stability of the bimetallic doped boron clusters considered can be understood from the stabilizing interactions between the anti-bonding MOs of metal-metal dimers and the levels of a disk aromatic configuration (for bimetallic cyclic structures), or the eigenstates of the B14 tubular form (in case of bimetallic tubular structure).

  3. Coordination polymer template synthesis of hierarchical MnCo2O4.5 and MnNi6O8 nanoparticles for electrochemical capacitors electrode

    Science.gov (United States)

    Wang, Kuaibing; Xu, Jiangyan; Lu, Aimin; Shi, Ying; Lin, Zixia

    2016-08-01

    Two types of ternary metal oxides, MnCo2O4.5 and MnNi6O8 nanoparticles have been separately synthesized through chemical transformation from the corresponding bimetallic coordination polymer particles precursor under high-heating conditions. Series of electrochemical measurements are performed to examine the MnCo2O4.5 and MnNi6O8 electrodes, and the result shows that MnCo2O4.5 structure, especially for Mn/Co-600, has much higher capacitance than that of MnNi6O8 nanoparticles, indicating MnCo2O4.5 electrode is more suitable for applying in neutral electrolyte system. The Mn/Co-600 electrode exhibits a specific capacitance of 158 F g-1 at 5 mV s-1, good rate capability of 53.8% with a 20 times current density increase, good cycle performance (92.9% capacitance retention after 1000 cycles) and high power density (a specific power of 5760 W kg-1 at 4.0 A g-1) with low charge transfer resistance value of 1.8 Ω.

  4. A theoretical analysis of bi-metallic (Cu–Agn = 1 − 7 nano alloy clusters invoking DFT based descriptors

    Directory of Open Access Journals (Sweden)

    Ranjan Prabhat

    2015-12-01

    Full Text Available Due to its large scale applications in the real field, the study of bi-metallic nano-alloy clusters is an active field of research. Though a number of experimental reports are available in this domain, a deep theoretical insight is yet to receive. Among several nano-clusters, the compound formed between Cu–Ag has gained a large importance due to its remarkable optical property. Density Functional Theory (DFT is one of the most popular approaches of quantum mechanics to study the electronic properties of materials. Conceptually, DFT based descriptors have turned to be indispensable tools for analyzing and correlating the experimental properties of compounds. In this venture, we have analyzed the experimental properties of the (Cu–Agn = 1 − 7 nano-alloy clusters invoking DFT methodology. A nice correlation has been found between optical properties of the aforesaid nano-clusters with our evaluated theoretical descriptors. The similar agreement between experimental bond length and computed data is also reflected in this analysis. Beside these, the effect of even-odd alternation behavior of nano compounds on the HOMO-LUMO gap is very important in our computation. It is probably the first attempt to establish such type of correlation.

  5. Molecular dynamics simulations of the structural and dynamic properties of graphite-supported bimetallic transition metal clusters

    Science.gov (United States)

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

    2005-11-01

    Molecular dynamics simulations were carried out for Pd-Pt , Pd-Rh , and Pd-Cu nanoclusters supported on a static graphite substrate using the quantum Sutton-Chen potential for the metal-metal interactions. The graphite substrate was represented as layers of fixed carbons sites and modeled with the Lennard-Jones potential model. Metal-graphite interaction potentials obtained by fitting experimental cohesive energies were utilized. Monte Carlo simulations employing the bond order simulation model were used to generate initial configurations. The melting temperatures for bimetallic nanoclusters of varying composition were estimated based on variations in thermodynamic properties such as potential energy and heat capacity. Melting transition temperatures were found to decrease with increasing Cu (for Pd-Cu ) and Pd (for Pd-Pt and Pd-Rh ) concentrations and are at least 100to200K higher than those of the same-sized free clusters. Density distributions perpendicular to the surface and components of the velocity autocorrelation functions in the plane of the surface indicate that one of the metals in the bimetallic nanoclusters wets the graphite surface more, and that this weak graphite substrate is able to structure the melted fluid in the first few monolayers. The wetting characteristics are dictated by the delicate balance between metal-metal and metal-graphite interactions. Components of velocity-autocorrelation functions characterizing diffusion of constituent atoms in these bimetallics suggest greater out-of-plane movement, which increases with Cu (for Pd-Cu ) and Pd (for Pd-Rh and Pd-Pt ) concentrations. Deformation parameters showed that the core (Pd in Pd-Cu , Rh in Pd-Rh and Pt in Pd-Pt ) atoms diffuse out and the surface-segregated (Cu in Pd-Cu , Pd in Pd-Rh and Pd-Pt ) atoms diffuse into the nanoclusters upon melting. Near linear dependence of melting temperature on composition was found for unsupported clusters in our recent work, which results from the

  6. Determination of structures, stabilities, and electronic properties for bimetallic cesium-doped gold clusters: a density functional theory study.

    Science.gov (United States)

    Cheng, Lu; Xiao-Yu, Kuang; Zhi-Wen, Lu; Ai-Jie, Mao; Yan-Ming, Ma

    2011-08-25

    The equilibrium geometric structures, stabilities, and electronic properties of bimetallic Au(n)Cs (n = 1-10) and pure gold Au(n) (n ≤ 11) clusters have been systematically investigated by using density functional theory with meta-generalized gradient approximation. The optimized geometries show that one Au atom capped on Au(n-1)Cs structures and Cs atom capped Au(n) structures for different sized Au(n)Cs (n = 1-10) clusters are two dominant growth patterns. Theoretical calculated results indicate that the most stable isomers have three-dimensional structures at n = 4 and 6-10. Averaged atomic binding energies, fragmentation energies, and second-order difference of energies exhibit a pronounced even-odd alternations phenomenon. The same even-odd alternations are found in the highest occupied-lowest unoccupied molecular orbital gaps, vertical ionization potential, vertical electron affinity, and hardnesses. In addition, it is found that the charge in corresponding Au(n)Cs clusters transfers from the Cs atom to the Au(n) host in the range of 0.851-1.036 electrons.

  7. Double magnetic resonance in MnCO3

    Directory of Open Access Journals (Sweden)

    Yu.M. Bunkov, A.V. Klochkov, T.R. Safin, K.R. Safiullin, M.S. Tagirov

    2015-12-01

    Full Text Available Results of experiments on MnCO3 investigations by double magnetic resonance are presented. Additional mode of oscillation has been observed in a created Bose-Einstein condensation of magnons state in MnCO3. The properties of observed signals are similar to Goldstone modes.

  8. Structural and magnetic properties of Fe7- n Pt n with n = 0, 1, 2, . . . 7, bimetallic clusters

    Science.gov (United States)

    Ponce-Tadeo, A. P.; Morán-López, J. L.; Ricardo-Chavez, J. L.

    2016-11-01

    An exhaustive study of the structural and magnetic properties of Fe7- n Pt n with n = 0, 1, 2, …7, bimetallic clusters is presented. Based on ab initio density functional theory that includes spin-orbit coupling (SOC) and graph theory, the ground state geometry, the local chemical order, and the orbital and spin magnetic moments are calculated. We show how the systems evolves from the 3-d Fe to the quasi-planar Pt clusters. These calculations show that SOC are necessary to describe correctly the composition dependence of the binding energy of these nanoalloys. We observe that the ground state geometries on the Fe rich side resemble the fcc structure adopted by bulk samples. Furthermore, we observe how the spin and orbital magnetic moments depend on the chemical concentration and chemical order. Based on these results, we estimated the magnetic anisotropy energy and found that the largest values correspond to some of the most symmetric structures, Fe5Pt2 and FePt6. To determine the degree of non-collinearity, we define an index that shows that in FePt6 the total magnetic moments, on each atom, are the less collinear.

  9. Computational study on the molecular structures and photoelectron spectra of bimetallic oxide clusters MW2O9(-/0) (M=V, Nb, Ta).

    Science.gov (United States)

    Chen, Wen-Jie; Zhang, Chang-Fu; Zhang, Xian-Hui; Zhang, Yong-Fan; Huang, Xin

    2013-05-15

    Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are carried out to investigate the electronic and structural properties of a series of bimetallic oxide clusters MW2O9(-/0) (M=V, Nb, Ta). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level yield singlet and doublet ground states for the bimetallic anionic and neutral clusters, respectively. All the clusters present the six-membered ring structures with different symmetries, except that the TaW2O9(-) cluster shows a chained style with a penta-coordinated tantalum atom. Spin density analyses reveal oxygen radical species in all neutral clusters, consistent with their structural characteristics. Moreover, additional calculations are performed to study the oxidation reaction of CO molecule with the W3O9(+) cation and the isoelectronic VW2O9 cluster, and results indicate that the introduction of vanadium at tungsten site can efficiently improve the oxidation reactivity. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Computational study on the molecular structures and photoelectron spectra of bimetallic oxide clusters MWO9-/0 (M = V, Nb, Ta)

    Science.gov (United States)

    Chen, Wen-Jie; Zhang, Chang-Fu; Zhang, Xian-Hui; Zhang, Yong-Fan; Huang, Xin

    2013-05-01

    Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are carried out to investigate the electronic and structural properties of a series of bimetallic oxide clusters MWO9-/0 (M = V, Nb, Ta). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level yield singlet and doublet ground states for the bimetallic anionic and neutral clusters, respectively. All the clusters present the six-membered ring structures with different symmetries, except that the TaWO9- cluster shows a chained style with a penta-coordinated tantalum atom. Spin density analyses reveal oxygen radical species in all neutral clusters, consistent with their structural characteristics. Moreover, additional calculations are performed to study the oxidation reaction of CO molecule with the WO9+ cation and the isoelectronic VW2O9 cluster, and results indicate that the introduction of vanadium at tungsten site can efficiently improve the oxidation reactivity.

  11. Atomic, electronic, and magnetic properties of bimetallic ZrCo clusters: A first-principles study

    Science.gov (United States)

    Chattaraj, D.; Bhattacharya, Saswata; Dash, Smruti; Majumder, C.

    2016-09-01

    Here, we report the atomic, electronic, and magnetic structures of small ZrmCon (m + n = 2, 4, 6, and 8) alloy clusters based on spin-polarized density functional theory under the plane wave based pseudo-potential approach. The ground state geometry and other low-lying stable isomers of each cluster have been identified using the cascade genetic algorithm scheme. On the basis of the relative energy, it is found that Zr2Co2 (for tetramer), Zr3Co3 (for hexamer), and Zr4Co4 (for octamer) are the most stable isomers than others. In order to underscore the hydrogen storage capacity of these small clusters, the hydrogen adsorption on the stable ZrmCon (m + n = 2, 4, 6, and 8) clusters has also been studied. The electronic structures of ZrmCon clusters with and without adsorbed hydrogen are described in terms of density of states spectra and charge density contours.

  12. 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.

  13. Two-dimensional magic numbers in mass abundances of photofragmented bimetallic clusters

    CERN Document Server

    Janssens, E; Neukermans, S; Silverans, R E; Lievens, P

    2003-01-01

    The stability of cationic gold clusters doped with one transition metal atom was investigated by a mass spectrometric analysis of fragments resulting from high fluence irradiation of a cluster beam. Strongly enhanced abundances are found for Au sub 5 X sup + , X = V, Mn, Cr, Fe, Co, Zn, which implies that these species are far more stable towards fragmentation than their neighbouring cluster sizes. Here we interpret the enhanced stability of these clusters within a shell model approach for two-dimensional (2D) systems: the number of delocalized electrons in Au sub 5 X sup + is six, which is a magic number for 2D systems. Quantum chemical calculations for Au sub N Zn sup + (N = 2-6) predict planar structures that are stabilized by the influence of the dopant atom. Also, the main features of the calculated molecular orbitals are well reproduced by a simple electron-in-a-box model. The present report constitutes the first observation of 2D magic numbers in size dependent properties of metal clusters.

  14. Ce@Au14: A Bimetallic Superatom Cluster with 18-Electron Rule

    Science.gov (United States)

    Gao, Yang; Liu, Xizhe; Wang, Zhigang

    2016-09-01

    Doping of gold clusters and nanoparticles has received substantial attention due to their ability to encapsulate atoms and molecules. Here, the geometric and electronic properties of the cerium-encapsulated nanocage Ce@Au14 are reported using density functional theory. Calculated results show that its ground electronic state is a singlet state and conforms to the superatomic 18-electron configuration of 1S 21P 61D 10 jellium state, both primarily involving the bonding interaction between s- and d-shell atomic orbitals of the Ce atom and superatomic orbitals of the hollow polyhedral Au14 cage. In addition, it should be noted that f electrons in rare earth atoms trend to retain their localized state, and their doping in gold clusters could easily lead to clusters with large magnetic moments. However, in the case of superatom clusters, the f-shell electrons will be the preferential arrangement at the unfilled d-shell to satisfy the superatomic electron structure. Further analysis of the electronic structure also proves that the unoccupied 1F superatomic orbitals mainly originate from the contribution of the 4f-shell. As a consequence, this work provides a theoretical basis for the future design and synthesis of f-elements-encapsulated gold nanoclusters.

  15. Ce@Au14: A Bimetallic Superatom Cluster with 18-Electron Rule

    Science.gov (United States)

    Gao, Yang; Liu, Xizhe; Wang, Zhigang

    2017-07-01

    Doping of gold clusters and nanoparticles has received substantial attention due to their ability to encapsulate atoms and molecules. Here, the geometric and electronic properties of the cerium-encapsulated nanocage Ce@Au14 are reported using density functional theory. Calculated results show that its ground electronic state is a singlet state and conforms to the superatomic 18-electron configuration of 1 S 21 P 61 D 10 jellium state, both primarily involving the bonding interaction between s- and d-shell atomic orbitals of the Ce atom and superatomic orbitals of the hollow polyhedral Au14 cage. In addition, it should be noted that f electrons in rare earth atoms trend to retain their localized state, and their doping in gold clusters could easily lead to clusters with large magnetic moments. However, in the case of superatom clusters, the f-shell electrons will be the preferential arrangement at the unfilled d-shell to satisfy the superatomic electron structure. Further analysis of the electronic structure also proves that the unoccupied 1 F superatomic orbitals mainly originate from the contribution of the 4 f-shell. As a consequence, this work provides a theoretical basis for the future design and synthesis of f-elements-encapsulated gold nanoclusters.

  16. The effect of metal cluster deposition route on structure and photocatalytic activity of mono- and bimetallic nanoparticles supported on TiO2 by radiolytic method

    Science.gov (United States)

    Klein, Marek; Nadolna, Joanna; Gołąbiewska, Anna; Mazierski, Paweł; Klimczuk, Tomasz; Remita, Hynd; Zaleska-Medynska, Adriana

    2016-08-01

    TiO2 (P25) was modified with small and relatively monodisperse mono- and bimetallic clusters (Ag, Pd, Pt, Ag/Pd, Ag/Pt and Pd/Pt) induced by radiolysis to improve its photocatalytic activity. The as-prepared samples were characterized by X-ray fluorescence spectrometry (XRF), photoluminescence spectrometry (PL), diffuse reflectance spectroscopy (DRS), X-ray powder diffractometry (XRD), scanning transition electron microscopy (STEM) and BET surface area analysis. The effect of metal type (mono- and bimetallic modification) as well as deposition method (simultaneous or subsequent deposition of two metals) on the photocatalytic activity in toluene removal in gas phase under UV-vis irradiation (light-emitting diodes- LEDs) and phenol degradation in liquid phase under visible light irradiation (λ > 420 nm) were investigated. The highest photoactivity under Vis light was observed for TiO2 co-loaded with platinum (0.1%) and palladium (0.1%) clusters. Simultaneous addition of metal precursors results in formation of larger metal nanoparticles (15-30 nm) on TiO2 surface and enhances the Vis-induced activity of Ag/Pd-TiO2 up to four times, while the subsequent metal ions addition results in formation of metal particle size ranging from 4 to 20 nm. Subsequent addition of metal precursors results in formation of BNPs (bimetallic nanoparticle) composites showing higher stability in four cycles of toluene degradation under UV-vis. Obtained results indicated that direct electron transfer from the BNPs to the conduction band of the semiconductor is responsible for visible light photoactivity, whereas superoxide radicals (such as O2rad- and rad OOH) are responsible for pollutants degradation over metal-TiO2 composites.

  17. Formation of bimetallic clusters in superfluid helium nanodroplets analysed by atomic resolution electron tomography

    Science.gov (United States)

    Haberfehlner, Georg; Thaler, Philipp; Knez, Daniel; Volk, Alexander; Hofer, Ferdinand; Ernst, Wolfgang E.; Kothleitner, Gerald

    2015-10-01

    Structure, shape and composition are the basic parameters responsible for properties of nanoscale materials, distinguishing them from their bulk counterparts. To reveal these in three dimensions at the nanoscale, electron tomography is a powerful tool. Advancing electron tomography to atomic resolution in an aberration-corrected transmission electron microscope remains challenging and has been demonstrated only a few times using strong constraints or extensive filtering. Here we demonstrate atomic resolution electron tomography on silver/gold core/shell nanoclusters grown in superfluid helium nanodroplets. We reveal morphology and composition of a cluster identifying gold- and silver-rich regions in three dimensions and we estimate atomic positions without using any prior information and with minimal filtering. The ability to get full three-dimensional information down to the atomic scale allows understanding the growth and deposition process of the nanoclusters and demonstrates an approach that may be generally applicable to all types of nanoscale materials.

  18. Multiferroic behavior in Lu2MnCoO6

    Science.gov (United States)

    Zapf, Vivien; Mun, E.-D.; Ueland, B. G.; Thompson, J. D.; Singleton, J.; Gardner, J.; Yáñez-Vilar, S.; Sánchez-Anduacute; jar; , M.; Señaris-Rodriguez, M. A.; Mira, J.; Biskup, N.; Batista, C. D.

    2012-02-01

    Lu2MnCoO6 is a new member of the multiferroics with coupling between net magnetization and net electric polarization. Similar to Ca3MnCoO6, an up-up-down-down order of the magnetic spins is found that breaks spatial-inversion symmetry and creates an electric polarization. Unlike Ca3MnCoO6, the Co and Mn ions are both in a S = 3/2 state, the ordering temperature is 42 K, and the magnetic field needed to suppress electric polarization is 2 T. We present an experimental study of the multiferroic properties and spin structure including neutron diffraction, electric polarization, magnetization, dielectric constant, and specific heat measurements.

  19. A comparative study on geometries, stabilities, and electronic properties between bimetallic AgnX (X=Au, Cu; n=1-8) and pure silver clusters

    Institute of Scientific and Technical Information of China (English)

    Ding Li-Ping; Kuang Xiao-Yu; Shao Peng; Zhao Ya-Ru; Li Yah-Fang

    2012-01-01

    Using the meta-generalized gradient approximation (meta-GGA) exchange correlation TPSS functional,the geometric structures,the relative stabilities,and the electronic properties of bimetallic AgnX (X=Au,Cu; n=l-8) clusters are systematically investigated and compared with those of pure silver clusters.The optimized structures show that the transition point from preferentially planar to three-dimensional structure occurs at n =6 for the AgnAu clusters,and at n =5 for AgnCu clusters.For different-sized AgnX clusters,one X (X=Au or Cu) atom substituted Agn+1 structure is a dominant growth pattern.The calculated fragmentation energies,second-order differences in energies,and the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy gaps show interesting odd-even oscillation behaviours,indicating that Ag2,4,6,8 and Ag1,3,5,7X (X=Au,Cu) clusters keep high stabilities in comparison with their neighbouring clusters.The natural population analysis reveals that the charges transfer from the Agn host to the impurity atom except for the Ag2Cu cluster.Moreover,vertical ionization potential (VIP),vertical electronic affinity (VEA),and chemical hardness (η) are discussed and compared in depth.The same odd-even oscillations are found for the VIP and ηof the AgnX (X=Au,Cu; n=1-8) clusters.

  20. The effect of metal cluster deposition route on structure and photocatalytic activity of mono- and bimetallic nanoparticles supported on TiO{sub 2} by radiolytic method

    Energy Technology Data Exchange (ETDEWEB)

    Klein, Marek [Department of Chemical Technology, Faculty of Chemistry, Gdansk University of Technology, 80-233 Gdansk (Poland); Institute of Fluid-Flow Machinery, Polish Academy of Sciences, 80-231 Gdansk (Poland); Nadolna, Joanna, E-mail: joanna.nadolna@ug.edu.pl [Department of Chemical Technology, Faculty of Chemistry, Gdansk University of Technology, 80-233 Gdansk (Poland); Department of Environmental Technology, University of Gdansk, 80-308 Gdansk (Poland); Gołąbiewska, Anna [Department of Chemical Technology, Faculty of Chemistry, Gdansk University of Technology, 80-233 Gdansk (Poland); Mazierski, Paweł [Department of Environmental Technology, University of Gdansk, 80-308 Gdansk (Poland); Klimczuk, Tomasz [Department of Solid State Physics, Faculty of Applied Physics and Mathematics, Gdansk University of Technology, 80-233 Gdansk (Poland); Remita, Hynd [Laboratoire de Chimie Physique, CNRS-UMR 8000, Université Paris-Sud, Université Paris-Saclay, 91405 Orsay (France); CNRS, Laboratoire de Chimie Physique, UMR 8000, 91405 Orsay (France); Zaleska-Medynska, Adriana [Department of Chemical Technology, Faculty of Chemistry, Gdansk University of Technology, 80-233 Gdansk (Poland); Department of Environmental Technology, University of Gdansk, 80-308 Gdansk (Poland)

    2016-08-15

    Highlights: • Pd-Pt decorated TiO{sub 2} shows the highest activity under visible light among all. • Concurrent addition of metal precursors results in rise of BNPs size and Vis-activity. • Subsequent addition of metal precursors enhances UV–vis stability of modified TiO{sub 2}. • Superoxide radicals are responsible for pollutants degradation over BNPs-TiO{sub 2}. - Abstract: TiO{sub 2} (P25) was modified with small and relatively monodisperse mono- and bimetallic clusters (Ag, Pd, Pt, Ag/Pd, Ag/Pt and Pd/Pt) induced by radiolysis to improve its photocatalytic activity. The as-prepared samples were characterized by X-ray fluorescence spectrometry (XRF), photoluminescence spectrometry (PL), diffuse reflectance spectroscopy (DRS), X-ray powder diffractometry (XRD), scanning transition electron microscopy (STEM) and BET surface area analysis. The effect of metal type (mono- and bimetallic modification) as well as deposition method (simultaneous or subsequent deposition of two metals) on the photocatalytic activity in toluene removal in gas phase under UV–vis irradiation (light-emitting diodes- LEDs) and phenol degradation in liquid phase under visible light irradiation (λ > 420 nm) were investigated. The highest photoactivity under Vis light was observed for TiO{sub 2} co-loaded with platinum (0.1%) and palladium (0.1%) clusters. Simultaneous addition of metal precursors results in formation of larger metal nanoparticles (15–30 nm) on TiO{sub 2} surface and enhances the Vis-induced activity of Ag/Pd-TiO{sub 2} up to four times, while the subsequent metal ions addition results in formation of metal particle size ranging from 4 to 20 nm. Subsequent addition of metal precursors results in formation of BNPs (bimetallic nanoparticle) composites showing higher stability in four cycles of toluene degradation under UV–vis. Obtained results indicated that direct electron transfer from the BNPs to the conduction band of the semiconductor is responsible for

  1. Properties of two-dimensional insulators: A DFT study of bimetallic oxide CrW{sub 2}O{sub 9} clusters adsorption on MgO ultrathin films

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Jia, E-mail: jia_zhu@jxnu.edu.cn [College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022 (China); Zhang, Hui; Zhao, Ling; Xiong, Wei [College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022 (China); Huang, Xin; Wang, Bin [Department of Chemistry, Fuzhou University, Fuzhou, Fujian, 350108 (China); Zhang, Yongfan, E-mail: zhangyf@fzu.edu.cn [Department of Chemistry, Fuzhou University, Fuzhou, Fujian, 350108 (China); State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou, Fujian, 350002 (China)

    2016-08-30

    Highlights: • Completely different properties of CrW{sub 2}O{sub 9} on films compared with that on surface. • The first example of CT by electron tunneling from film to bimetallic oxide cluster. • A progressive Lewis acid site, better catalytic activities for adsorbed CrW{sub 2}O{sub 9}. - Abstract: Periodic density functional theory calculations have been performed to study the electronic properties of bimetallic oxide CrW{sub 2}O{sub 9} clusters adsorbed on MgO/Ag(001) ultrathin films (<1 nm). Our results show that after deposition completely different structures, electronic properties and chemical reactivity of dispersed CrW{sub 2}O{sub 9} clusters on ultrathin films are observed compared with that on the thick MgO surface. On the thick MgO(001) surface, adsorbed CrW{sub 2}O{sub 9} clusters are distorted significantly and just a little electron transfer occurs from oxide surface to clusters, which originates from the formation of adsorption dative bonds at interface. Whereas on the MgO/Ag(001) ultrathin films, the resulting CrW{sub 2}O{sub 9} clusters keep the cyclic structures and the geometries are similar to that of gas-phase [CrW{sub 2}O{sub 9}]{sup −}. Interestingly, we predicted the occurrence of a net transfer of one electron by direct electron tunneling from the MgO/Ag(001) films to CrW{sub 2}O{sub 9} clusters through the thin MgO dielectric barrier. Furthermore, our work reveals a progressive Lewis acid site where spin density preferentially localizes around the Cr atom not the W atoms for CrW{sub 2}O{sub 9}/MgO/Ag(001) system, indicating a potentially good bimetallic oxide for better catalytic activities with respect to that of pure W{sub 3}O{sub 9} clusters. As a consequence, present results reveal that the adsorption of bimetallic oxide CrW{sub 2}O{sub 9} clusters on the MgO/Ag(001) ultrathin films provide a new perspective to tune and modify the properties and chemical reactivity of bimetallic oxide adsorbates as a function of the thickness

  2. Reactivity studies of group 15 Zintl ions towards homoleptic post-transition metal organometallics: a 'bottom-up' approach to bimetallic molecular clusters.

    Science.gov (United States)

    Knapp, Caroline; Zhou, Binbin; Denning, Mark S; Rees, Nicholas H; Goicoechea, Jose M

    2010-01-14

    Reactions between ethylenediamine (en) solutions of the intermetallic Zintl phases K(3)E(7) (E = P, As) and a series of homoleptic post-transition metal organometallics such as Cu(5)(Mes)(5), M(C(6)H(5))(2) (M = Zn, Cd) and In(C(6)H(5))(3) have yielded a family of novel bimetallic cluster anions. These new species were isolated as [K(2, 2,2-crypt)](+) salts in [K(2,2,2-crypt)](4)Cu(2)E(14) (E = P (1), As (2)), [K(2,2,2-crypt)](4)ZnE(14) (E = P (3), As (4)), [K(2,2,2-crypt)](4)CdP(14) x 6py (5) and [K(2,2,2-crypt)](2)E(7)InPh(2) (E = P (6), As (7)). Species 2, 3, 5 and 6 were crystallographically characterised by single-crystal X-ray diffraction. The stability of all of the cluster anions in solution was confirmed by electrospray mass-spectrometry and by (1)H, (13)C{(1)H} and (31)P{(1)H} NMR spectroscopy when possible.

  3. The geometrical structure, electronic structure and magnetism of bimetallic AunM2 (n=1, 2; M=Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd) clusters

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The geometrical structure, stability, magnetism, and electronic structure of bimetallic clusters AuM2 and Au2M2, where M are 4d transition metal elements, are investigated systematically by using the first-principles method based on density functional theory. The calculation results show that there is a large amount of low-energy isomers with the very similar structure. AuM2 and Au2M2 clusters display dramatic magnetism. The magnetic moment of the 4d element is either enhanced or weakened with respect to the bulk value, which is largely dependent on the orbital exchange-splitting.

  4. Critical field of two-dimensional superconducting Sn1-x/Six bimetallic composite cluster assembled films with energetic cluster impact deposition

    Science.gov (United States)

    Kurokawa, Yuichiro; Hihara, Takehiko; Ichinose, Ikuo

    2013-05-01

    Sn1-x/Six cluster assembled films have been prepared by an energetic cluster impact deposition using a plasma-gas-condensation cluster beam deposition apparatus. Transmission electron microscope images indicated that individual clusters have composite morphologies, where Sn and Si were separated from each other. The superconducting critical magnetic fields, Hc, of Sn1-x/Six cluster assembled films were measured and found to be much higher than the critical magnetic field of the bulk Sn. We estimated the Hc values by using a theory of the superconducting thin film. The estimated values are in good agreement with the experiments, indicating that the Sn1-x/Six cluster assembled films can be regarded as a two-dimensional system although thickness, t, of Sn1-x/Six cluster assembled films (t ≈ 1000 nm) is thicker than conventional superconducting thin film (t < 100 nm).

  5. Dual-phase spinel MnCo2O4 and spinel MnCo2O4/nanocarbon hybrids for electrocatalytic oxygen reduction and evolution.

    Science.gov (United States)

    Ge, Xiaoming; Liu, Yayuan; Goh, F W Thomas; Hor, T S Andy; Zong, Yun; Xiao, Peng; Zhang, Zheng; Lim, Suo Hon; Li, Bing; Wang, Xin; Liu, Zhaolin

    2014-08-13

    Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential reactions for energy-storage and -conversion devices relying on oxygen electrochemistry. High-performance, nonprecious metal-based hybrid catalysts are developed from postsynthesis integration of dual-phase spinel MnCo2O4 (dp-MnCo2O4) nanocrystals with nanocarbon materials, e.g., carbon nanotube (CNT) and nitrogen-doped reduced graphene oxide (N-rGO). The synergic covalent coupling between dp-MnCo2O4 and nanocarbons effectively enhances both the bifunctional ORR and OER activities of the spinel/nanocarbon hybrid catalysts. The dp-MnCo2O4/N-rGO hybrid catalysts exhibited comparable ORR activity and superior OER activity compared to commercial 30 wt % platinum supported on carbon black (Pt/C). An electrically rechargeable zinc-air battery using dp-MnCo2O4/CNT hybrid catalysts on the cathode was successfully operated for 64 discharge-charge cycles (or 768 h equivalent), significantly outperforming the Pt/C counterpart, which could only survive up to 108 h under similar conditions.

  6. Bimetallic cages

    Science.gov (United States)

    Fournier, René; Afzal-Hussain, Sabeen

    2013-02-01

    We report the results of density functional theory for 39 clusters AxBy (x + y = 10 or 12) where A and B are metals from group 1, 2, 11, 12, 13, or 14 of the periodic table. The chemical compositions were chosen to satisfy an electronic shell closing criterion. We performed an unbiased search for the global minimum (GM) by taboo search in descriptor space in each case. Eight of the 39 putative GM are cages even though none of the clusters contains gold, a metal with a well known propensity to form cages. These cages are large enough to accommodate a dopant atom with an atomic radius varying between 0.7 Å and 1.2 Å. The chemical compositions most likely to produce cages have an element of group 11 alloyed with an element of group 2, 12, or 13.

  7. Electrochemical performance enhancement in MnCo2O4 nanoflake/graphene nanoplatelets composite

    Science.gov (United States)

    Al-Rubaye, Shaymaa; Rajagopalan, Ranjusha; Subramaniyam, Chandrasekar M.; Yu, Zheyin; Dou, Shi Xue; Cheng, Zhenxiang

    2016-08-01

    The synthesis and characterization of MnCo2O4 nanoflake/graphene nanoplatelets composite is reported here for high performance supercapacitor electrode applications. The MnCo2O4 nanoflakes with different morphologies were synthesized successfully via a hydrothermal technique by changing the amount of NH4F. The MnCo2O4 nanoflakes in combination with the graphene nanoplatelets was deposited on Ni foam using an electrophoretic deposition technique. The as prepared composite electrode showed superior performance in terms of specific capacitance and cycling stability, as compared to the pristine MnCo2O4 system, due to the enhanced electronic conductivity resulted from bond formation between carbon and MnCo2O4. A high specific capacitance of ∼1268 F g-1 was observed at 1 mV s-1 scan rate. Noteworthy cycling stability was observed even at the end of 10,000 cycles of consecutive charging and discharging at a current density of 7.81Ag-1.

  8. Microstructural and electrical characterization of Mn-Co spinel protective coatings for solid oxide cell interconnects

    DEFF Research Database (Denmark)

    Molin, S.; Sabato, A. G.; Bindi, M.

    2017-01-01

    Electrophoretic deposition, thermal co-evaporation and RF magnetron sputtering methods are used for the preparation of Mn-Co based ceramic coatings for solid oxide fuel cell steel interconnects. Both thin and relatively thick coatings (1–15 μm) are prepared and characterised for their potential...... protective behaviour. Mn-Co coated Crofer22APU samples are electrically tested for 5000 h at 800 °C under a 500 mA cm−2 current load to determine their Area Specific Resistance increase due to a growing chromia scale. After tests, samples are analysed by scanning and transmission electron microscopy....... Analysis is focused on the potential chromium diffusion to or through the coating, the oxide scale thickness and possible reactions at the interfaces. The relationships between the coating type, thickness and effectiveness are reviewed and discussed. Out of the three Mn-Co coatings compared in this study...

  9. Electrospun graphene decorated MnCo2O4 composite nanofibers for glucose biosensing.

    Science.gov (United States)

    Zhang, Yuting; Liu, Shuai; Li, Yu; Deng, Dongmei; Si, Xiaojing; Ding, Yaping; He, Haibo; Luo, Liqiang; Wang, Zhenxin

    2015-04-15

    Graphene decorated MnCo2O4 composite nanofibers (GMCFs) were synthesized by electrospinning and subsequent calcination in an Ar atmosphere. The structural and morphological characterizations of GMCFs were performed using X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, energy-dispersive spectroscopy, scanning electron microscopy and transmission electron microscopy. The synthesized GMCFs combine the catalytic activity of spinel-type MnCo2O4 with the remarkable conductivity of graphene. In addition, electrospinning can process MnCo2O4 materials into nanosized architectures with large surface area to prevent magnetic nanoparticles from aggregating. The obtained GMCFs were applied as a novel platform for glucose biosensing. Electrochemical studies show that the developed biosensor exhibits excellent electrocatalytic activity towards glucose oxidation over a wide linear range of 0.005-800µM with a low detection limit of 0.001µM.

  10. Chemical effect on the K shell fluorescence yield of Fe, Mn, Co, Cr and Cu compounds

    Indian Academy of Sciences (India)

    U Turgut

    2004-11-01

    Chemical effects on the K shell fluorescence yields of Fe, Mn, Co, Cr and Cu compounds were investigated. Samples were excited using 59.5 keV energy photons from a 241Am radioisotope source. K X-rays emitted by samples were counted by a Si(Li) detector with a resolution 160 eV at 5.9 keV. Chemical effects on the K shell fluorescence yields (K) for Fe, Mn, Co, Cr and Cu compounds were observed. The values are compared with theoretical, semiempirical fit and experimental ones for the pure elements.

  11. Biosensors Incorporating Bimetallic Nanoparticles

    Directory of Open Access Journals (Sweden)

    John Rick

    2015-12-01

    Full Text Available This article presents a review of electrochemical bio-sensing for target analytes based on the use of electrocatalytic bimetallic nanoparticles (NPs, which can improve both the sensitivity and selectivity of biosensors. The review moves quickly from an introduction to the field of bio-sensing, to the importance of biosensors in today’s society, the nature of the electrochemical methods employed and the attendant problems encountered. The role of electrocatalysts is introduced with reference to the three generations of biosensors. The contributions made by previous workers using bimetallic constructs, grouped by target analyte, are then examined in detail; following which, the synthesis and characterization of the catalytic particles is examined prior to a summary of the current state of endeavor. Finally, some perspectives for the future of bimetallic NPs in biosensors are given.

  12. Biosensors Incorporating Bimetallic Nanoparticles.

    Science.gov (United States)

    Rick, John; Tsai, Meng-Che; Hwang, Bing Joe

    2015-12-31

    This article presents a review of electrochemical bio-sensing for target analytes based on the use of electrocatalytic bimetallic nanoparticles (NPs), which can improve both the sensitivity and selectivity of biosensors. The review moves quickly from an introduction to the field of bio-sensing, to the importance of biosensors in today's society, the nature of the electrochemical methods employed and the attendant problems encountered. The role of electrocatalysts is introduced with reference to the three generations of biosensors. The contributions made by previous workers using bimetallic constructs, grouped by target analyte, are then examined in detail; following which, the synthesis and characterization of the catalytic particles is examined prior to a summary of the current state of endeavor. Finally, some perspectives for the future of bimetallic NPs in biosensors are given.

  13. 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.

  14. Giant magnetocaloric effect near room temperature in the off-stoichiometric Mn-Co-Ge alloy

    Science.gov (United States)

    Sharma, V. K.; Manekar, M. A.; Srivastava, Himanshu; Roy, S. B.

    2016-12-01

    We report a giant magnetocaloric effect near room temperature in an off-stoichiometric Mn-Co-Ge alloy, across the magnetostructural transition. The isothermal entropy change accompanying this transition has a peak value of nearly 40 J kg-1 K-1 near 297 K for a field excursion of 70 kOe, and a refrigerant capacity of 270 J kg-1 with the hot end at 302.5 K and cold end at 293.5 K. We also present an experimental protocol to avoid spurious peaks in the magnetocaloric effect across a sharp first order magnetostructural transition, not confined to Mn-Co-Ge alone, where metastability during the transition could influence the measured magnetization and thus the estimated entropy change. The estimated entropy change in the present off-stoichiometric Mn-Co-Ge alloy is possibly the highest reported value near room temperature in undoped Mn-Co-Ge alloys and underlines the potential of the alloy for technological applications in room temperature magnetic refrigeration.

  15. Giant magnetocaloric effect in MnCoGe with minimal Ga substitution

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Danlu [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Nie, Zhihua, E-mail: zhihua_nie@yahoo.com [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Wang, Zilong; Huang, Lian; Zhang, Qinghua [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Wang, Yan-dong, E-mail: ydwang@mail.neu.edu.cn [The State Key Laboratory of Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083 (China)

    2015-08-01

    The effects of Ga-doping on the phase transition behaviors and magnetocaloric properties of MnCoGe alloys are systematically investigated through calorimetry and magnetic measurements. The magneto-structural coupling between the structural and magnetic transitions is achieved in the MnCoGe{sub 1–x}Ga{sub x} alloys by decreasing the structural transition temperature via Ga substitution. An 80 K Curie-temperature window is established between Curie temperatures of austenite and martensite phases. Within the window, a magnetic entropy change of 34 J kg{sup −1} K{sup −1} can be obtained near room temperature under the application of a 5 T magnetic field. - Highlights: • The magnetostructural coupling is achieved in MnCoGe alloys with Ga substitution. • An 80 K Curie-temperature window is established in MnCoGe{sub 1–x}Ga{sub x} alloys. • A magnetic entropy change of 34 J kg{sup −1} K{sup −1} is obtained under magnetic field of 5 T.

  16. Enhanced exchange anisotropy in IrMn/CoFeB systems and its correlation with uncompensated interfacial spins

    DEFF Research Database (Denmark)

    Du, Yuqing; Pan, Genhua; Moate, Roy;

    2010-01-01

    Bottom pinned exchange bias systems of IrMn/CoFe and IrMn/CoFeB on CoFe seed layers were studied. Enhanced exchange anisotropy has been observed for IrMn/CoFeB samples annealed at 350 °C. The ferromagnetic and antiferromagnetic layers of both samples are polycrystalline and textured {110} for the......Bottom pinned exchange bias systems of IrMn/CoFe and IrMn/CoFeB on CoFe seed layers were studied. Enhanced exchange anisotropy has been observed for IrMn/CoFeB samples annealed at 350 °C. The ferromagnetic and antiferromagnetic layers of both samples are polycrystalline and textured {110......} for the CoFe and CoFeB, and {111} for IrMn. Results demonstrated that the enhanced exchange anisotropy in the IrMn/CoFeB system is closely associated with the increased uncompensated interfacial spins as evidenced by the enhanced Mn x-ray magnetic circular dichroism (XMCD) signal strength. A quantitative...

  17. Structural, magnetic and dielectric properties of polyaniline/MnCoFe{sub 2}O{sub 4} nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Chitra, Palanisamy [PG and Research Department of Chemistry, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore 641020, Tamil Nadu (India); Muthusamy, Athianna, E-mail: muthusrkv@gmail.com [PG and Research Department of Chemistry, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore 641020, Tamil Nadu (India); Jayaprakash, Rajan [Department of Physics, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore 641020, Tamil Nadu (India)

    2015-12-15

    Ferromagnetic PANI containing MnCoFe{sub 2}O{sub 4} nanocomposites were synthesized by in-situ chemical polymerization of aniline incorporated MnCoFe{sub 2}O{sub 4} nanoparticles (20%, 10% w/w of fine powders) with and without ultrasonic treatment. The MnCoFe{sub 2}O{sub 4} nanoparticles were synthesized by auto combustion method. The PANI/MnCoFe{sub 2}O{sub 4} nanocomposites were characterized with Fourier transform infrared (FTIR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The average particle size of the resulting PANI/MnCoFe{sub 2}O{sub 4} nanocomposites was confirmed from the TEM and XRD analysis. The structure and morphology of the composites were confirmed by FT-IR spectroscopy, XRD and SEM. In addition, the electrical and magnetic properties of the nanocomposites were investigated. The PANI/MnCoFe{sub 2}O{sub 4} nanocomposites under applied magnetic field exhibited the hysteresis loops of ferromagnetic nature at room temperature. The variation of Dielectric constant, Dielectric loss, and AC conductivity of PANI/MnCoFe{sub 2}O{sub 4} nanocomposites at room temperature as a function of frequency in the range 50 Hz–5 MHz has been studied. Effect of ultrasonication on the PANI/MnCoFe{sub 2}O{sub 4} nanocomposites was also investigated. - Highlights: • An auto-combustion method support to prepare less size of particles. • The particle size influences more on dielectric property. • Effect of ultrasonication on the PANI/MnCoFe{sub 2}O{sub 4} was also investigated.

  18. Magnetocaloric Effect in MnCo_(1-x)Al_xGe Compounds

    Institute of Scientific and Technical Information of China (English)

    Weiguang Zhang; O. Tegus; Yongli Wu; Yirgeltu; Huanying Yan; Song Lin

    2009-01-01

    The effects of substitution of Al for Co on magnetic and magnetocaloric properties of MnCo_(1-x)Al_xGe (x=0.00, 0.03, 0.05, 0.08, 0.10, 0.13, 0.15, and 0.20) compounds have been investigated by X-ray diffraction (XRD) and magnetization measurements. XRD exhibits that MnCo_(1-x)Al_xGe compounds crystallize in the orthorhombic TiNiSi-type structure for x0.03. Magnetic measurements show that the Curie temperature can be tuned between 286 and 347 K by changing the Co/Al ratio. The maximum magnetic entropy change determined from the isothermal magnetization measurement by Maxwell relation reaches 1.52 J/(kgK) for x=0.08 in a field change from 0 to 1.5 T around 310 K.

  19. Intra-ring haptotropic rearrangements of Mn(CO3 in fluorenyl ligands

    Directory of Open Access Journals (Sweden)

    Souhila Laib

    2017-02-01

    Full Text Available Geometric parameters, and intra-ring haptotropic rearrangements π–π (intra-ring-HRs ŋ5⇌ŋ3 of the manganesetricarbonyl complexes (ŋ5-9-R-C13H8Mn(CO3, R = But and Ph in 18e zero-valence are carried out using density functional theory DFT at PBE/TZP level. The calculated activation barriers to ŋ5⇌ŋ3 intra-ring HR in (ŋ5-9-R-C13H8Mn(CO3, R = But and Ph are (28.5 and 69.5 kcal.mol−1 respectively. The compute of HOMA and FLU indexes indicates the reduction of aromaticity when going from free to coordinated complex. The energy decomposition analysis reveals the dominant ionic character in manganese–Cp bond in the presence of covalent contribution.

  20. High-pressure compressibility and vibrational properties of (Ca,Mn)CO 3

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jin; Caracas, Razvan; Fan, Dawei; Bobocioiu, Ema; Zhang, Dongzhou; Mao, Wendy L.

    2016-12-01

    Knowledge of potential carbon carriers such as carbonates is critical for our understanding of the deep-carbon cycle and related geological processes within the planet. Here we investigated the high-pressure behavior of (Ca,Mn)CO3 up to 75 GPa by synchrotron single-crystal X-ray diffraction, laser Raman spectroscopy, and theoretical calculations. MnCO3-rich carbonate underwent a structural phase transition from the CaCO3-I structure into the CaCO3-VI structure at 45–48 GPa, while CaCO3-rich carbonate transformed into CaCO3-III and CaCO3-VI at approximately 2 and 15 GPa, respectively. The equation of state and vibrational properties of MnCO3-rich and CaCO3-rich carbonates changed dramatically across the phase transition. The CaCO3-VI-structured CaCO3-rich and MnCO3-rich carbonates were stable at room temperature up to at least 53 and 75 GPa, respectively. The addition of smaller cations (e.g., Mn2+, Mg2+, and Fe2+) can enlarge the stability field of the CaCO3-I phase as well as increase the pressure of the structural transition into the CaCO3-VI phase.

  1. Sb/Mn co-doped oxyfluoride silicate glasses for potential applications in photosynthesis

    OpenAIRE

    Zhu, Chaofeng; ZHANG, XIANGHUA; Ma, Hongli

    2016-01-01

    International audience; A series of Sb/Mn co-doped oxyfluoride silicate glasses were prepared via the melt-quenching method to explore red luminescent materials for potential applications in photosynthesis of green plants, and these glasses are investigated by means of luminescence decay curves, absorption, emission, and excitation spectra. We find that the as-prepared glasses are transparent in the visible region and can emit strong red light under ultraviolet, purple, and green light excita...

  2. Global optimization of bimetallic cluster structures. I. Size-mismatched Ag-Cu, Ag-Ni, and Au-Cu systems

    Science.gov (United States)

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

    2005-05-01

    A genetic algorithm approach is applied to the optimization of the potential energy of a wide range of binary metallic nanoclusters, Ag-Cu, Ag-Ni, Au-Cu, Ag-Pd, Ag-Au, and Pd-Pt, modeled by a semiempirical potential. The aim of this work is to single out the driving forces that make different structural motifs the most favorable at different sizes and chemical compositions. Paper I is devoted to the analysis of size-mismatched systems, namely, Ag-Cu, Ag-Ni, and Au-Cu clusters. In Ag-Cu and Ag-Ni clusters, the large size mismatch and the tendency of Ag to segregate at the surface of Cu and Ni lead to the location of core-shell polyicosahedral minimum structures. Particularly stable polyicosahedral clusters are located at size N =34 (at the composition with 27 Ag atoms) and N =38 (at the composition with 32 and 30 Ag atoms). In Ag-Ni clusters, Ag32Ni13 is also shown to be a good energetic configuration. For Au-Cu clusters, these core-shell polyicosahedra are less common, because size mismatch is not reinforced by a strong tendency to segregation of Au at the surface of Cu, and Au atoms are not well accommodated upon the strained polyicosahedral surface.

  3. A density functional theory study on size-dependent structures, stabilities, and electronic properties of bimetallic MnAgm (M=Na, Li; n + m ≤ 7) clusters

    Institute of Scientific and Technical Information of China (English)

    Sun Hao-Ran; Kuang Xiao-Yu; Li Yan-Fang; Shao Peng; Zhao Ya-Ru

    2012-01-01

    The equilibrium geometries,relative stabilities,and electronic properties of MnAgm(M=-Na,Li; n +-m ≤ 7) as well as pure Agn,Nan,Lin (n ≤ 7) clusters are systematically investigated by means of the density functional theory.The optimized geometries reveal that for 2 ≤ n ≤ 7,there are significant similarities in geometry among pure Agn,Nan,and Lin clusters,and the transitions from planar to three-dimensional configurations occur at n =7,7,and 6,respectively.In contrast,the first three-dimensional (3D) structures are observed at n + m =5 for both NanAgm and LinAgm clusters.When n + m ≥ 5,a striking feature is that the trigonal bipyramid becomes the main subunit of LinAgm.Furthermore,dramatic odd-even alternative behaviours are obtained in the fragmentation energies,secondorder difference energies,highest occupied and lowest unoccupied molecular orbital energy gaps,and chemical hardness for both pure and doped clusters.The analytic results exhibit that clusters with an even electronic configuration (2,4,6) possess the weakest chemical reactivity and more enhanced stability.

  4. 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.

  5. Study on a green synthetic method of TRPPMCI (M = Fe, Mn, Co)

    Institute of Scientific and Technical Information of China (English)

    Jing FAN; Yuanbin SHE; Aixin WANG

    2009-01-01

    A green synthetic method using mixted solvents of di-methyl formamide (DMF) and acids instead of single DMF to synthesize metalloporphyrins (TRPPMCI) from TRPPH2 and MC12 metallization was proposed in this paper. A series of TRPPMCI (M = Fe, Mn, Co) were synthesized through this innovative synthetic method, and these complexes were characterized with various spectroscopic techniques, including IR and UV-Vis spectroscopy. The results showed that the metallization time was markedly reduced from about 10h to 0.5 h in contrast with the conventional synthetic methods.

  6. Angular dependence of the exchange bias and coercivity of IrMn/Co bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Nicolodi, S. [Instituto de Fisica-UFRGS, CP 15051, 91501-970 Porto Alegre, RS (Brazil)]. E-mail: nicolodi@if.ufrgs.br; Pereira, L.G. [Instituto de Fisica-UFRGS, CP 15051, 91501-970 Porto Alegre, RS (Brazil); Schmidt, J.E. [Instituto de Fisica-UFRGS, CP 15051, 91501-970 Porto Alegre, RS (Brazil); Nagamine, L.C.C.M. [Instituto de Fisica-UFRGS, CP 15051, 91501-970 Porto Alegre, RS (Brazil); Viegas, A.D.C. [Departamento de Fisica, CCNE, UFSM, 97105-900, Santa Maria, RS (Brazil); Deranlot, C. [Unite Mixte de Physique CNRS/Thales, 91767 Palaiseau and Universite Paris-Sud, 91405 Orsay (France); Petroff, F. [Unite Mixte de Physique CNRS/Thales, 91767 Palaiseau and Universite Paris-Sud, 91405 Orsay (France); Geshev, J. [Instituto de Fisica-UFRGS, CP 15051, 91501-970 Porto Alegre, RS (Brazil)

    2006-10-01

    In this study we present the in-plane angular dependences of the exchange-bias and coercive fields of magnetron-sputtered IrMn/Co exchange-coupled system before and after magnetic field annealing. Two experimental techniques were employed for the magnetic characterization of the samples, i.e., alternate gradient field magnetometry and anisotropic magnetoresistance measurements, which gave practically the same value for the exchange-bias field shift. An increase of the exchange-bias field and a substantial decrease of the coercivity are observed after the annealing. A phenomenological model was also used to adjust the data and to derive the anisotropy characteristics.

  7. Seal glass compatibility with bare and (Mn,Co) 3O 4 coated Crofer 22 APU alloy in different atmospheres

    Science.gov (United States)

    Mahapatra, M. K.; Lu, K.

    To prevent gas mixing and leakage during solid oxide fuel/electrolyzer cell operation, the interconnect/seal glass interface should bond well and remain stable. A SrO-La 2O 3-Al 2O 3-SiO 2 (SABS-0) seal glass has been bonded to bare Crofer 22 APU alloy and (Mn,Co) 3O 4 coated Crofer 22 APU alloy. The stability of the interconnect/SABS-0 interface has been studied in air and H 2/H 2O atmospheres at 800 °C for 1000 h. The interconnect/seal glass interaction involves the oxidation of the bare and (Mn,Co) 3O 4 coated Crofer 22 APU alloy surfaces, inter-diffusion of elements, chemical reaction, and the devitrification of the SABS-0 glass. The study shows that the thermal treatment atmosphere greatly affects the interfacial stability of both bare Crofer 22 APU/SABS-0 and (Mn,Co) 3O 4 coated Crofer 22 APU/SABS-0 samples. The interfacial stability is better in the H 2/H 2O atmosphere for both samples. The instability of the (Mn,Co) 3O 4 coating under the thermal treatment conditions degrades the interfacial compatibility of the (Mn,Co) 3O 4 coated Crofer 22 APU/SABS-0 sample.

  8. Phase Transitions and Magnetocaloric Properties in MnCo1−xZrxGe Compounds

    Directory of Open Access Journals (Sweden)

    Anil Aryal

    2017-01-01

    Full Text Available The structural, magnetic, and magnetocaloric properties of MnCo1-xZrxGe (0.01≤x≤0.04 have been studied through X-ray diffraction, differential scanning calorimetry, and magnetization measurements. Results indicate that the partial substitution of Zr for Co in MnCo1-xZrxGe decreases the martensitic transition temperature (TM. For x = 0.02, TM was found to coincide with the ferromagnetic transition temperature (TC resulting in a first-order magnetostructural transition (MST. A further increase in zirconium concentration (x = 0.04 showed a single transition at TC. The MST from the paramagnetic to ferromagnetic state results in magnetic entropy changes (-ΔSM of 7.2 J/kgK for ΔH = 5 T at 274 K for x = 0.02. The corresponding value of the relative cooling power (RCP was found to be 266 J/kg for ΔH = 5 T. The observed large value of MCE and RCP makes this system a promising material for magnetic cooling applications.

  9. Tailoring interlayer coupling and coercivity in Co/Mn/Co trilayers by controlling the interface roughness

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Bin; Wu, Chii-Bin; Kuch, Wolfgang, E-mail: kuch@physik.fu-berlin.de [Institut für Experimentalphysik, Freie Universität Berlin, Arnimallee 14, 14195 Berlin (Germany)

    2014-06-21

    Epitaxial Co/Mn/Co trilayers with a wedged Mn layer were grown on Cu(001) and studied by magneto-optical Kerr effect measurements. The bottom Co film as well as the Mn film exhibits a layer-by-layer growth mode, which allows to modify both interface roughnesses on the atomic scale by tuning the thicknesses of the films to achieve a certain filling of their topmost atomic layers. The onset of antiferromagnetic order in the Mn layer at room temperature was found at thicknesses of 4.1 (4.8) and 3.4 (4.0) atomic monolayers (ML) for a filled (half-filled) topmost atomic layer of the bottom Co film in Mn/Co bilayers and Co/Mn/Co trilayers, respectively. Magnetization loops with only one step were found for a trilayer with half-filled topmost atomic layer of the bottom Co film, while loops with two separate steps have been observed in trilayers with an integer number of atomic layers in the bottom Co film. The coercivity of the top Co film shows an oscillation with 1 ML period as a function of the Mn thickness above 10 ML, which is interpreted as the influence of the atomic-scale control of the interface roughness on the interface exchange coupling between the antiferromagnetic Mn and the top ferromagnetic (FM) Co layer. The strength of the magnetic interlayer coupling between the top and bottom Co layers through the Mn layer for an integer number of atomic layers in the bottom Co layer, deduced from minor-loop measurements, exhibits an oscillation with a period of 2 ML Mn thickness, indicative of direct exchange coupling through the antiferromagnetic Mn layer. In addition, a long-period interlayer coupling of the two FM layers with antiparallel coupling maxima at Mn thicknesses of 2.5, 8.2, and 13.7 ML is observed and attributed to indirect exchange coupling of the Rudermann-Kittel-Kasuya-Yosida type.

  10. Annealing effect on the structural and electrical performance of Mn-Co-Ni-O films

    Directory of Open Access Journals (Sweden)

    Fei Zhang

    2015-11-01

    Full Text Available Thin films of Mn1.95Co0.77Ni0.28O4are deposited on amorphous Al2O3 substrate by the magnetron sputtering method with the thickness of 6.5 μm. The effects of annealing treatment are studied on the film structural performance as well as the entropy of Mn-Co-Ni-O(MCNO films by annealed at 400 ∘C, 500 ∘C, 600 ∘C, 700 ∘C, 800 ∘C respectively. It shows that the crystallinity of the thin film is the best annealed at 700 ∘C and the entropy is the largest because the number of different kinds of ions belonging to the same element equals with each other. After 800 ∘C annealing, the film resistivity is the minimal with the maximal entropy which means the highest stability.

  11. Hierarchical chestnut-like MnCo2O4 nanoneedles grown on nickel foam as binder-free electrode for high energy density asymmetric supercapacitors

    Science.gov (United States)

    Hui, Kwun Nam; Hui, Kwan San; Tang, Zikang; Jadhav, V. V.; Xia, Qi Xun

    2016-10-01

    Hierarchical chestnut-like manganese cobalt oxide (MnCo2O4) nanoneedles (NNs) are successfully grown on nickel foam using a facile and cost-effective hydrothermal method. High resolution TEM image further verifies that the chestnut-like MnCo2O4 structure is assembled by numerous 1D MnCo2O4 nanoneedles, which are formed by numerous interconnected MnCo2O4 nanoparticles with grain diameter of ∼10 nm. The MnCo2O4 electrode exhibits high specific capacitance of 1535 F g-1 at 1 A g-1 and good rate capability (950 F g-1 at 10 A g-1) in a 6 M KOH electrolyte. An asymmetric supercapacitor is fabricated using MnCo2O4 NNs on Ni foam (MnCo2O4 NNs/NF) as the positive electrode and graphene/NF as the negative electrode. The device shows an operation voltage of 1.5 V and delivers a high energy density of ∼60.4 Wh kg-1 at a power density of ∼375 W kg-1. Moreover, the device exhibits an excellent cycling stability of 94.3% capacitance retention after 12000 cycles at 30 A g-1. This work demonstrates that hierarchical chestnut-like MnCo2O4 NNs could be a promising electrode for the high performance energy storage devices.

  12. Synthesis and crystal structure of the novel transition- metal substituted tin hydride H2Sn2[Mn(CO)5]4

    NARCIS (Netherlands)

    Bos, K.D.; Bulten, E.J.; Noltes, J.G.

    1975-01-01

    Dicyclopentadienyltin reacts with manganese pentacarbonyl hydride to give the first transition-metal substituted ditin dihydride, H[Mn(CO)5]2Sn---Sn- [Mn(CO)5]2H, the structure of which has been determined by X-ray analysis. The compound crystallizes in the monoclinic space group with four molecul

  13. Influence of Mn-Co Spinel Coating on Oxidation Behavior of Ferritic SS Alloys for SOFC Interconnect Applications

    DEFF Research Database (Denmark)

    Venkatachalam, Vinothini; Molin, Sebastian; Kiebach, Wolff-Ragnar

    2014-01-01

    of the promising candidates to prevent chromium outward diffusion, improve oxidation resistance and ensure high electrical conductivity over the lifetime of interconnects. In the present study, uniform and well adherent Mn-Co spinel coatings were produced on Crofer 22APU using electrophoretic deposition (EPD...

  14. Selective adsorption of manganese onto cobalt for optimized Mn/Co/TiO2 Fischer-Tropsch catalysts

    NARCIS (Netherlands)

    Feltes, T.E.; Espinosa-Alonso, L.; de Smit, E.; D'Souza, L.; Meyer, R.J.; Weckhuysen, B.M.; Regalbuto, J.R.

    2013-01-01

    The Strong Electrostatic Adsorption (SEA) method was applied to the rational design of a promoted Co catalyst for Fischer–Tropsch (FT) synthesis. A series of Mn/Co/TiO2 catalysts were prepared by selective deposition of the [MnO4] anion onto the supported Co3O4 phase. Qualitative ICP-OES and XPS mea

  15. Large exchange bias enhancement in (Pt(or Pd)/Co)/IrMn/Co trilayers with ultrathin IrMn thanks to interfacial Cu dusting

    Energy Technology Data Exchange (ETDEWEB)

    Vinai, G. [SPINTEC, UMR 8191 CEA/CNRS/UJF/Grenoble-INP, CEA/INAC, 17, rue des Martyrs, 38054 Grenoble (France); Crocus Technology, 4 Place Robert Schuman, 38054 Grenoble (France); Moritz, J. [Institut Jean Lamour, UMR 7198 CNRS - Université de Lorraine, Bd des Aiguillettes, BP 70239, F-54506 Vandoeuvre-les-Nancy Cedex (France); Bandiera, S. [Crocus Technology, 4 Place Robert Schuman, 38054 Grenoble (France); Prejbeanu, I. L.; Dieny, B. [SPINTEC, UMR 8191 CEA/CNRS/UJF/Grenoble-INP, CEA/INAC, 17, rue des Martyrs, 38054 Grenoble (France)

    2014-04-21

    The magnitude of exchange bias (H{sub ex}) at room temperature can be significantly enhanced in IrMn/Co and (Pt(or Pd)/Co)/IrMn/Co structures thanks to the insertion of an ultrathin Cu dusting layer at the IrMn/Co interface. The combination of trilayer structure and interfacial Cu dusting leads to a three-fold increase in H{sub ex} as compared to the conventional IrMn/Co bilayer structure, with an increased blocking temperature (T{sub B}) and a concave curvature of the temperature dependence H{sub ex}(T), ideal for improved Thermally Assisted-Magnetic Random Access Memory storage layer. This exchange bias enhancement is ascribed to a reduction of the spin frustration at the IrMn/Co interface thanks to interfacial Cu addition.

  16. Chemical Preparation of Supported Bimetallic Catalysts. Gold-Based Bimetallic, a Case Study

    OpenAIRE

    Louis, Catherine

    2016-01-01

    International audience; This review focuses on the chemical methods used to prepare supported bimetallic heterogeneous catalysts, i.e., bimetallic nanoparticles deposited on a support. The review is limited to the preparation of gold-based bimetallic catalysts and moreover to bimetallic nanoparticles supported on powder inorganic supports, i.e., on the surface or in the porosity, and not on model supports such as single crystals.

  17. Low temperature processed MnCo2O4 and MnCo1.8Fe0.2O4 as effective protective coatings for solid oxide fuel cell interconnects at 750 °C

    DEFF Research Database (Denmark)

    Molin, Sebastian; Jasinski, P.; Mikkelsen, Lars

    2016-01-01

    In this study two materials, MnCo2O4 and MnCo1.8Fe0.2O4 are studied as potential protective coatings for Solid Oxide Fuel Cell interconnects working at 750 °C. First powder fabrication by a modified Pechini method is described followed by a description of the coating procedure. The protective...... action of the coating applied on Crofer 22 APU is evaluated by following the area specific resistance (ASR) of the scale/coating for 5500 h including several thermal cycles. The coating is prepared by brush painting and has a porous structure after deposition. Post mortem microstructural characterization...... performed on the coated samples shows good protection against chromium diffusion from the chromia scale ensured by a formation of a dense reaction layer. This study shows, that even without high temperature sintering and/or reactive sintering it is possible to fabricate protective coatings based on Mn...

  18. Manufacturing of advanced Li(NiMnCo)O2 electrodes for lithium-ion batteries

    Science.gov (United States)

    Smyrek, P.; Pröll, J.; Rakebrandt, J.-H.; Seifert, H. J.; Pfleging, W.

    2015-03-01

    Lithium-ion batteries require an increase in cell life-time as well as an improvement in cycle stability in order to be used as energy storage systems, e.g. for stationary devices or electric vehicles. Nowadays, several cathode materials such as Li(NiMnCo)O2 (NMC) are under intense investigation to enhanced cell cycling behavior by simultaneously providing reasonable costs. Previous studies have shown that processing of three-dimensional (3D) micro-features in electrodes using nanosecond laser radiation further increases the active surface area and therefore, the lithium-ion diffusion cell kinetics. Within this study, NMC cathodes were prepared by tape-casting and laser-structured using nanosecond laser radiation. Furthermore, laser-induced breakdown spectroscopy (LIBS) was used in a first experimental attempt to analyze the lithium distribution in unstructured NMC cathodes at different state-of-charges (SOC). LIBS will be applied to laser-structured cathodes in order to investigate the lithium distribution at different SOC. The results will be compared to those obtained for unstructured electrodes to examine advantages of 3D micro-structures with respect to lithium-ion diffusion kinetics.

  19. Behavior of antiferromagnetic MnCoSi in a magnetic field under pressure

    Energy Technology Data Exchange (ETDEWEB)

    Zavorotnev, Yu.D., E-mail: zavorotnev.yurii@gmail.com [Donetsk Institute for Physics and Engineering, NAS of Ukraine, 72 R. Luxemburg St., 83114 Donetsk (Ukraine); Medvedeva, L.I.; Todris, B.M.; Dvornikov, E.A. [Donetsk Institute for Physics and Engineering, NAS of Ukraine, 72 R. Luxemburg St., 83114 Donetsk (Ukraine); Popova, O.Yu. [Donetsk National Technical University, 58 Artema St., 83001 Donetsk (Ukraine)

    2011-11-15

    Experimental data on magnetization of the antiferromagnetic (AFM) polycrystalline samples in the temperature range of 20-300 K, for pressures of 2 kbar and in magnetic field of 300 kOe, are presented in the paper. In the fields of 250 kOe, the magnetization curve demonstrates a jump explained by exchange-interaction sign change. In the region of 50-70 kOe, on the differential susceptibility versus magnetic field curve, there is a break of the 2nd order corresponding to the anomalous behavior of the magnetization. The obtained results were processed on the basis of the phenomenological Landau theory. It is shown that the ferromagnetic vector occurrence is forced during the formation of AFM spiral structure. The behavior of thermodynamic potential factors has been determined. Three more anomalies have been revealed and explained by a jump-like magnetization change of the Co-subsystem. - Highlights: > MnCoSi alloy is studied under pressure of 2 kbar, at magnetic field of 300 kOe. > Temperature range was 20-300 K. > Pressure-dependent magnetization jump is due to sign change of exchange interaction. > Magnetization anomaly is conditioned by intersection of the lowest levels of Co ions. > Temperature extrema at magnetization are realized within the jump region.

  20. Magneto-optic properties and optical parameter of thin MnCo films

    Directory of Open Access Journals (Sweden)

    E Attaran Kakhki

    2009-09-01

    Full Text Available Having precise hysterics loop of thin ferroelectric and ferromagnetic layers for optical switching and optical storages are important. A hysterieses loop can be achieved from a phenomenon call the magneto-optic effect. The magneto-optic effect is the rotation of a linear polarized electromagnetic wave propagated through a ferromagnetic medium. When light is transmitted through a layer of magnetic material the result is called the Faraday effects and in the reflection mode Kerr effect. In the present work we prepared a thin layer of MnxCo3-xO4 (0≤ x ≤ 1 and a binary form of MnO/Co3O4 by the spray pyrolysis method. The films have been characterized by a special set up of magneto-optic hysterics loop plotter containing a polarized He- Ne laser beam and a special electronic circuit. Faraday rotation were measured for these films by hysterics loop plotter and their optical properties were also obtained by spatial software designed for this purpose according to Swane Poel theoretical method. The measurements show that the samples at diluted Mn study has are ferromagnetic and the magneto-optic rotation show a good enhance respect to the single Co layers. Also, the study has shown that the MnCo oxide layer have two different energy gaps and by increasing of Mn this energy decreases and fall to 0.13 eV.

  1. Heterometallic Complexes with Selenolate Ligands: Crystal Structures of [(CO)(3)Mn(&mgr;-SePh)(3)Co(&mgr;-SePh)(3)Mn(CO)(3)](-), (CO)(4)Mn(&mgr;-SeMe)(2)Co(CO)(&mgr;-SeMe)(3)Mn(CO)(3), and [(CO)(3)Mn(&mgr;-SePh)(3)Mn(CO)(3)](-).

    Science.gov (United States)

    Liaw, Wen-Feng; Lee, Way-Zen; Wang, Chun-Yuan; Lee, Gene-Hsiang; Peng, Shie-Ming

    1997-03-12

    Oxidation of Co(2+) by diphenyl diselenide in the presence of cis-[PPN][Mn(CO)(4)(SePh)(2)], followed by carbonyl shift from Mn(I) to Co(III) and a benzeneselenolate group rearranging to bridge two metals, led directly to the thermally unstable (CO)(4)Mn(&mgr;-SePh)(2)Co(CO)(&mgr;-SePh)(3)Mn(CO)(3). Dropwise addition of [PPN][SePh] to the neutral (CO)(4)Mn(&mgr;-SePh)(2)Co(CO)(&mgr;-SePh)(3)Mn(CO)(3) resulted in formation of a linear trinuclear complex possessing a hexaselenolatecobalt(III) core, [PPN][(CO)(3)Mn(&mgr;-SePh)(3)Co(&mgr;-SePh)(3)Mn(CO)(3)]. This complex crystallized in the triclinic space group P&onemacr; with a = 10.878(1) Å, b = 15.095(2) Å, c = 25.372(4) Å, alpha = 95.04(1) degrees, beta = 95.00(1) degrees, gamma = 91.52(2) degrees, V = 4132(2) Å(3), and Z = 2; final R = 0.042 and R(w) = 0.042. In contrast, the thermally unstable cis-[PPN][Mn(CO)(4)(SeMe)(2)], which was reacted with Co(ClO(4))(2).6H(2)O and (MeSe)(2) in THF under a nitrogen atmosphere, led to the isolation of the stable heterometallic selenolate (CO)(4)Mn(&mgr;-SeMe)(2)Co(CO)(&mgr;-SeMe)(3)Mn(CO)(3). Crystal data: monoclinic space group C2/c, a = 28.413(7) Å, b = 11.091(3) Å, c = 22.849(6) Å, beta = 125.06(3) degrees, V = 5894(3) Å(3), and Z = 8; final R = 0.047 and R(w) = 0.048. The results indicated that the distinct electronic effects between methaneselenolate and benzeneselenolate play a key role in stabilizing the neutral Mn(I)-Co(III)-Mn(I)-selenolate complexes.

  2. Characterization and Preparation of Bimetallic Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    Bing; Joe; Hwang; Ching; Hsiang; Chen; Loka; Subramanyam; Sarma; Din-gao; Liu; Jyh; Fu; Lee

    2007-01-01

    1 Results Bimetallic particles in the nanometer size range are of substantial interest due to their vast applications in catalysis[1].The synthesis of bimetallic nanoparticles with definite size with a well-control over their nanostructure remains a challenging problem.Thus there exists a great demand for both synthesis and atomic level characterization of nanostructure of bimetallic nanoparticles (NPs).With the recent advent of high-intensity tunable sources of X-rays,now available at synchrotron radia...

  3. Magnetic and magnetotransport properties of MnCo0.8V0.2Ge alloy

    Science.gov (United States)

    Dutta, P.; Pramanick, S.; Das, D.; Chatterjee, S.

    2017-05-01

    Different magnetic and magnetotransport properties of a hexagonal Ni2In-type MnCo0.8V0.2Ge magnetic shape memory alloy are investigated. The parent MnCoGe alloy undergoes first order martensitic phase transition (MPT) at 650 K during cooling and orders ferromagnetically (FM) below 345 K. V-doping at the cobalt site decreases the MPT temperature and affects the lattice parameters that induces a short range antiferromagnetic (AFM) interaction in this intrinsically FM system at low temperature. The studied alloy shows three important magnetofunctional properties namely exchange bias effect, magnetocaloric effect, and magnetoresistance which indicate that the alloy may be a potential candidate for practical applications.

  4. Assesment of (Mn,Co)33O4 powders for possible coating material for SOFC/SOEC interconnects

    Science.gov (United States)

    Szymczewska, D.; Molin, S.; Venkatachalam, V.; Chen, M.; Jasinski, P.; Hendriksen, P. V.

    2016-01-01

    In this work (Mn,Co)3O4 spinel powders with different Mn:Co ratio (1:1 and 1:2) and from different commercial suppliers are evaluated for possible powder for production of interconnect coatings. Sinterability of the powders is evaluated on pressed pellets sintered in oxidizing and in reducing/oxidizing atmospheres. For selected powder, coatings are then prepared by the electrophoretic deposition method on Crofer 22 APU stainless steel coupons. Effects of dispersant/iodine content and deposition voltage and times are evaluated. Thickness as a function of deposition parameters is described. Results show that with appropriate powder it is possible to produce adherent protective coating with a well-controlled thickness.

  5. Assesment of (Mn,Co)3O4 powders for possible coating material for SOFC/SOEC interconnects

    DEFF Research Database (Denmark)

    Szymczewska, D.; Molin, Sebastian; Venkatachalam, Vinothini

    2015-01-01

    In this work (Mn,Co)3O4 spinel powders with different Mn:Co ratio (1:1 and 1:2) and from different commercial suppliers are evaluated for possible powder for production of interconnect coatings. Sinterability of the powders is evaluated on pressed pellets sintered in oxidizing and in reducing....../oxidizing atmospheres. For selected powder, coatings are then prepared by the electrophoretic deposition method on Crofer 22 APU stainless steel coupons. Effects of dispersant/iodine content and deposition voltage and times are evaluated. Thickness as a function of deposition parameters is described. Results show...... that with appropriate powder it is possible to produce adherent protective coating with a well-controlled thickness....

  6. Influence of Mn-Co Spinel Coating on Oxidation Behavior of Ferritic SS Alloys for SOFC Interconnect Applications

    OpenAIRE

    Venkatachalam, Vinothini; Molin, Sebastian; Kiebach, Wolff-Ragnar; Ming CHEN; Hendriksen, Peter Vang

    2014-01-01

    Chromia forming ferritic stainless steels (SS) are being considered for intermediate temperature solid oxide fuel cell interconnect applications. However, protective coatings are in general needed to avoid chromium volatilization and poisoning of cathodes from chromium species. Mn-Co spinel is one of the promising candidates to prevent chromium outward diffusion, improve oxidation resistance and ensure high electrical conductivity over the lifetime of interconnects. In the present study, unif...

  7. A first-principles study of Pt–Ni bimetallic cluster adsorption on the anatase TiO{sub 2} (1 0 1) surface: Probing electron effect of Ni in TiO{sub 2} (1 0 1)-bimetallic cluster (Pt–Ni) on the adsorption and dissociation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Feila, E-mail: liufeila@u.washington.edu [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Department of Materials Science and Engineering, University of Washington, Seattle, WA 98195 (United States); Xiao, Peng, E-mail: xiaopeng@cqu.edu.cn [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Uchaker, Evan, E-mail: uchaker@u.washington.edu [Department of Materials Science and Engineering, University of Washington, Seattle, WA 98195 (United States); He, Huichao, E-mail: hehuichao985@gmail.com [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Zhou, Ming, E-mail: Zhoumingcqu2007@163.com [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Zhou, Xin, E-mail: zhoux@hit.edu.cn [State Key Laboratory of Urban Water Resource and Environment, Institute of Theoretical and Simulation Chemistry, Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150080 (China); Zhang, Yunhuai, E-mail: xp2031@163.com [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China)

    2014-10-01

    Graphical abstract: - Highlights: • Condensed Fukui function is used to predict the regioselectivity of clusters. • Pt–Ni alloy and TiO{sub 2} can effectively oxidize methanol compared with pure Pt. • The methanol dehydrogenation over Pt{sub 3}Ni/TiO{sub 2} is an optimal reaction pathway. • The alloying of Ni can effectively alleviate CO poisoning. - Abstract: A density functional theory (DFT) based method in conjunction with the projector augmented wave and pseudopotential methods have been applied to investigate the adsorption of Pt{sub 4} and Pt{sub 3}Ni on the anatase TiO{sub 2} (1 0 1) surface. Two stable Pt{sub 3}Ni adsorptions with considerable adsorption energies on the anatase TiO{sub 2} (1 0 1) surface were identified. Analysis of the partial density (PDOS) of states and Bader charge suggest that the electronic structure of Pt is modified by Ni due to the electron transfer from Ni to Pt atoms in the Pt{sub 3}Ni clusters. The 2cO (3cO)-PtNi-5cTi conformation of the adsorbed Pt{sub 3}Ni on the anatase TiO{sub 2} (1 0 1) surface provides a more feasible model for electron injection through the Pt{sub 3}Ni/TiO{sub 2} interface. The reactivity of Pt{sub 3}Ni/TiO{sub 2} is superior to Pt{sub 4}/TiO{sub 2} and effectively manifests itself in the eased decomposition of O-H bonds derived by methanol and alleviative CO adsorption.

  8. Synthesis by Microwaves of Bimetallic Nano-Rhodium-Palladium

    Directory of Open Access Journals (Sweden)

    M. Ugalde

    2013-01-01

    Full Text Available An improved acrylamide sol-gel technique using a microwave oven in order to synthesize bimetallic Rh-Pd particles is reported and discussed. The synthesis of Pd and Rh nanoparticles was carried out separately. The polymerization to form the gel of both Rh and Pd was carried out at 80°C under constant agitations. The method chosen to prepare the Rh and Pd xerogels involved the decomposition of both gels. The process begins by steadily increasing the temperature of the gel inside a microwave oven (from 80°C to 170°C. In order to eliminate the by-products generated during the sol-gel reaction, a heat treatment at a temperature of 1000°C for 2 h in inert atmosphere was carried out. After the heat treatment, the particle size increased from 50 nm to 200 nm, producing the bimetallic Rh-Pd clusters. It can be concluded that the reported microwave-assisted, sol-gel method was able to obtain nano-bimetallic Rh-Pd particles with an average size of 75 nm.

  9. Electronic and magnetic properties of double perovskite Dy{sub 2}MnCoO{sub 6} by first-principles calculation

    Energy Technology Data Exchange (ETDEWEB)

    Ganeshraj, C.; Santhosh, P. N., E-mail: santhosh@physics.iitm.ac.in [Low Temperature Physics Laboratory, Department of Physics, Indian Institute of Technology Madras, Chennai 600 036, Tamilnadu (India)

    2014-05-07

    Using first-principles calculation, we investigate electronic and magnetic properties of Dy{sub 2}MnCoO{sub 6}. A detailed structural optimization has been done and found that the orthorhombic structure with Mn (Co) ions aligning along the longest axis type is the most stable structure. Within the generalized gradient approximation, the spin polarized calculations predict Dy{sub 2}MnCoO{sub 6} to be a half-metallic with ferromagnetic interaction between Mn and Co ions and antiferromagnetic interaction between Dy and Mn/Co ions. We also investigate the effect of Hubbard parameter (U) on the ground state magnetic structure. For all values of Hubbard U parameter the Co ions have nonzero magnetic moment; they do not lie in low-spin state, as in DyCoO{sub 3}.

  10. Concentrations of heavy metals (Mn, Co, Ni, Cr, Ag, Pb) in coffee.

    Science.gov (United States)

    Nędzarek, Arkadiusz; Tórz, Agnieszka; Karakiewicz, Beata; Clark, Jeremy Simon; Laszczyńska, Maria; Kaleta, Agnieszka; Adler, Grażyna

    2013-01-01

    Technologies involved in roasting coffee beans, as well as the methods used to prepare infusions, vary according to culture, and contribute to differences in the concentration of elements in the drink. Concentrations of six elements: manganese (Mn), cobalt (Co), nickel (Ni), chrome (Cr), silver (Ag) and lead (Pb) were investigated in coffee infusions from eleven samples of coffee, roasted and purchased in four countries: Bosnia and Herzegovina, Brazil, Lebanon and Poland. Metal concentrations were determined using an induction coupled plasma technique in combination with mass spectrometry (ICP-MS, Perkin Elmer) which measures total metal (ionic and non-ionic) content. Metal intake estimated for individual countries (in the respective order; mean consumption per person per year) was as follows: Mn: 26.8-33.1, 28.3-29.5, 29.7, 12.6-18.9 mg; Co: 0.33-0.48, 0.42-0.35, 0.32, 0.12-0.17 mg; Ni: 3.83-5.68, 4.85-5.51, 4.04, 2.06-2.24 mg; Cr: 0.17-0.41, 0.21-0.47, 0.17, 0.09-0.28 mg; Ag: 0.16-1.13, 0.26-0.70, 0.61, 0.33-1.54 mg, Pb: 4.76-7.56, 3.59-5.13, 3.33, 1.48-2.43 mg. This finding gives new data for Mn, Co, Ni, Cr, and Ag intake from coffee , and suggests that the amounts are negligible. However, the data for Pb consumption in heavy drinkers, for example in Bosnia and Herzegovina, indicate that Pb intake from coffee may contribute to the disease burden. The high lead level in some coffees suggests the need for a more precise control of coffee contamination.

  11. Noble metal-based bimetallic nanoparticles: the effect of the structure on the optical, catalytic and photocatalytic properties.

    Science.gov (United States)

    Zaleska-Medynska, Adriana; Marchelek, Martyna; Diak, Magdalena; Grabowska, Ewelina

    2016-03-01

    Nanoparticles composed of two different metal elements show novel electronic, optical, catalytic or photocatalytic properties from monometallic nanoparticles. Bimetallic nanoparticles could show not only the combination of the properties related to the presence of two individual metals, but also new properties due to a synergy between two metals. The structure of bimetallic nanoparticles can be oriented in random alloy, alloy with an intermetallic compound, cluster-in-cluster or core-shell structures and is strictly dependent on the relative strengths of metal-metal bond, surface energies of bulk elements, relative atomic sizes, preparation method and conditions, etc. In this review, selected properties, such as structure, optical, catalytic and photocatalytic of noble metals-based bimetallic nanoparticles, are discussed together with preparation routes. The effects of preparation method conditions as well as metal properties on the final structure of bimetallic nanoparticles (from alloy to core-shell structure) are followed. The role of bimetallic nanoparticles in heterogeneous catalysis and photocatalysis are discussed. Furthermore, structure and optical characteristics of bimetallic nanoparticles are described in relation to the some features of monometallic NPs. Such a complex approach allows to systematize knowledge and to identify the future direction of research.

  12. Surface composition tuning of Au-Pt bimetallic nanoparticles for enhanced carbon monoxide and methanol electro-oxidation.

    Science.gov (United States)

    Suntivich, Jin; Xu, Zhichuan; Carlton, Christopher E; Kim, Junhyung; Han, Binghong; Lee, Seung Woo; Bonnet, Nicéphore; Marzari, Nicola; Allard, Lawrence F; Gasteiger, Hubert A; Hamad-Schifferli, Kimberly; Shao-Horn, Yang

    2013-05-29

    The ability to direct bimetallic nanoparticles to express desirable surface composition is a crucial step toward effective heterogeneous catalysis, sensing, and bionanotechnology applications. Here we report surface composition tuning of bimetallic Au-Pt electrocatalysts for carbon monoxide and methanol oxidation reactions. We establish a direct correlation between the surface composition of Au-Pt nanoparticles and their catalytic activities. We find that the intrinsic activities of Au-Pt nanoparticles with the same bulk composition of Au0.5Pt0.5 can be enhanced by orders of magnitude by simply controlling the surface composition. We attribute this enhancement to the weakened CO binding on Pt in discrete Pt or Pt-rich clusters surrounded by surface Au atoms. Our finding demonstrates the importance of surface composition control at the nanoscale in harnessing the true electrocatalytic potential of bimetallic nanoparticles and opens up strategies for the development of highly active bimetallic nanoparticles for electrochemical energy conversion.

  13. Reaction of (. eta. sup 5 -C sub 13 H sub 9 )Mn(CO) sub 3 with alkylphosphines: Formation and isolation of. eta. sup 1 -fluorenyl complexes

    Energy Technology Data Exchange (ETDEWEB)

    Biagioni, R.N.; Lorkovic, I.M.; Skelton, J.; Hartung, J.B. (Grinnell College, IA (USA))

    1990-03-01

    Reaction of ({eta}{sup 5}-C{sub 13}H{sub 9})Mn(CO){sub 3} with L = PEt{sub 3} or PBu{sub 3} leads to formation of ({eta}{sup 1}-C{sub 13}H{sub 9})Mn(CO){sub 3}L{sub 2}. The L = PEt{sub 3} complex was isolated analytically pure in moderate yield and characterized as the trans-meridional isomer by {sup 1}H, {sup 31}P, and {sup 13}C NMR and IR spectroscopies. ({eta}{sup 1}-C{sub 13}H{sub 9})Mn(CO){sub 3}L{sub 2} decomposes via Mn-C bond homolysis to the C{sub 13}H{sub 9} radical and Mn(CO){sub 3}L{sub 2}{sup {sm bullet}}, which reacts further to yield HMn(CO){sub 3}L{sub 2}. ({eta}{sup 1}-C{sub 13}H{sub 9})Mn(CO){sub 3}L{sub 2} can also be prepared by reacting L with ({eta}{sup 6}-C{sub 13}H{sub 9})Mn(CO){sub 3}, apparently via a novel {eta}{sup 6} to {eta}{sup 1} shift.

  14. An Approach to Heterometallic Complexes with Selenolate and Tellurolate Ligands: Crystal Structures of cis-[Mn(CO)(4)(SePh)(2)](-), [(CO)(3)Mn(&mgr;-SeMe)(3)Mn(CO)(3)](-), (CO)(4)Mn(&mgr;-TePh)(2)Co(CO)(&mgr;-SePh)(3)Mn(CO)(3), and (CO)(3)Mn(&mgr;-SePh)(3)Fe(CO)(3).

    Science.gov (United States)

    Liaw, Wen-Feng; Chuang, Chih-Yuan; Lee, Way-Zen; Lee, Chen-Kang; Lee, Gene-Hsiang; Peng, Shie-Ming

    1996-04-24

    Oxidative addition of diorganyl diselenides to the coordinatively unsaturated, low-valent transition-metal-carbonyl fragment [Mn(CO)(5)](-) produced cis-[Mn(CO)(4)(SeR)(2)](-). The complex cis-[PPN][Mn(CO)(4)(SePh)(2)] crystallized in triclinic space group P&onemacr; with a = 10.892(8) Å, b = 10.992(7) Å, c = 27.021(4) Å, alpha = 101.93(4) degrees, beta = 89.79(5) degrees, gamma = 116.94(5) degrees, V = 2807(3) Å(3), and Z = 2; final R = 0.085 and R(w) = 0.094. Thermolytic transformation of cis-[Mn(CO)(4)(SeMe)(2)](-) to [(CO)(3)Mn(&mgr;-SeMe)(3)Mn(CO)(3)](-) was accomplished in high yield in THF at room temperature. Crystal data for [Na-18-crown-6-ether][(CO)(3)Mn(&mgr;-SeMe)(3)Mn(CO)(3)]: trigonal space group R&thremacr;, a = 13.533(3) Å, c = 32.292(8) Å, V = 5122(2) Å(3), Z = 6, R = 0.042, R(w) = 0.041. Oxidation of Co(2+) to Co(3+) by diphenyl diselenide in the presence of chelating metallo ligands cis-[Mn(CO)(4)(SePh)(2)](-) and cis-[Mn(CO)(4)(TePh)(2)](-), followed by a bezenselenolate ligand rearranging to bridge two metals and a labile carbonyl shift from Mn to Co, led directly to [(CO)(4)Mn(&mgr;-TePh)(2)Co(CO)(&mgr;-SePh)(3)Mn(CO)(3)]. Crystal data: triclinic space group P&onemacr;, a = 11.712(3) Å, b = 12.197(3) Å, c = 15.754(3) Å, alpha = 83.56(2) degrees, beta = 76.13(2) degrees, gamma = 72.69(2) degrees, V = 2083.8(7) Å(3), Z = 2, R = 0.040, R(w) = 0.040. Addition of fac-[Fe(CO)(3)(SePh)(3)](-) to fac-[Mn(CO)(3)(CH(3)CN)(3)](+) resulted in formation of (CO)(3)Mn(&mgr;-SePh)(3)Fe(CO)(3). This neutral heterometallic complex crystallized in monoclinic space group P2(1)/n with a = 8.707(2) Å, b = 17.413(4) Å, c = 17.541(4) Å, beta = 99.72(2) degrees, V = 2621(1) Å(3), and Z = 4; final R = 0.033 and R(w) = 0.030.

  15. Catalysis on singly dispersed bimetallic sites

    Science.gov (United States)

    Zhang, Shiran; Nguyen, Luan; Liang, Jin-Xia; Shan, Junjun; Liu, Jingyue; Frenkel, Anatoly I.; Patlolla, Anitha; Huang, Weixin; Li, Jun; Tao, Franklin

    2015-08-01

    A catalytic site typically consists of one or more atoms of a catalyst surface that arrange into a configuration offering a specific electronic structure for adsorbing or dissociating reactant molecules. The catalytic activity of adjacent bimetallic sites of metallic nanoparticles has been studied previously. An isolated bimetallic site supported on a non-metallic surface could exhibit a distinctly different catalytic performance owing to the cationic state of the singly dispersed bimetallic site and the minimized choices of binding configurations of a reactant molecule compared with continuously packed bimetallic sites. Here we report that isolated Rh1Co3 bimetallic sites exhibit a distinctly different catalytic performance in reduction of nitric oxide with carbon monoxide at low temperature, resulting from strong adsorption of two nitric oxide molecules and a nitrous oxide intermediate on Rh1Co3 sites and following a low-barrier pathway dissociation to dinitrogen and an oxygen atom. This observation suggests a method to develop catalysts with high selectivity.

  16. Broadband ferromagnetic resonance characterization of anisotropies and relaxation in exchange-biased IrMn/CoFe bilayers

    Science.gov (United States)

    Beik Mohammadi, Jamileh; Jones, Joshua Michael; Paul, Soumalya; Khodadadi, Behrouz; Mewes, Claudia K. A.; Mewes, Tim; Kaiser, Christian

    2017-02-01

    The magnetization dynamics of exchange-biased IrMn/CoFe bilayers have been investigated using broadband and in-plane angle-dependent ferromagnetic resonance spectroscopy. The interface energy of the exchange bias effect in these bilayers exceeds values previously reported for metallic antiferromagnets. A strong perpendicular magnetic anisotropy and a small in-plane uniaxial anisotropy are also observed in these films. The magnetization relaxation of the bilayers has a strong unidirectional contribution, which is in part caused by two-magnon scattering. However, a detailed analysis of in-plane angle- and thickness-dependent linewidth data strongly suggests the presence of a previously undescribed unidirectional relaxation mechanism.

  17. Bimetallic nanoparticles for arsenic detection.

    Science.gov (United States)

    Moghimi, Nafiseh; Mohapatra, Mamata; Leung, Kam Tong

    2015-06-02

    Effective and sensitive monitoring of heavy metal ions, particularly arsenic, in drinking water is very important to risk management of public health. Arsenic is one of the most serious natural pollutants in soil and water in more than 70 countries in the world. The need for very sensitive sensors to detect ultralow amounts of arsenic has attracted great research interest. Here, bimetallic FePt, FeAu, FePd, and AuPt nanoparticles (NPs) are electrochemically deposited on the Si(100) substrate, and their electrochemical properties are studied for As(III) detection. We show that trace amounts of As(III) in neutral pH could be determined by using anodic stripping voltammetry. The synergistic effect of alloying with Fe leads to better performance for Fe-noble metal NPs (Au, Pt, and Pd) than pristine noble metal NPs (without Fe alloying). Limit of detection and linear range are obtained for FePt, FeAu, and FePd NPs. The best performance is found for FePt NPs with a limit of detection of 0.8 ppb and a sensitivity of 0.42 μA ppb(-1). The selectivity of the sensor has also been tested in the presence of a large amount of Cu(II), as the most detrimental interferer ion for As detection. The bimetallic NPs therefore promise to be an effective, high-performance electrochemical sensor for the detection of ultratrace quantities of arsenic.

  18. Hybrid supercapacitor devices based on MnCo2O4 as the positive electrode and FeMn2O4 as the negative electrode

    Science.gov (United States)

    Nagamuthu, Sadayappan; Vijayakumar, Subbukalai; Lee, Seong-Hun; Ryu, Kwang-Sun

    2016-12-01

    MnCo2O4 nanosheets and FeMn2O4 nanospheres were synthesized using a hydrothermal method. Choline chloride was used as the capping agent during the preparation of the nanoparticles. XRD patterns confirmed the spinel structure of MnCo2O4 and FeMn2O4. XPS measurements were used to determine the oxidation state of the prepared spinel metal oxides. HRTEM images revealed the formation of hexagonal nanosheets of MnCo2O4 and nanospheres of FeMn2O4. Electrochemical measurements were made for both positive and negative electrodes using three electrode systems. MnCo2O4 Exhibits 282C g-1 and FeMn2O4 yields 110C g-1 at a specific current of 1 A g-1. Hybrid supercapacitor device was fabricated using MnCo2O4 as the positive and FeMn2O4 as the negative electrode material. The hybrid supercapacitor device was delivered a maximum power of 37.57 kW kg-1.

  19. Time-resolved infrared spectral studies of intermediates formed in the laser flash photolysis of Mn(CO){sub 5}CH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Boese, W.T.; Ford, P.C. [Univ. of California, Santa Barbara, CA (United States)

    1994-09-01

    Laser flash photolysis (308 nm) of Mn(CO){sub 5}CH{sub 3} (I) in different solvents leads predominantly to CO photodissociation and the formation of reactive intermediates formulated as the solvento complexes cis-Mn(CO){sub 4}(solv)CH{sub 3}. This conclusion is based upon the solvent sensitivity of the time-resolved infrared spectra and the dynamics of reactions with various ligands. For example, the reaction of cis-Mn(CO){sub 4}(solv)CH{sub 3} with CO displays second-order kinetics with a rate constant k{sub co} nearly 8 orders of magnitude larger for solv = perfluoro-(methylcyclohexane) than for solv = tetrahydrofuran. The k{sub l} values for the second-order reaction of cis-Mn(CO){sub 4}(solv)CH{sub 3} in cyclohexane with various ligands L follow the approximate order 4-phenylpyridine H{sub 2}O THF > P(OMe){sub 3} PPh{sub 3} > CO N{sub 2}. The quantitative behaviors of intermediates seen in the flash photolysis of I are compared with those seen in similar studies of the acetyl complex Mn(Co){sub 5}(COCH){sub 3} (II). 24 refs., 6 figs., 2 tabs.

  20. Cation distribution in spinel (Mn,Co,Cr){sub 3}O{sub 4} at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Purwanto, A.; Fajar, A.; Mugirahardjo, H. [National Nuclear Energy Agency (BATAN), Serpong Tengerang (Indonesia). Center for Technology of Nuclear Industrial Materials; Fergus, J.W.; Wang, K. [Auburn Univ., AL (United States). Materials Research and Education Center

    2010-06-15

    As part of a study of the long-term operation of solid-oxide fuel cells, three (Mn,Co,Cr){sub 3}O{sub 4} samples have been synthesized and characterized. X-ray and neutron diffraction patterns from the powder samples at room temperature were measured and the data were co-refined. The neutron data were indispensible in locating Mn, Co and Cr within the crystallographic unit cell with their respective atomic occupancies. Two of these samples have been identified as cubic Mn{sub 0.76}Co{sub 0.58}Cr{sub 1.66}O{sub 4} and Mn{sub 1.28}Co{sub 1.72}O{sub 4}. The third is a twophase sample containing cubic Mn{sub 1.66}Co{sub 1.34}O{sub 4} and tetragonal Mn{sub 2.05}Co{sub 0.91}O{sub 4} in a 59.1 (6):40.9 (6)% mass fraction ratio. Cr, which might be introduced from reaction with chromia during oxidation of interconnect materials, exhibits a preference for the octahedral site rather than the tetrahedral site. Without Cr, Mn dominates the octahedral site. (orig.)

  1. Electrophoretic deposition of (Mn,Co)3O4 spinel coating for solid oxide fuel cell interconnects

    Science.gov (United States)

    Zhang, Hui; Zhan, Zhaolin; Liu, Xingbo

    2011-10-01

    We discuss here our attempt to develop (Mn,Co)3O4 spinel coatings on the surface of Cr-containing steel through electrophoretic deposition (EPD) followed by reduced-atmosphere sintering for solid oxide fuel cell (SOFC) interconnect application. The effects of EPD voltages and sintering atmospheres on the microstructure, electrical conductivity and long-term stability of the coated interconnects are examined by means of scanning electron microscopy (SEM), energy dispersion spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), and four-probe resistance techniques. For the spinel coatings generated using smaller voltage than 400 V, the interconnect surfaces exhibit good packing behavior and high conductivity. The reduced atmosphere during sintering has a beneficial impact on the minimizing chromia subscale formation and thus reducing the area specific resistance (ASR) of the coated interconnects. Moreover, it is interesting to note that a more stable long-term performance is achieved for the spinel coating sintered in H2/H2O atmosphere with thin chromia sub-scale and no Cr penetration. Based on the current results, EPD followed by reduced-atmosphere sintering is a fast and economic way to deposit (Mn,Co)3O4 coating for SOFC interconnect applications.

  2. Laser deposition of bimetallic island films

    Science.gov (United States)

    Kucherik, A. O.; Arakelyan, S. M.; Kutrovskaya, S. V.; Osipov, A. V.; Istratov, A. V.; Vartanyan, T. A.; Itina, T. E.

    2016-08-01

    In this work the results of a bimetallic Au-Ag structure deposition from the colloidal system by nanosecond laser radiation are presented. The formation of the extended arrays of gold and silver nanoparticles with controlled morphology is examined. We report the results of formation bimetallic islands films with various electrical and optical properties. The changes in the optical properties of the obtained thin films are found to depend on their morphology.

  3. Effects of the Mn/Co ratio on the magnetic transition and magnetocaloric properties of Mn1+χCo1-χGe alloys

    Institute of Scientific and Technical Information of China (English)

    Ma Sheng-Can; Wang Dun-Hui; Xuan Hai-Cheng; Shen Ling-Jia; Cao Qing-Qi; Du You-Wei

    2011-01-01

    We have investigated the magnetic transition and magnetocaloric effects of Mn1+χCo1-χGe alloys by tuning the ratio of Mn/Co. With increasing Mn content, a series of first-order magnetostructural transitions from ferromagnetic to paramagnetic states with large changes of magnetization are observed at room temperature. Further increasing the content of Mn (χ = 0.11) gives rise to a single second-order magnetic transition. Interestingly, large low-field magnetic entropy changes with almost zero magnetic hysteresis are observed in these alloys. The effects of Mn/Co ratio on magnetic transition and magnetocaloric effects are discussed in this paper.

  4. Facile preparation of ordered mesoporous MnCo2O4 for low-temperature selective catalytic reduction of NO with NH3

    Science.gov (United States)

    Qiu, Mingying; Zhan, Sihui; Yu, Hongbing; Zhu, Dandan; Wang, Shengqiang

    2015-01-01

    Ordered mesoporous MnCo2O4 nanomaterials were successfully prepared through the nanocasting route using SBA-15 and KIT-6 as hard templates. These mesoporous nanomaterials were characterized using XRD, BET, TEM, NH3-TPD, H2-TPR, NO-TPD, XPS and DRIFT. The low temperature selective catalytic reduction (SCR) activity of NO with NH3 was investigated, which revealed that 3D-MnCo2O4 using KIT-6 as a template can totally clean all NO over a wide temperature range of 100-250 °C with a gas hourly space velocity (GHSV) of 32 000 h-1, while 2D-MnCo2O4 with SBA-15 as a template had 95% conversion rate at the same condition. 3D-MnCo2O4 showed the best performance to clean NO due to its typical three-dimensional porous structure, large specific surface area, abundant active surface oxygen species and Lewis acid sites. All the results indicate that a novel, cheap catalyst for catalytic removal of NO can be designed by controlling the morphology at the nanoscale.Ordered mesoporous MnCo2O4 nanomaterials were successfully prepared through the nanocasting route using SBA-15 and KIT-6 as hard templates. These mesoporous nanomaterials were characterized using XRD, BET, TEM, NH3-TPD, H2-TPR, NO-TPD, XPS and DRIFT. The low temperature selective catalytic reduction (SCR) activity of NO with NH3 was investigated, which revealed that 3D-MnCo2O4 using KIT-6 as a template can totally clean all NO over a wide temperature range of 100-250 °C with a gas hourly space velocity (GHSV) of 32 000 h-1, while 2D-MnCo2O4 with SBA-15 as a template had 95% conversion rate at the same condition. 3D-MnCo2O4 showed the best performance to clean NO due to its typical three-dimensional porous structure, large specific surface area, abundant active surface oxygen species and Lewis acid sites. All the results indicate that a novel, cheap catalyst for catalytic removal of NO can be designed by controlling the morphology at the nanoscale. Electronic supplementary information (ESI) available: Low-angle XRD

  5. Magnetic Properties and AC Losses in AFe2O4 (A = Mn, Co, Ni, Zn Nanoparticles Synthesized from Nonaqueous Solution

    Directory of Open Access Journals (Sweden)

    Oleksandr Yelenich

    2015-01-01

    Full Text Available Nanosized particles of AFe2O4 (A = Mn, Co, Ni, or Zn spinel ferrites were synthesized by coprecipitation from nonaqueous solutions using nitrate salts as starting reagents. The particles were characterized by X-ray diffraction, transmission electron microscopy, and magnetic measurements. Quasistatic magnetic measurements show superparamagnetic behavior with blocking temperature below room temperature for cobalt, nickel, and zinc spinel ferrite nanoparticles. Characteristic magnetic parameters of the particles including average magnetic moment of an individual nanoparticle and blocking temperature have been determined. The specific loss power which is released on the exposure of an ensemble of synthesized particles to a magnetic field is calculated and measured experimentally. It is shown that among all nanoferrites under study, the ZnFe2O4 nanoparticles demonstrate the highest heating efficiency in AC magnetic fields. The key parameters responsible for the heating efficiency in AC magnetic field have been determined. The directions to enhance the SLP value have been outlined.

  6. Formation of graphene-like 2D spinel MnCo2O4 and its lithium storage properties

    DEFF Research Database (Denmark)

    Huang, Guoyong; Guo, Xueyi; Cao, Xiao

    2017-01-01

    Two-dimensional (2D) materials fulfill the requirements for fast lithium storage due to the large exposed surface area and the open shortened path for Li insertion/extraction. Novel graphene-like 2D spinel MnCo2O4 powders have been synthesized, which inherit the morphology and structure of special.......0 mAhg-1 at 0.4 Ag-1 after 200 cycles). Remarkably, the 2D layered structure is retained perfectly after 200 cycles at 0.4 Ag-1. Hence, the type of unique self-assembly metal-organic precursors could provide a flexible and general way to synthesize 2D layered metal oxides as templates for high...

  7. Structural, morphological, optical, and magnetic properties of Gd-doped and (Gd, Mn) co-doped ZnO nanoparticles

    Science.gov (United States)

    Poornaprakash, B.; Chalapathi, U.; Babu, S.; Park, Si-Hyun

    2017-09-01

    Undoped, Gd doped, and (Gd, Mn) co-doped ZnO nanoparticles were fabricated via a hydrothermal method and their structural, morphological, optical, and magnetic properties were examined. X-ray diffraction and Raman spectroscopy studies confirmed that the Gd and Mn ions successfully entered the ZnO hexagonal lattice as substitute ions without changing the internal structure of the lattice. Morphology studies revealed that the synthesized nanoparticles were monodisperse and closely hexagonal shaped. The reflectance spectra showed a red shift of the absorption edge in both doped and co-doped samples. The diamagnetic ZnO sample was altered into a ferromagnetic material when doped with Gd ions, but this behavior was suppressed when Mn ions were co-doped into the matrix.

  8. Evolution of magnetostructural transition and magnetocaloric effect with Al doping in MnCoGe1-xAlx compounds

    KAUST Repository

    Bao, Lifu

    2014-01-03

    The effect of Al doping in MnCoGe1-xAlx compounds has been investigated. The substitution of Al for Ge enhances Mn-Mn covalent bonding by shortening the distance of nearest Mn atom layers, and thus stabilizes the hexagonal structure. As a result, first-order magnetostructural transition between ferromagnetic martensite and paramagnetic austenite takes place for the optimized compositions (x = 0.01, 0.02). Accompanied with the magnetostructural transition, large magnetocaloric effect (MCE) is observed. More doping of Al(x = 0.03, 0.04) leads to the separation of magnetic and structural transitions and remarkable reduction of MCE. © 2014 IOP Publishing Ltd.

  9. Synthesis and Characterization of Optically Active Fractal Seed Mediated Silver Nickel Bimetallic Nanoparticles

    Directory of Open Access Journals (Sweden)

    Joseph Adeyemi Adekoya

    2014-01-01

    Full Text Available The synthesis of new seed mediated AgNi allied bimetallic nanocomposites was successfully carried out by the successive reduction of the metal ions in diethylene glycol, ethylene glycol, glycerol, and pentaerythritol solutions, with concomitant precipitation of Ag/Ni bimetal sols. The optical measurement revealed the existence of distinct band edge with surface plasmon resonance (SPR in the region of 400–425 nm and excitonic emission with maximum peak at 382 nm which were reminiscent of cluster-in-cluster surface enriched bimetallic silver-nickel sols. The morphological characterization by transmission electron microscopy, high resolution transmission electron microscopy, and X-ray diffraction analyses complimented by surface scan using X-ray photoelectron spectroscopy strongly supported the formation of intimately alloyed face-centered silver/nickel nanoclusters.

  10. Magnetic and structural results on (Mn,Co3(Si,P and (Fe,Co3(Si,P alloys

    Directory of Open Access Journals (Sweden)

    J.V. Leitão

    2014-01-01

    Previously reported value for transition temperatures and compositional limits have been found to be incorrect for the (Fe,Co3P system and a novel inverse magnetocaloric effect compound has been discovered as a consequence of the study performed in the (Mn,Co3(Si,P system.

  11. The solubility of rhodochrosite (MnCO3) and siderite (FeCO3) in anaerobic aquatic environments

    DEFF Research Database (Denmark)

    Jensen, Dorthe Lærke; Boddum, J.K.; Tjell, Jens Christian

    2002-01-01

    Natural groundwaters are often reported to be highly supersaturated with the carbonate minerals siderite (FeCO3) and rhodochrosite (MnCO3). The kinetics of precipitation and dissolution were determined in the light of new determinations of the solubility products of siderite and rhodochrosite. La...

  12. Theoretical study on the electronic and magnetic properties of double perovskite La2-xSrxMnCoO6 (x = 0,1,2)

    Science.gov (United States)

    Lan, X.; Kong, S.; Zhang, W. Y.

    2011-12-01

    In this paper, the electronic and magnetic properties of double perovskite La2- x Sr x MnCoO6 ( x = 0,1,2) have been studied using the local-spin-density approximation + U method. For the three compositions investigated, the low symmetry P21/ n structure yields consistently lower energy than that of the high symmetry Fmbar{3m} Fm3̅ m structure. The strong electronic correlation and the orbital polarization of Co- d electrons play crucial roles. In agreement with experiments, we find that La2MnCoO6 is a ferromagnetic insulator with both Mn and Co ions in their high-spin states. The tilting of oxygen octahedrons is most significant in this case and is responsible for its insulating behavior; for LaSrMnCoO6, the ground state remains a ferromagnetic insulator with Mn and Co ions in their high-spin states. The optimized P21/ n and Fmbar{3m} Fm3̅ m crystal structures are nearly the same, and the P21/ n structure is stabilized by the spontaneous layer-wise antiferro-orbital ordering of Co- d electrons. We also predict that Sr2MnCoO6 is a ferromagnetic metal, and its electronic structure can be viewed as a rigid band shifting from that of LaSrMnCoO6. Due to the strong covalency between transition metal and oxygen ions, the valences of Mn and Co ions differ considerably from those derived from purely ionic model. Also, doping induced holes mainly go to oxygen sites though the density of states near the Fermi energy has strong mixed character. This feature, together with the orbital ordering phenomenon, should be observable via the X-ray near-edge absorption spectroscopy and the polarized X-ray diffraction spectra.

  13. Synthesis of Anchored Bimetallic Catalysts via Epitaxy

    Directory of Open Access Journals (Sweden)

    Jiaxin Liu

    2016-06-01

    Full Text Available The development of thermodynamically stable supported bimetallic catalysts for high-temperature reaction is significant and highly desirable but remains a grand challenge. In this work, we report a novel approach that relies on the interaction of metal nanoparticles with the support material to form unique bimetallic nanoparticles, which epitaxially anchor onto the support surface. Such unique nanostructured systems are catalytically active and ultrastable during selected catalytic reactions. In this paper, we describe the synthesis processes of ultrastable PtZn nanoparticles epitaxially anchored onto ZnO nanowires, which primarily consist of {10−10} nanoscale facets. Such anchored PtZn nanoparticles demonstrated good stability during high temperature treatments and selected catalytic reactions. The synthesis approach reported in this work provides a new strategy to develop thermodynamically stable supported bimetallic catalysts.

  14. Density functional theory study of small X-doped Mg(n) (X = Fe, Co, Ni, n = 1-9) bimetallic clusters: equilibrium structures, stabilities, electronic and magnetic properties.

    Science.gov (United States)

    Kong, Fanjie; Hu, Yanfei

    2014-03-01

    The geometries, stabilities, and electronic and magnetic properties of Mg(n) X (X = Fe, Co, Ni, n = 1-9) clusters were investigated systematically within the framework of the gradient-corrected density functional theory. The results show that the Mg(n)Fe, Mg(n)Co, and Mg(n)Ni clusters have similar geometric structures and that the X atom in Mg(n)X clusters prefers to be endohedrally doped. The average atomic binding energies, fragmentation energies, second-order differences in energy, and HOMO-LUMO gaps show that Mg₄X (X = Fe, Co, Ni) clusters possess relatively high stability. Natural population analysis was performed and the results showed that the 3s and 4s electrons always transfer to the 3d and 4p orbitals in the bonding atoms, and that electrons also transfer from the Mg atoms to the doped atoms (Fe, Co, Ni). In addition, the spin magnetic moments were analyzed and compared. Several clusters, such as Mg₁,₂,₃,₄,₅,₆,₈,₉Fe, Mg₁,₂,₄,₅,₆,₈,₉Co, and Mg₁,₂,₅,₆,₇,₉Ni, present high magnetic moments (4 μ(B), 3 μ(B), and 2 μ(B), respectively).

  15. Magneto-optical response in bimetallic metamaterials

    CERN Document Server

    Atmatzakis, Evangelos; Fedotov, Vassili; Vienne, Guillaume; Zheludev, Nikolay I

    2016-01-01

    We demonstrate resonant Faraday polarization rotation in plasmonic arrays of bimetallic nano-ring resonators consisting of Au and Ni sections. This metamaterial design allows to optimize the trade-off between the enhancement of magneto-optical effects and plasmonic dissipation. Although Ni sections correspond to as little as ~6% of the total surface of the metamaterial, the resulting magneto-optically induced polarization rotation is equal to that of a continuous film. Such bimetallic metamaterials can be used in compact magnetic sensors, active plasmonic components and integrated photonic circuits.

  16. Segregation and phase dynamics in supported bimetallic nanoparticles

    Science.gov (United States)

    Nashner, Michael Sydney

    1997-12-01

    A set of supported bimetallic catalysts, designated lbrack Resb7Ir-Nrbrack,\\ lbrack Resb7Ir-Prbrack,\\ lbrack Resb5IrResb2-Prbrack, and lbrack Resb5IrResb2-Prbrack, has been prepared from two structural isomers of the cluster compound (Z) sb2lbrack Resb7IrC(CO)sb{23}rbrack\\ (Zsp+=NEtsb4sp+,\\ N(PPhsb3)sb2sp+) by deposition onto high surface area alumina ({≤}1% Re) and activation in Hsb2 at 773 K. The more active catalysts (lbrack Resb7Ir-N) and lbrack Resb5IrResb2-Nrbrack) are modeled by a hemisphere of close-packed (hcp) metal atoms (avg. diameter 1 nm) with Ir at the core. On the other hand the less active catalysts (lbrack Resb7Ir-Prbrack and lbrack Resb5IrResb2-Prbrack) are better described as two-dimensional layer structures. Supported bimetallic particles were obtained by reduction of the neutral molecular carbonyl cluster precursor PtRusb5C(CO)sb{16} with hydrogen. A detailed structural model of the nanoparticles has been deduced on the basis of studies by in-situ extended x-ray absorption fine structure spectroscopy (EXAFS), scanning transmission electron microscopy (STEM), microprobe energy dispersive x-ray (EDX) analysis, and electron microdiffraction. These experiments show that the bimetallic nanoparticles have a Pt:Ru composition of 1:5, an average diameter of ca. 1.5 nm, and adopt a face-centered cubic (fcc) closest packing structure. The local metal coordination environment, revealed by multiple scattering analysis of the EXAFS data, shows Pt segregation to the particle surfaces under an ambient Hsb2 atmosphere. The incipient lbrack PtRusb5rbrack nanoparticles were found to nucleate from a disordered structure where Pt is found in highly coordinating environments (i.e., the core) at temperatures as low as 473 K. This structure inverts to form the structure with surface segregated Pt. The reaction between a silicon monolayer deposited on Pt(111) by chemical vapor deposition (CVD) using silane (SiHsb4) is described. Using Auger electron

  17. Surface structures and compositions of Au-Rh bimetallic nanoclusters supported on thin-film Al2O3/NiAl(100) probed with CO

    Science.gov (United States)

    Lee, Hsuan; Liao, Zhen-He; Hsu, Po-Wei; Hung, Ting-Chieh; Wu, Yu-Cheng; Lin, Yuwei; Wang, Jeng-Han; Luo, Meng-Fan

    2017-07-01

    The surface structures and compositions of Au-Rh bimetallic nanoclusters on an ordered thin film of Al2O3/NiAl(100) were investigated, primarily with infrared reflection absorption spectra and temperature-programmed desorption of CO as a probe molecule under ultrahigh-vacuum conditions and calculations based on density-functional theory. The bimetallic clusters were formed by sequential deposition of vapors of Au and Rh onto Al2O3/NiAl(100) at 300 K. Alloying in the clusters was active and proceeded toward a specific structure—a fcc phase, (100) orientation, and Rh core-Au shell structure, regardless of the order of metal deposition. For Au clusters incorporating deposited Rh, the Au atoms remained at the cluster surface through position exchange and became less coordinated; for deposition in reverse order, deposited Au simply decorated the surfaces of Rh clusters. Both adsorption energy and infrared absorption intensity were enhanced for CO on Au sites of the bimetallic clusters; both of them are associated with the bonding to Rh and also a decreased coordination number of CO-binding Au. These enhancements can thus serve as a fingerprint for alloying and atomic inter-diffusion in similar bimetallic systems.

  18. Metal segregation in supported bimetallic catalysts:. gamma. -Al/sub 2/O/sub 3/-supported CO hydrogenation catalysts prepared from RhOs/sub 3/, Rh/sub 4/, and FeOs/sub 3/ clusters

    Energy Technology Data Exchange (ETDEWEB)

    Budge, J.R.; Lucke, B.F.; Gates, B.C.; Toran, J.

    1985-02-01

    Al/sub 2/O/sub 3/-supported metals were prepared from (H/sub 2/RhOs/sub 3/(CO)/sub 10/(acetylacetonate)), (Rh/sub 4/(CO)/sub 12/), and (H/sub 2/FeOs/sub 3/(CO)/sub 13/). The samples were characterized by infrared spectroscopy after reaction with CO + H/sub 2/ and tested as catalysts for conversion of CO + H/sub 2/ in a flow reactor at 200 and 270/sup 0/C and 10 atm. Used catalysts were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and elemental analysis. The catalyst lost Os during operation, presumably as a result of formation of volatile carbonyls. The catalytic reaction products were a nearly Schulz-Flory-Anderson distribution of hydrocarbons with small yields of dimethyl ether (formed from methanol). The performance of the catalyst prepared from the RhOs/sub 3/ clusters was closely similar to that of the catalyst prepared from the Rh/sub 4/ cluster. Characterization of the samples after treatment in CO + H/sub 2/ and after catalysis demonstrated that the RhOs/sub 3/ clusters broke apart, first giving triosmium clusters and mononuclear Rh complexes and then, at higher temperatures, giving Rh crystallites and mononuclear Os complexes. The catalytic activity for hydrocarbon synthesis is attributed to the Rh metal; the activity for methanol synthesis is tentatively associated with ionic Rh complexes. The FeOs/sub 3/ catalyst was two orders of magnitude less active than the Rh Os/sub 3/ catalyst, apparently consisting of small iron oxide particles and mononuclear Os complexes. The selectivity of this catalyst for dimethyl ether formation increased markedly with time onstream in the flow reactor; after 55 h, 36 mol% of the organic product was ether. 25 refs., 5 figs., 3 tabs.

  19. Near room temperature magnetocaloric properties and the universal curve of MnCoGe1-xCux

    Science.gov (United States)

    Si, Xiaodong; Liu, Yongsheng; Lu, Xiaofei; Shen, Yulong; Wang, Wenli; Yu, Wenying; Zhou, Tao; Gao, Tian

    2017-05-01

    Intermetallic compounds based on MnCoGe have drawn attention due to the coupled magnetic and structural transformations and the large magnetocaloric entropy. Here, we provide a systematic comparison of experimental data under different magnetic fields with magnetic and the magnetocaloric properties. The ferromagnetic transition temperature (TC) increases from 353.4(6) K for x = 0.01 to 363.4(4) K for x = 0.04 with increasing nominal copper content. The maximum magnetic entropy change |ΔSM| in a magnetic field change of 5 T is found to be 18.3(2) J/(kg K) with a large relative cooling power (RCP) value of 292.5(4) J/kg for x = 0.01, revealing that the present system can provide an acceptable magnetocaloric effect at a cheaper price for magnetic refrigeration materials. Making attempt to contrast a master curve for the present system, we find the experimental values of magnetic field dependence of the magnetic entropy change are consistent with a phenomenological universal curve.

  20. Calendar and cycle life study of Li(NiMnCo)O2-based 18650 lithium-ion batteries

    Science.gov (United States)

    Ecker, Madeleine; Nieto, Nerea; Käbitz, Stefan; Schmalstieg, Johannes; Blanke, Holger; Warnecke, Alexander; Sauer, Dirk Uwe

    2014-02-01

    An extensive set of accelerated aging tests has been carried out employing a Li-ion high energy 18650 system (2.05 Ah), negative electrode: carbon, positive electrode: Li(NiMnCo)O2). It is manufactured by Sanyo, labeled UR18650E, and is a commercial off-the-shelf product. The tests comprise both calendar life tests at different ambient temperatures and constant cell voltages and cycle life tests operating the cells within several voltage ranges and levels using standard test profiles. In total, 73 cells have been tested. The calendar life test matrix especially investigates the influence of SOC on aging in detail, whereas the cycle life matrix focuses on a detailed analysis of the influence of cycle depth. The study shows significant impact of the staging behavior of the carbon electrode on cycle life. Furthermore a strong influence of the carbon potential on calendar aging has been detected. Observed relations between aging and the different influence factors as well as possible degradation mechanisms are discussed. Analysis of C/4 discharge voltage curves suggests that cycle aging results in different aging processes and changes in material properties compared to calendar aging. Cycling, especially with cycles crossing transitions between voltage plateaus of the carbon electrode seems to destroy the carbon structure.

  1. Tuning structural instability toward enhanced magnetocaloric effect around room temperature in MnCo1−xZnxGe

    Science.gov (United States)

    Choudhury, D.; Suzuki, T.; Tokura, Y.; Taguchi, Y.

    2014-01-01

    Magnetocaloric effect is the phenomenon that temperature change of a magnetic material is induced by application of a magnetic field. This effect can be applied to environmentally-benign magnetic refrigeration technology. Here we show a key role of magnetic-field-induced structural instability in enhancing the magnetocaloric effect for MnCo1−xZnxGe alloys (x = 0–0.05). The increase in x rapidly reduces the martensitic transition temperature while keeping the ferromagnetic transition around room temperature. Fine tuning of x around x = 0.03 leads to the concomitant structural and ferromagnetic transition in a cooling process, giving rise to enhanced magnetocaloric effect as well as magnetic-field-induced structural transition. Analyses of the structural phase diagrams in the T-H plane in terms of Landau free-energy phenomenology accounts for the characteristic x-dependence of the observed magnetocaloric effect, pointing to the importance of the magnetostructural coupling for the design of high-performance magnetocalorics. PMID:25519919

  2. Tuning structural instability toward enhanced magnetocaloric effect around room temperature in MnCo(1-x)Zn(x)Ge.

    Science.gov (United States)

    Choudhury, D; Suzuki, T; Tokura, Y; Taguchi, Y

    2014-12-18

    Magnetocaloric effect is the phenomenon that temperature change of a magnetic material is induced by application of a magnetic field. This effect can be applied to environmentally-benign magnetic refrigeration technology. Here we show a key role of magnetic-field-induced structural instability in enhancing the magnetocaloric effect for MnCo(1-x)Zn(x)Ge alloys (x = 0-0.05). The increase in x rapidly reduces the martensitic transition temperature while keeping the ferromagnetic transition around room temperature. Fine tuning of x around x = 0.03 leads to the concomitant structural and ferromagnetic transition in a cooling process, giving rise to enhanced magnetocaloric effect as well as magnetic-field-induced structural transition. Analyses of the structural phase diagrams in the T-H plane in terms of Landau free-energy phenomenology accounts for the characteristic x-dependence of the observed magnetocaloric effect, pointing to the importance of the magnetostructural coupling for the design of high-performance magnetocalorics.

  3. MnCo{sub 2}O{sub 4} spinel chromium barrier coatings for SOFC interconnect by HVOF

    Energy Technology Data Exchange (ETDEWEB)

    Lagerbom, J.; Varis, T.; Pihlatie, M.; Himanen, O.; Saarinen, V.; Kiviaho, J.; Turunen, E. [VTT Technical Research Centre of Finland, Espoo (Finland); Puranen, J. [Tampere Univ. of Technology (Finland). Inst. of Materials Science

    2010-07-01

    Chromia released from steel parts used for interconnect plates by evaporation and condensation can quickly degrade the cell (cathode) performance in solid oxide fuel cell SOFC. Coatings on top of the IC plate can work as a chromium evaporation barrier. The coating material should have good electrical conductivity, high temperature stability and nearly the same coefficient of thermal expansion as the cell materials. One candidate for the coating material is MnCo{sub 2}O{sub 4} spinel because of its suitable properties. High velocity oxy fuel (HVOF) spraying was used for the coating application on Crofer 22 APU steel samples. Using commercial and self made spray dried powders together with an HV2000 spray gun it was possible to successfully manufacture, well adhering, dense and reasonably uniform coatings. The samples were tested in oxidation exposure tests in air followed by post analysis in SEM. Powders and coatings microstructures are presented here, both before and after exposure. It was found out that together with spraying parameters the powder characteristics used influence clearly to the coating quality. Especially as very thin coatings was aimed with dense structure fine powders was found to be essential. (orig.)

  4. Néel walls between tailored parallel-stripe domains in IrMn/CoFe exchange bias layers

    Energy Technology Data Exchange (ETDEWEB)

    Ueltzhöffer, Timo, E-mail: timo.ueltzhoeffer@physik.uni-kassel.de; Schmidt, Christoph; Ehresmann, Arno [Institute of Physics and Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel, Heinrich-Plett-Str. 40, 34132 Kassel (Germany); Krug, Ingo [Peter Gruenberg Institute and JARA-FIT, FZ Juelich, D-52425 Juelich (Germany); Institut für Optik und Atomare Physik, Technische Universität Berlin, Berlin (Germany); Nickel, Florian; Gottlob, Daniel [Peter Gruenberg Institute and JARA-FIT, FZ Juelich, D-52425 Juelich (Germany)

    2015-03-28

    Tailored parallel-stripe magnetic domains with antiparallel magnetizations in adjacent domains along the long stripe axis have been fabricated in an IrMn/CoFe Exchange Bias thin film system by 10 keV He{sup +}-ion bombardment induced magnetic patterning. Domain walls between these domains are of Néel type and asymmetric as they separate domains of different anisotropies. X-ray magnetic circular dichroism asymmetry images were obtained by x-ray photoelectron emission microscopy at the Co/Fe L{sub 3} edges at the synchrotron radiation source BESSY II. They revealed Néel-wall tail widths of 1 μm in agreement with the results of a model that was modified in order to describe such walls. Similarly obtained domain core widths show a discrepancy to values estimated from the model, but could be explained by experimental broadening. The rotation senses in adjacent walls were determined, yielding unwinding domain walls with non-interacting walls in this layer system.

  5. The enthalpy change of the hcp {yields} fcc martensitic transformation in Fe-Mn-Co alloys: composition dependence and thermal cycling effects

    Energy Technology Data Exchange (ETDEWEB)

    Marinelli, P.; Fernandez Guillermet, A.; Sade, M

    2004-05-25

    Extending a recent calorimetric study of the Fe-Mn system the enthalpy change associated with the fcc{yields}hcp martensitic transformation in the Fe-Mn-Co system has been determined in alloys with 13{<=}at.% Mn{<=}30 and up to 9 at.% Co. The heat effect has been measured by differential scanning calorimetry, whereas the fraction of material that transformed martensitically was determined by combining a dilatometric technique with the known molar volume versus composition relations. A detailed description of the various experimental and data processing procedures is reported. The enthalpy change is discussed as a function of composition and of the number of thermal cycles of transformation and retransformation. The picture of the energetics of the fcc{yields}hcp martensitic transformation emerging from the present study should be useful in future attempts to model the thermodynamics and phase stability relations in the Fe-Mn-Co system.

  6. CuAAC click functionalization of azide-modified nanodiamond with a photoactivatable CO-releasing molecule (PhotoCORM) based on [Mn(CO)3(tpm)]+.

    Science.gov (United States)

    Dördelmann, G; Meinhardt, Thomas; Sowik, Thomas; Krueger, Anke; Schatzschneider, Ulrich

    2012-12-01

    The copper-catalyzed 1,3-dipolar azide-alkyne cycloaddition (CuAAC) was used for the first time to attach a biologically active carbon monoxide delivery agent to modified nanodiamond (ND) as a highly biocompatible carrier. The [Mn(CO)(3)(tpm)](+) photoactivatable CO-releasing molecule (PhotoCORM) on the surface retained the carbon monoxide release properties of the parent compound as shown with the myoglobin assay.

  7. Synthesis of MnFe2O4@Mn-Co oxide core-shell nanoparticles and their excellent performance for heavy metal removal.

    Science.gov (United States)

    Ma, Zichuan; Zhao, Dongyuan; Chang, Yongfang; Xing, Shengtao; Wu, Yinsu; Gao, Yuanzhe

    2013-10-21

    Magnetic nanomaterials that can be easily separated and recycled due to their magnetic properties have received considerable attention in the field of water treatment. However, these nanomaterials usually tend to aggregate and alter their properties. Herein, we report an economical and environmentally friendly method for the synthesis of magnetic nanoparticles with core-shell structure. MnFe2O4 nanoparticles have been successfully coated with amorphous Mn-Co oxide shells. The synthesized MnFe2O4@Mn-Co oxide nanoparticles have highly negatively charged surface in aqueous solution over a wide pH range, thus preventing their aggregation and enhancing their performance for heavy metal cation removal. The adsorption isotherms are well fitted to a Langmuir adsorption model, and the maximal adsorption capacities of Pb(II), Cu(II) and Cd(II) on MnFe2O4@Mn-Co oxide are 481.2, 386.2 and 345.5 mg g(-1), respectively. All the metal ions can be completely removed from the mixed metal ion solutions in a short time. Desorption studies confirm that the adsorbent can be effectively regenerated and reused.

  8. Carbon-Coated Honeycomb Ni-Mn-Co-O Inverse Opal: A High Capacity Ternary Transition Metal Oxide Anode for Li-ion Batteries

    Science.gov (United States)

    McNulty, David; Geaney, Hugh; O’Dwyer, Colm

    2017-01-01

    We present the formation of a carbon-coated honeycomb ternary Ni-Mn-Co-O inverse opal as a conversion mode anode material for Li-ion battery applications. In order to obtain high capacity via conversion mode reactions, a single phase crystalline honeycombed IO structure of Ni-Mn-Co-O material was first formed. This Ni-Mn-Co-O IO converts via reversible redox reactions and Li2O formation to a 3D structured matrix assembly of nanoparticles of three (MnO, CoO and NiO) oxides, that facilitates efficient reactions with Li. A carbon coating maintains the structure without clogging the open-worked IO pore morphology for electrolyte penetration and mass transport of products during cycling. The highly porous IO was compared in a Li-ion half-cell to nanoparticles of the same material and showed significant improvement in specific capacity and capacity retention. Further optimization of the system was investigated by incorporating a vinylene carbonate additive into the electrolyte solution which boosted performance, offering promising high-rate performance and good capacity retention over extended cycling. The analysis confirms the possibility of creating a ternary transition metal oxide material with binder free accessible open-worked structure to allow three conversion mode oxides to efficiently cycle as an anode material for Li-ion battery applications. PMID:28186183

  9. Mesoporous MnCo2O4 with a flake-like structure as advanced electrode materials for lithium-ion batteries and supercapacitors.

    Science.gov (United States)

    Mondal, Anjon Kumar; Su, Dawei; Chen, Shuangqiang; Ung, Alison; Kim, Hyun-Soo; Wang, Guoxiu

    2015-01-19

    A mesoporous flake-like manganese-cobalt composite oxide (MnCo2O4) is synthesized successfully through the hydrothermal method. The crystalline phase and morphology of the materials are characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and Brunauer-Emmett-Teller methods. The flake-like MnCo2O4 is evaluated as the anode material for lithium-ion batteries. Owing to its mesoporous nature, it exhibits a high reversible capacity of 1066 mA h g(-1), good rate capability, and superior cycling stability. As an electrode material for supercapacitors, the flake-like MnCo2O4 also demonstrates a high supercapacitance of 1487 F g(-1) at a current density of 1 A g(-1), and an exceptional cycling performance over 2000 charge/discharge cycles. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Effects of Cu doping on the electronic structure and magnetic properties of MnCo2O4 nanostructures

    Science.gov (United States)

    Pramanik, Prativa; Thota, Subhash; Singh, Sobhit; Joshi, Deep Chandra; Weise, Bruno; Waske, Anja; Seehra, M. S.

    2017-10-01

    Reported here are the results and their analysis from our detailed investigations of the effects of Cu doping (x ≤slant 0.2 ) on the electronic structure and magnetic properties of the spinel MnCo2 O4. A detailed comparison is given for the x = 0 and x = 0.2 cases for both the bulk-like samples and nanoparticles. The electronic structure determined from x-ray photoelectron spectroscopy and Rietveld analysis of x-ray diffraction patterns shows the structure to be: (Co3+ )A [Mn3+ Co2+(1-x) Cu2+x ]B O4 i.e. Cu2+ substitutes for Co2+ on the octahedral B-sites. For the bulk samples, the ferrimagnetic T_C= 184 K for x = 0 is lowered to TC = 167 K for the x = 0.2 sample, this decrease being due to the effect of Cu doping. For the nanosize x = 0 (x = 0.2 ) sample, the lower TC = 165 K (TC = 155 K) is observed using \\partial (χdcT)/\\partial T analysis, this lowering being due to finite size effects. For T > TC , fits of dc paramagnetic susceptibility data of χ-1 versus T in nanosize samples to the Néel expression are used to determine the exchange interactions between the A and B sites with exchange constants: JAA / kB ∼ 8.4 K (4.1 K), JBB/kB ∼21.2 K (16.3 K) and JAB / kB ∼ 13.9 K (13.8 K) for x = 0 (0.2) . The temperature dependence of ac susceptibilities χ\\prime(T) and χ\\prime\\prime(T) at different frequencies shows that in bulk samples of x = 0 and x=0.2 , the transition at T C is the normal second order transition. But for the nanosize x = 0 and 0.2 samples, analysis of the ac susceptibilities shows that the ferrimagnetic transition at T C is followed by a re-entrant spin-glass transition at lower temperatures T_SG ∼ 162 K (138 K) for x = 0 (x = 0.20 ). Analysis of the ac susceptibilities, χ\\prime(T) and χ\\prime\\prime(T) , versus T data is done in terms of two scaling laws: (i) Vogel–Fulcher law [τ = τo \\exp(Ea/(kB(T-To)))] ; and (ii) power law of critical slowing-down τ / τo = [(TP/TSG)-1]-zν . These fits confirm the existence

  11. Oximato bridged Rh$^{\\text{III}}_2$MII and RhIIIMI species (MII = Mn, Co, Ni; MI = Cu, Ag)

    Indian Academy of Sciences (India)

    Indranil Bhattacharyya; Sanjib Ganguly; Bikash Kumar Panda; Animesh Chakravorty

    2008-01-01

    The reaction of [RhCl2(HPhL)(PhL)] with MII(ClO4)2.6H2O in presence of alkali has furnished trinuclear [RhCl2(PhL)2]2M(H2O)2.H2O (HPhL is phenylazobenzaldoxime; M = Mn, Co, Ni). A similar reaction with MI(PPh3)2NO3 yielded binuclear [RhCl2(PhL)2]M(PPh3)2 (M = Cu, Ag). In these molecules the oximato group acts as a bridge between RhIII (bonded at N) and MII or MI (bonded at O). In structurally characterized [RhIIICl2(PhL)2]2Mn(H2O)2.H2O the centrosymmetric distorted octahedral MnO6 coordination sphere is spanned by four oximato oxygen atoms and two water molecules lying in trans position. In the lattice the neighbouring molecules are held together by H2O$\\cdots$H2O$\\cdots$H2O hydrogen bonds generating infinite zigzag chains. The manganese atoms lie parallel to the C-axis, the shortest Mn…Mn distance being 7.992 Å. Magnetic exchange interactions if any are small as seen in room temperature magnetic moments. The manganese system displays a strong EPR signal near = 2.00. In the complex [RhCl2(PhL)2]Cu(PPh3)2 the copper atom is coordinated to two oximato oxygen atoms and the two phosphorus atoms in a distorted tetrahedral geometry. The softness of the phosphine ligand is believed to sustain the stable coordination of hard oximato oxygen to soft CuI. The coordination sphere of the RhIII atom in both the complexes is uniformly trans-RhN4Cl2.

  12. Binuclear metal carbonyl DAB complexes. II. The syntheses and coordination properties of Mn(CO)5M'(CO)3DAB (M' = Mn, Re; DAB = 1,4-diazabutadiene)

    NARCIS (Netherlands)

    Koten, G. van; Staal, L.H.; Vrieze, K.

    1979-01-01

    Mn(CO){5}M'(CO){3}DAB complexes (M' = Mn, Re; DAB = R{1}N=C(R{2})-C(R'{2})=NR{1}) can be easily obtained from the reaction between Mn(CO){5}}-{ and M'(CO){3}X(DAB) (M' = Mn, Re; X = Cl, Br, I). The complexes are formed by a nucleophilic mechanism, while a redistribution is responsible for the

  13. Stainless Steel to Titanium Bimetallic Transitions

    Energy Technology Data Exchange (ETDEWEB)

    Kaluzny, J. A. [Fermilab; Grimm, C. [Fermilab; Passarelli, D. [Fermilab

    2015-01-01

    In order to use stainless steel piping in an LCLS-II (Linac Coherent Light Source Upgrade) cryomodule, stainless steel to titanium bimetallic transitions are needed to connect the stainless steel piping to the titanium cavity helium vessel. Explosion bonded stainless steel to titanium transition pieces and bimetallic transition material samples have been tested. A sample transition tube was subjected to tests and x-ray examinations between tests. Samples of the bonded joint material were impact and tensile tested at room temperature as well as liquid helium temperature. The joint has been used successfully in horizontal tests of LCLS-II cavity helium vessels and is planned to be used in LCLS-II cryomodules. Results of material sample and transition tube tests will be presented.

  14. BIMETALLIC CONDUCTOR’S SPECIFIC RESISTANCE

    Directory of Open Access Journals (Sweden)

    Markitantova Natal'ya Konstantinovna

    2013-04-01

    Full Text Available Improvement of conductors of electric energy and signals is considered by the authors. The subject of the research consists in cable conductors, and their improvement is analyzed on the macro-level. The authors have derived the final formula designated for the calculation of the value of the specific electric resistance of bimetallic conductors. MathCAD-14 software was employed to perform the calculations. The analysis of dependencies derived by the authors allowed the authors to make the conclusion that the thinner the copper layer, the higher the specific electric resistance of the bimetallic conductor. Moreover, the authors succeeded in making a quantitative presentation of the aforementioned characteristic, which is a relevant contribution into its further systemic analysis.

  15. Copper-silver bimetallic system on natural clinoptilolite: thermal reduction of Cu2+ and Ag+ exchanged.

    Science.gov (United States)

    Rodríguez-Iznaga, Inocente; Petranovskii, Vitalii; Castillón-Barraza, Felipe; Concepción-Rosabal, Beatriz

    2011-06-01

    Copper-silver bimetallic system supported on natural clinoptilolite from Tasajeras deposit (Cuba) was studied. Bimetallic samples were prepared by simultaneous ion exchange, and reduced in a wide temperature range in a hydrogen flow. The main goal of the work was analysis of the mutual influence of both metals on their reduction process and the properties of the resultant particles. Analysis was done by combined use of XRD and UV-Vis spectroscopy. The reduction of Cu2+ and Ag+ cations shows existence of notable inter-influence between both cations during this process. The Cu2+ reduction is favored by the presence of Ag+, which should be related with the synergetic influence of silver cations and/or clusters formed on the first stages of reduction on Cu(2+)-framework interaction, facilitating the Cu2+ reduction even at low temperature (25 and 50 degrees C). The aggregation of the reduced highly dispersed species both for copper and silver is limited in this bimetallic system. The introduction of Ag+ as the second cation in the copper-exchanged zeolites favors the copper reduction at lower temperatures (25 and 50 degrees C), and appears to be the efficient tool for the control of the size of the resultant reduced nanoparticles (it means their dispersion).

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

    Energy Technology Data Exchange (ETDEWEB)

    Villa, Alberto [Universita di Milano, Italy; Prati, Laura [Universita di Milano, Italy; Su, Dangshen [Fritz Haber Institute of the Max Planck Society, Berlin, Germany; Wang, Di [Fritz Haber Institute of the Max Planck Society, Berlin, Germany; Veith, Gabriel M [ORNL

    2010-01-01

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

  17. Bimetallic redox synergy in oxidative palladium catalysis.

    Science.gov (United States)

    Powers, David C; Ritter, Tobias

    2012-06-19

    Polynuclear transition metal complexes, which are embedded in the active sites of many metalloenzymes, are responsible for effecting a diverse array of oxidation reactions in nature. The range of chemical transformations remains unparalleled in the laboratory. With few noteworthy exceptions, chemists have primarily focused on mononuclear transition metal complexes in developing homogeneous catalysis. Our group is interested in the development of carbon-heteroatom bond-forming reactions, with a particular focus on identifying reactions that can be applied to the synthesis of complex molecules. In this context, we have hypothesized that bimetallic redox chemistry, in which two metals participate synergistically, may lower the activation barriers to redox transformations relevant to catalysis. In this Account, we discuss redox chemistry of binuclear Pd complexes and examine the role of binuclear intermediates in Pd-catalyzed oxidation reactions. Stoichiometric organometallic studies of the oxidation of binuclear Pd(II) complexes to binuclear Pd(III) complexes and subsequent C-X reductive elimination from the resulting binuclear Pd(III) complexes have confirmed the viability of C-X bond-forming reactions mediated by binuclear Pd(III) complexes. Metal-metal bond formation, which proceeds concurrently with oxidation of binuclear Pd(II) complexes, can lower the activation barrier for oxidation. We also discuss experimental and theoretical work that suggests that C-X reductive elimination is also facilitated by redox cooperation of both metals during reductive elimination. The effect of ligand modification on the structure and reactivity of binuclear Pd(III) complexes will be presented in light of the impact that ligand structure can exert on the structure and reactivity of binuclear Pd(III) complexes. Historically, oxidation reactions similar to those discussed here have been proposed to proceed via mononuclear Pd(IV) intermediates, and the hypothesis of mononuclear Pd

  18. Formation and structures of Au-Rh bimetallic nanoclusters supported on a thin film of Al2O3/NiAl(100).

    Science.gov (United States)

    Hsu, Po-Wei; Liao, Zhen-He; Hung, Ting-Chieh; Lee, Hsuan; Wu, Yu-Cheng; Lai, Yu-Ling; Hsu, Yao-Jane; Lin, Yuwei; Wang, Jeng-Han; Luo, Meng-Fan

    2017-06-07

    Self-organized alloying of Au with Rh in nanoclusters on an ordered thin film of Al2O3/NiAl(100) was investigated via various surface probe techniques under ultrahigh-vacuum conditions and calculations based on density-functional theory. The bimetallic clusters were formed on the sequential deposition of vapors of Au and Rh onto Al2O3/NiAl(100) at 300 K. The formation was more effective on the oxide seeded with Rh, since all post-deposited Au joined the pregrown Rh clusters; for metal deposition in the reverse order, some separate Rh clusters were formed. The contrasting behavior is rationalized through the easier nucleation of Rh on the oxide surface, due to the stronger Rh-oxide and Rh-Rh bonds. The alloying in the clusters proceeded, regardless of the order of metal deposition, toward a specific structure: an fcc phase, (100) orientation and Rh core-Au shell structure. The orientation, structural ordering and lattice parameters of the Au-Rh bimetallic clusters resembled Rh clusters, rather than Au clusters, on Al2O3/NiAl(100), even with Rh in a minor proportion. The Rh-predominated core-shell structuring corresponds to the binding energies in the order Rh-Rh > Rh-Au > Au-Au. The core-shell segregation, although active, was somewhat kinetically hindered, since elevating the sample temperature induced further encapsulation of Rh. The bimetallic clusters became thermally unstable above 500 K, for which both Rh and Au atoms began to diffuse into the substrate. Moreover, the electronic structures of surface elements on the bimetallic clusters, controlled by both structural and electronic effects, show a promising reactivity.

  19. Surface Modification of Mono-dispersal MnCO3 Particles by Citric Acid%柠檬酸对碳酸锰单分散粒子表面的电荷改性

    Institute of Scientific and Technical Information of China (English)

    吕春玲; 张景林

    2011-01-01

    用柠檬酸作为吸附剂,对MnCO3微粒表面电荷进行了改性.研究了柠檬酸溶液浓度、pH值和吸附温度对柠檬酸在MnCO3微粒表面吸附改性的影响.结果表明:随柠檬酸浓度的增加,MnCO3微粒表面对柠檬酸的吸附量逐渐增大,在柠檬酸浓度为1.0g/L附近达到吸附平衡;当pH值在6~11时,MnCO3颗粒表面ζ电位的绝对值均大于30mV:在吸附温度为30~45℃范围内,MnCO3微粒表面对柠檬酸的吸附量随吸附温度的提高而增大;柠檬酸在MuCO3颗粒表面的吸附符合Langmuir吸附模型,其瞬间单分子层吸附过程符合一级动力学方程.在柠檬酸溶液浓度为1.0g/L,超声频率为60kHz,pH值为7,吸附反应时间为40min,吸附反应温度为45℃的优化条件下,改性后MnCO3颗粒表面带负电,且改性后的MnCO3微粒悬浮液体系能保持良好稳定性.%The surface of MnCO3 particles was modified using citric acid as an absorbent. Effects of concentration of citric acid, pH value and adsorption reaction temperature on the surface modification of MnCO3 particles were investigated. The results show that the adsorptive capacity of citric acid on the surface of MnCO3 particles increases with increasing citric acid concentration, and reaches the adsorption equilibrium at the 1.0 g/L. The zeta-potential was over 30 mV when the pH value increased from 6 to 11. The adsorptive capacity of citric acid on the surface of MnCO3 particles increased with increasing temperature from 30 ℃ to 45℃. The adsorption of citric acid on the surface of MnCO3 particles followed the Langmuir isotherm, and the adsorption process of temporal monolayer followed the first-order reaction kinetic integral equation. The electric property on the surface of MnCO3 particles modified by citric acid was eleetronegative at citric acid concentration of 1.0 g/L, ultrasonic frequency of 60 kHz, pH value of 7, adsorption reaction time of 40 min and adsorption reaction temperature of 45℃. The

  20. Analysis of Manufacturing Bimetallic Tubes by the Cold Drawing Process

    Directory of Open Access Journals (Sweden)

    Halaczek D.

    2016-03-01

    Full Text Available Drawing processes apply to obtain the bimetallic tubes from the different metals and alloys, combined in the solid state, which significantly affects the specificity of this process. The manufacturing of bimetallic tubes by drawing process depends on many factors which include: preparation of the surface of materials joined in the solid state, the geometric parameters of the working tool, technological parameters of the drawing process (drawing speed, type of lubricant, the use of back pull etc.. Generally, the cold drawing process of producing the bimetallic tubes refers to metals which have high ductility (copper, aluminum, etc.. The tube sinking (tube drawing without a mandrel of bimetallic tubes together with joining them at the interface of the two metal in the solid-state is applied for tubes of the diameter range between 6 to 20 mm and based on of the reducing the diameter of the tube. However, a slight increase of wall thickness ca. 0.05 ÷ 0.10 mm can appear, which is not dangerous phenomenon in case of producing the bimetallic tubes by joining in the solid-state. The aim of the research was to investigate the technology of tubes drawing process from non-ferrous metal, drawing process of bimetallic tubes and the production of bimetallic tubes in layers composition: cooper Cu-ETP - brass CuZn37 and CuZn37 brass - copper Cu-ETP in the tube sinking process. The research program included: production of bimetallic tubes with a different composition (Cu- ETP-CuZn37 and CuZn37-Cu-ETP and a different percentage of the cross-section components; analysis of changes of tube wall thickness and the layer composition of the bimetallic tube, based on measurements on the workshop microscope; analysis of the material flow in the process of the bimetallic tubes production based on the measurements results of a profilograph CP-200.

  1. EPR spectrum of a manganese center observed in. gamma. -irradiated (CH/sub 3/)/sub 3/SnMn(CO)/sub 5/ single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Morton, J.R.; Preston, K.F.; Thibodeau, D.L. (National Research Council of Canada, Ottawa, Ontario. Div. of Chemistry)

    1982-06-01

    An EPR spectrum detected in ..gamma..-irradiated single crystals of trimethyltin-manganese pentacarbonyl was analyzed in terms of anisotropic interactions between a single unpaired electron, a manganese nucleus, and the magnetic field. At 100 K, the principal components of the g and /sup 55/Mn-hyperfine tensors are 2.0399, 2.0279, 2.0018 and 84.1 MHz, 106.3 MHz, 162.3 MHz, respectively. The free radical is believed to be (CH/sub 3/)/sub 3/SnMn(CO)/sub 4//sup -/, formed from the parent carbonyl by electron addition and loss of an equatorial ligand.

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

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

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

  3. Bimetallic nanoparticles: Preparation, properties, and biomedical applications.

    Science.gov (United States)

    Nasrabadi, Hamid Tayefi; Abbasi, Elham; Davaran, Soodabeh; Kouhi, Mohammad; Akbarzadeh, Abolfazl

    2016-01-01

    Many studies of non-supported bimetallic nanoparticle (BMNP) dispersions, stabilized by ligands or polymers, and copolymers, were started only about 10 years ago. Several preparative procedures have been proposed, and full characterizations on BMNPs have been approved. Studies on BMNPs received huge attention from both scientific and technological communities because most of the NPs' catalytic activity depends on their structural aspects. In this study, we focus on the preparation, properties, and bio-application of BMNPs and introduction of the recent advance in these NPs.

  4. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Chunshan, Song; Kirby, S.; Schmidt, E. [Pennsylvania State Univ., University Park, PA (United States)] [and others

    1995-12-31

    The objective of this project is to explore bimetallic dispersed catalysts for more efficient coal liquefaction. Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting various aromatic units and the reactions of various oxygen functional groups. This paper describes recent results on (1) hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors; and (2) activity and selectivity of dispersed Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-naphthylmethyl) bibenzyl. The results showed that some iron containing catalysts have higher activity in the sulfur-free form, contrary to conventional wisdom. Adding sulfur to Fe precursors with Cp-ligands decreased the activity of the resulting catalyst. This is in distinct contrast to the cases with iron pentacarbonyl and superfine Fe{sub 2}O{sub 3}, where S addition increased their catalytic activity substantially. A positive correlation between sulfur addition and increased activity can be seen, but a reversed trend between Fe cluster size and hydrocracking conversion could be observed, for carbonyl-type Fe precursors. It is apparent that the activity and selectivity of Fe catalysts for NMBB conversion depends strongly on both the type of ligand environment, the oxidation state and the number of intermetal bonds in the molecular precursor.

  5. Fabrication of cubic spinel MnCo2O4 nanoparticles embedded in graphene sheets with their improved lithium-ion and sodium-ion storage properties

    Science.gov (United States)

    Chen, Chang; Liu, Borui; Ru, Qiang; Ma, Shaomeng; An, Bonan; Hou, Xianhua; Hu, Shejun

    2016-09-01

    Cubic Spinel MnCo2O4/graphene sheets (MCO/GS) nanocomposites are synthesized by a facile hydrothermal method with a subsequent annealing process. Nano-sized MnCo2O4 particles are evenly embedded in paper-like graphene sheets, possessing a unique nanoparticles-on-sheets hybrid nanostructure, with particle size around 20-50 nm. Owing to the special nanoparticles-on-sheets structures, MCO/GS nanocomposites have an outstanding electrochemical performance for rechargeable energy storage devices. As an anode material for lithium-ion batteries, MCO/GS electrodes exhibit high reversible discharge capacities (1350.4 mAh g-1 at the initial rate of 100 mA g-1), excellent rate capability (462.1 mAh g-1 at a current rate of 4000 mA g-1) and outstanding cycling performance (584.3 mAh g-1 at 2000 mA g-1 after 250 cycles). Meanwhile, as an anode material for sodium-ion batteries, MCO/GS electrodes also exhibit comparably promising electrochemical characteristics. Greatly improved electrochemical properties can be assigned to the special advantageous nanostructures. Besides, the existence of graphene sheets is beneficial to the transportation of ions/electrons during battery operation. The outstanding electrochemical performance demonstrates that the lithium/sodium storage capability of MCO/GS nanocomposites is highly promising for high-capacity batteries.

  6. Discrepancy of the magnetic behaviors and crystalline structure on the Co/FeMn and FeMn/Co interfaces with ultrathin Pt spacer

    Institute of Scientific and Technical Information of China (English)

    LIU Yang; FU Yanqiang; JIN Chuan; FENG Chun

    2010-01-01

    The exchange coupling at the ferromagnetic/antiferromagnetic (FM/AFM) interface is influenced by both the magnetic structure and the crystalline micro-structure.Co/FeMn/Co thin films with 0.4 nm Pt spacer layer inserted into the Co/FeMn and FeMn/Co interface respectively were deposited by means of magnetron sputtering.The two interfaces upon and beneath the FeMn layer show distinct behaviors before and after the Pt spacer inserted.There is a remarkable shrink of the interfacial uncompensated spins within the FeMn bottom interfacial monolayers,whereas a relaxation of the pinning strength of the FeMn interfacial spins along the out-of-plane direction occurs at the top interrace.XRD analysis indicates the Pt layer upon the FeMn layer forms an fcc (002) texture,implying the magnetic discrepancy between the top and bottom FeMn interfaces has crystalline structural origins.

  7. In operando neutron diffraction study of a commercial graphite/(Ni, Mn, Co) oxide-based multi-component lithium ion battery

    Science.gov (United States)

    Nazer, N. S.; Yartys, V. A.; Azib, T.; Latroche, M.; Cuevas, F.; Forseth, S.; Vie, P. J. S.; Denys, R. V.; Sørby, M. H.; Hauback, B. C.; Arnberg, L.; Henry, P. F.

    2016-09-01

    In situ neutron diffraction was employed to investigate the structural evolution of the electrode materials in an ICR 10440 commercial cylindrical lithium-ion battery, which has a discharge capacity of 360 mAh and a nominal voltage of 3.7 V. A three-phase mixture of Li(Ni,Mn,Co)O2, LiCoO2 and LiMn2O4 was identified as the active material of the cathode, with graphite acting as the anode material. The study revealed that the graphite anode underwent structural changes to form a series of insertion-type lithiated derivatives, with up to 12.7% volume expansion for the Li-saturated compound LiC6. The charge-discharge behavior was more complex for the cathode. Here, the charge process was associated with partial lithium depletion from the initially Li-saturated compounds, leading to volume shrinkage for Li(Ni,Mn,Co)O2, in contrast to (Ni,Mn)-free LiCoO2. Electrochemical discharge experiments performed under a fast regime (2 C) at 5, 25 and 45 °C revealed that the discharge capacity followed the trend of an increased diffusion rate of Li+ ions in the electrolyte and Li atoms in both electrodes, being highest for 45 °C. At the lowest tested temperature (5 °C), a rapid drop in the discharge capacity took place using the same kinetic regime.

  8. Sr and Mn co-doped sol-gel derived BiFeO3 ceramics with enhanced magnetism and reduced leakage current

    Science.gov (United States)

    Sharma, Nandni; Kumar, Sanjeev; Mall, Ashish Kumar; Gupta, Rajeev; Garg, Ashish

    2017-01-01

    In this manuscript, we report the effect of Sr and Mn doping on the electrical and magnetic characteristics of BiFeO3 nanoparticles, synthesized by sol-gel technique. While powder diffraction analysis of the samples suggested absence of any structural distortion in both Sr-doped and Sr and Mn co-doped BiFeO3 nanoparticles, Rietveld refinement of the data suggested that the unit cell volume decreases with doping. Room temperature Raman studies of the samples confirmed the incorporation of Sr and Mn in BiFeO3. It was seen that Sr doping of BiFeO3 showed substantial reduction in the leakage current whilst co-doping with Sr and Mn led to lower reduction in the leakage current through offering better performance over undoped BiFeO3, due to changes brought in the defect chemistry upon doping. Additionally, Sr and Mn co-doped BiFeO3 samples exhibit enhanced magnetization in comparison to undoped and Sr doped BiFeO3, possibly due to interruptions in the spin cycloid of BiFeO3.

  9. Mesoporous MFe{sub 2}O{sub 4} (M = Mn, Co, and Ni) for anode materials of lithium-ion batteries: Synthesis and electrochemical properties

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Lianfeng, E-mail: duanlf@mail.ccut.edu.cn [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Key Laboratory of Advanced Structural Materials, Ministry of Education, and Department of Materials Science and Engineering, Changchun University of Technology, Changchun 130012 (China); Wang, Yuanxin; Wang, Linan [Key Laboratory of Advanced Structural Materials, Ministry of Education, and Department of Materials Science and Engineering, Changchun University of Technology, Changchun 130012 (China); Zhang, Feifei [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Wang, Limin [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)

    2015-01-15

    Highlights: • MFe{sub 2}O{sub 4} (M = Mn, Co, and Ni) are synthesized by a template-free hydrothermal method. • The mesoporous morphology is formed by self-assembly of crystal nucleus. • The mesporous MnFe{sub 2}O{sub 4} have the active phase and the synergy for Li-ion storage. - Abstract: The MFe{sub 2}O{sub 4} (M = Mn, Co, and Ni) mesoporous spheres with an average diameter of 250 nm were synthesized through a template-free hydrothermal method. The mesoporous MnFe{sub 2}O{sub 4} with a large surface area of 87.5 m{sup 2}/g and an average pore size of 27.52 nm were obtained. As the anode materials for Li-ion batteries, the mesoporous MnFe{sub 2}O{sub 4} exhibits excellent initial charge and discharge capacities of 1010 and 642.5 mA h/g. After 50 cycles, the discharge capacity could still remain at 379 mA h/g. The results showed that the active phase and the synergy between different metal oxides greatly improved the electrochemical performance, and the mesoporous composite could stabilize the structure of the electrodes.

  10. Oxygen permeation flux through 10Sc1YSZ-MnCo2O4 asymmetric membranes prepared by two-step sintering

    DEFF Research Database (Denmark)

    Pirou, Stéven; Gurauskis, Jonas; Gil, Vanesa;

    2016-01-01

    Asymmetric membranes based on a dual phase composite consisting of (Y2O3)0.01(Sc2O3)0.10(ZrO2)0.89 (10Sc1YSZ) as ionic conductor and MnCo2O4 as electronic conductor were prepared and characterized with respect to sinterability, microstructure and oxygen transport properties. The composite membranes...... were prepared by tape casting, lamination and fired in a two-step sintering process. Microstructural analysis showed that a gastight thin membrane layer with the desired ratio of ionic/electronic conducting phases could be fabricated. Oxygen permeation fluxes across the 10SclYSZ/MnCo2O4 (70/30 vol......%) composite membrane were measured from 750 to 940 degrees C using air or pure oxygen as feed gases and N2 or CO2 as sweep gases. Fluxes up to 2.3 mlN min-1 cm-2 were obtained for the 7 μm thick membrane. A degradation test over 1730 h showed an initial degradation of 21% during the first 1100 h after which...

  11. In situ synthesis and characterization of fine-patterned La and Mn co-doped BiFeO{sub 3} film

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Fuxue, E-mail: yanfuxue@126.com; Zhao, Gaoyang, E-mail: zhaogy@xaut.edu.cn; Song, Na; Zhao, Nana; Chen, Yuanqing

    2013-09-05

    Highlights: •La and Mn co-doped BiFeO{sub 3} film was prepared by a photosensitive sol–gel method. •XRD and Raman spectra confirmed single-phase rhombohedral structure with space group R3c. •Fine-patterned BLFMO film was obtained by a direct-patterning technique. •The saturation magnetization and Pr were enhanced in the fine-patterned BLFMO film. -- Abstract: La and Mn co-doped BiFeO{sub 3} (BLFMO) film was prepared by a photosensitive sol–gel method utilizing bismuth nitrate, lanthanum nitrate, manganese nitrate and ferric nitrate as starting materials. After a chelating reaction between benzoylacetone (BzAcH) and metallic ions, the precursor solution presented photosensitivity. Through a direct patterning process, a fine-patterned BLFMO film was obtained. The phase constituents, morphology, electric and magnetic properties of the as-prepared BLFMO film were characterized by X-ray diffractometer (XRD), Raman spectroscopy, scanning electron microscopy (SEM), ferroelectric testing unit, LCR Meter and vibrating sample magnetometer (VSM). The Mn dopant enhanced the saturation magnetization and remnant polarization of the BLFMO film.

  12. The role of the (111) texture on the exchange bias and interlayer coupling effects observed in sputtered NiFe/IrMn/Co trilayers

    Energy Technology Data Exchange (ETDEWEB)

    Castro, I. L.; Nascimento, V. P.; Passamani, E. C.; Takeuchi, A. Y.; Larica, C. [Universidade Federal do Espirito Santo, Vitoria, ES 29075-910 (Brazil); Tafur, M. [Universidade Federal de Itajuba, Campus Itabira, Itabira, MG 37500-903 (Brazil); Pelegrini, F. [Universidade Federal de Goias, Goiania, GO 74001-970 (Brazil)

    2013-05-28

    Magnetic properties of sputtered NiFe/IrMn/Co trilayers grown on different seed layers (Cu or Ta) deposited on Si (100) substrates were investigated by magnetometry and ferromagnetic resonance measurements. Exchange bias effect and magnetic spring behavior have been studied by changing the IrMn thickness. As shown by X-ray diffraction, Ta and Cu seed layers provoke different degrees of (111) fcc-texture that directly affect the exchange bias and indirectly modify the exchange spring coupling behavior. Increasing the IrMn thickness, it was observed that the coupling angle between the Co and NiFe ferromagnetic layers increases for the Cu seed system, but it reduces for the Ta case. The results were explained considering (i) different anisotropies of the Co and IrMn layers induced by the different degree of the (111) texture and (ii) the distinct exchange bias set at the NiFe/IrMn and IrMn/Co interfaces in both systems. The NiFe and Co interlayer coupling angle is strongly correlated with both exchange bias and exchange magnetic spring phenomena. It was also shown that the highest exchange bias field occurs when an unstressed L1{sub 2} IrMn structure is stabilized.

  13. BIMETALLIC LITHIUM BOROHYDRIDES TOWARD REVERSIBLE HYDROGEN STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Au, M.

    2010-10-21

    Borohydrides such as LiBH{sub 4} have been studied as candidates for hydrogen storage because of their high hydrogen contents (18.4 wt% for LiBH{sub 4}). Limited success has been made in reducing the dehydrogenation temperature by adding reactants such as metals, metal oxides and metal halides. However, full rehydrogenation has not been realized because of multi-step decomposition processes and the stable intermediate species produced. It is suggested that adding second cation in LiBH{sub 4} may reduce the binding energy of B-H. The second cation may also provide the pathway for full rehydrogenation. In this work, several bimetallic borohydrides were synthesized using wet chemistry, high pressure reactive ball milling and sintering processes. The investigation found that the thermodynamic stability was reduced, but the full rehydrogenation is still a challenge. Although our experiments show the partial reversibility of the bimetallic borohydrides, it was not sustainable during dehydriding-rehydriding cycles because of the accumulation of hydrogen inert species.

  14. Observation of three different ferromagnetic phases with predictable T sub c s in La sub 2 MnCo sub 0 sub . sub 5 Ni sub 0 sub . sub 5 O sub 6

    CERN Document Server

    Joly, V L J; Joy, P A

    2003-01-01

    The perovskite-type oxide La sub 2 MnCo sub 0 sub . sub 5 Ni sub 0 sub . sub 5 O sub 6 has been found to form in three different ferromagnetic phases with different transition temperatures, when a low-temperature synthesized sample is annealed at different temperatures. The interesting magnetic behaviour of the compound is due to the combination of different spin states of Mn, Co and Ni in the different phases of the compound. The magnetic transition temperatures of the three phases of the compound can be predicted from the T sub c s of La sub 2 MnCoO sub 6 and La sub 2 MnNiO sub 6. (letter to the editor)

  15. The atomic structural dynamics of γ-Al2O3 supported Ir-Pt nanocluster catalysts prepared from a bimetallic molecular precursor: a study using aberration-corrected electron microscopy and X-ray absorption spectroscopy.

    Science.gov (United States)

    Small, Matthew W; Sanchez, Sergio I; Menard, Laurent D; Kang, Joo H; Frenkel, Anatoly I; Nuzzo, Ralph G

    2011-03-16

    This study describes a prototypical, bimetallic heterogeneous catalyst: compositionally well-defined Ir-Pt nanoclusters with sizes in the range of 1-2 nm supported on γ-Al(2)O(3). Deposition of the molecular bimetallic cluster [Ir(3)Pt(3)(μ-CO)(3)(CO)(3)(η-C(5)Me(5))(3)] on γ-Al(2)O(3), and its subsequent reduction with hydrogen, provides highly dispersed supported bimetallic Ir-Pt nanoparticles. Using spherical aberration-corrected scanning transmission electron microscopy (C(s)-STEM) and theoretical modeling of synchrotron-based X-ray absorption spectroscopy (XAS) measurements, our studies provide unambiguous structural assignments for this model catalytic system. The atomic resolution C(s)-STEM images reveal strong and specific lattice-directed strains in the clusters that follow local bonding configurations of the γ-Al(2)O(3) support. Combined nanobeam diffraction (NBD) and high-resolution transmission electron microscopy (HRTEM) data suggest the polycrystalline γ-Al(2)O(3) support material predominantly exposes (001) and (011) surface planes (ones commensurate with the zone axis orientations frequently exhibited by the bimetallic clusters). The data reveal that the supported bimetallic clusters exhibit complex patterns of structural dynamics, ones evidencing perturbations of an underlying oblate/hemispherical cuboctahedral cluster-core geometry with cores that are enriched in Ir (a result consistent with models based on surface energetics, which favor an ambient cluster termination by Pt) due to the dynamical responses of the M-M bonding to the specifics of the adsorbate and metal-support interactions. Taken together, the data demonstrate that strong temperature-dependent charge-transfer effects occur that are likely mediated variably by the cluster-support, cluster-adsorbate, and intermetallic bonding interactions.

  16. A photoactive bimetallic framework for direct aminoformylation of nitroarenes

    Data.gov (United States)

    U.S. Environmental Protection Agency — A bimetallic catalyst, AgPd@g-C3N4, synthesized by reducing silver and palladium salts over graphitic carbon nitride (g-C3N4), enables the concerted reductive...

  17. Modeling the melting temperature of nanoscaled bimetallic alloys.

    Science.gov (United States)

    Li, Ming; Zhu, Tian-Shu

    2016-06-22

    The effect of size, composition and dimension on the melting temperature of nanoscaled bimetallic alloys was investigated by considering the interatomic interaction. The established thermodynamics model without any arbitrarily adjustable parameters can be used to predict the melting temperature of nanoscaled bimetallic alloys. It is found that, the melting temperature and interatomic interaction of nanoscaled bimetallic alloys decrease with the decrease in size and the increasing composition of the lower surface energy metal. Moreover, for the nanoscaled bimetallic alloys with the same size and composition, the dependence of the melting temperature on the dimension can be sequenced as follows: nanoparticles > nanowires > thin films. The accuracy of the developed model is verified by the recent experimental and computer simulation results.

  18. Time-resolved infrared observation of a long-lived transient in the photo-decarbonylation of Mn(CO)5C(O)CH3: Potential relevance to the CO migratory insertion mechanism

    OpenAIRE

    Boese, WT; Lee, B; Ryba, DW; Belt, ST; Ford, PC

    1993-01-01

    Flash photolysis experiments have been carried out at ambient temperature to probe potential reaction intermediates in the carbonylation of the methylmanganese complex CH3Mn(CO)5 (M) to give the acyl product CH3C(O)Mn(CO)5 (A). Photo-decarbonylation of A gives a long-lived transient C, whose time-resolved infrared spectrum shows but modest sensitivity to the coordinating ability of the solvent such as cyclohexane, perfluoromethylcyclohexane, tetrahydrofuran, and 2,5-dimethyl-THF. Notably, C h...

  19. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  20. PROPERTIES OF POLYMER SUPPORTED Ni-Cu BIMETALLIC CATALYSTS PREPARED BY SOLVATED METAL ATOM IMPREGNATION

    Institute of Scientific and Technical Information of China (English)

    WU Shihua; ZHU Changying; HUANG Wenqiang

    1996-01-01

    D-72 resin supported nickel-copper catalysts prepared by solvated metal atom impregnation (SMAI) were studied by magnetic measurements and X-ray photoelectron spectroscopy (XPS). The Ni particles on the catalysts are very highly dispersed and display superparamagnetic behaviour. Ni-Cu alloy clusters were found to be formed. The surface compositions are different from the bulk concentrations. In contrast with the surface enrichment in copper generally observed on conventional Ni-Cu catalysts, the surfaces of these catalysts are enriched in nickel. The nickel is in both zero and valent states, while copper is mainly in metallic state. Catalytic data show that the formation of Ni-Cu alloy clusters has a profound effect on the catalytic activities of the catalysts in the hydrogenation of furfural. The activity of the Ni:Cu ratio of one bimetallic catalysts is much higher than that of the Ni or Cu monometallic catalyst.

  1. Bimetallic Microswimmers Speed Up in Confining Channels

    Science.gov (United States)

    Liu, Chang; Zhou, Chao; Wang, Wei; Zhang, H. P.

    2016-11-01

    Synthetic microswimmers are envisioned to be useful in numerous applications, many of which occur in tightly confined spaces. It is therefore important to understand how confinement influences swimmer dynamics. Here we study the motility of bimetallic microswimmers in linear and curved channels. Our experiments show swimmer velocities increase, up to 5 times, with the degree of confinement, and the relative velocity increase depends weakly on the fuel concentration and ionic strength in solution. Experimental results are reproduced in a numerical model which attributes the swimmer velocity increase to electrostatic and electrohydrodynamic boundary effects. Our work not only helps to elucidate the confinement effect of phoretic swimmers, but also suggests that spatial confinement may be used as an effective control method for them.

  2. Resistive switching properties of Ce and Mn co-doped BiFeO3 thin films for nonvolatile memory application

    Directory of Open Access Journals (Sweden)

    Zhenhua Tang

    2013-12-01

    Full Text Available The Ce and Mn co-doped BiFeO3 (BCFMO thin films were synthesized on Pt/Ti/SiO2/Si substrates using a sol-gel method. The unipolar resistive switching (URS and bipolar resistive switching (BRS behaviors were observed in the Pt/BCFMO/Pt device structure, which was attributed to the formation/rupture of metal filaments. The fabricated device exhibits a large ROFF/RON ratio (>80, long retention time (>105 s and low programming voltages (<1.5 V. Analysis of linear fitting current-voltage curves suggests that the space charge limited leakage current (SCLC and Schottky emission were observed as the conduction mechanisms of the devices.

  3. Characterization and Catalytic Activity of Mn-Co/TiO2 Catalysts for NO Oxidation to NO2 at Low Temperature

    Directory of Open Access Journals (Sweden)

    Lu Qiu

    2016-01-01

    Full Text Available A series of Mn-Co/TiO2 catalysts were prepared by wet impregnation method and evaluated for the oxidation of NO to NO2. The effects of Co amounts and calcination temperature on NO oxidation were investigated in detail. The catalytic oxidation ability in the temperature range of 403–473 K was obviously improved by doping cobalt into Mn/TiO2. These samples were characterized by nitrogen adsorption-desorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscope (TEM and hydrogen temperature programmed reduction (H2-TPR. The results indicated that the formation of dispersed Co3O4·CoMnO3 mixed oxides through synergistic interaction between Mn-O and Co-O was directly responsible for the enhanced activities towards NO oxidation at low temperatures. Doping of Co enhanced Mn4+ formation and increased chemical adsorbed oxygen amounts, which also accelerated NO oxidation.

  4. Magnetodielectric coupling in frustrated spin systems: the spinels MCr{sub 2}O{sub 4} (M = Mn, Co and Ni)

    Energy Technology Data Exchange (ETDEWEB)

    Mufti, N; Nugroho, A A; Blake, G R; Palstra, T T M [Solid State Chemistry Laboratory, Zernike Institute for Advanced Materials, Rijksuniversiteit Groningen, Nijenborgh 4, 9747AG Groningen (Netherlands)

    2010-02-24

    We have studied the magnetodieletric coupling of polycrystalline samples of the spinels MCr{sub 2}O{sub 4} (M = Mn, Co and Ni). Dielectric anomalies are clearly observed at the onset of the magnetic spiral structure (T{sub s}) and at the 'lock-in' transition (T{sub f}) in MnCr{sub 2}O{sub 4} and CoCr{sub 2}O{sub 4}, and also at the onset of the canted structure (T{sub s}) in NiCr{sub 2}O{sub 4}. The strength of the magnetodielectric coupling in this system can be explained by spin-orbit coupling. Moreover, the dielectric response in an applied magnetic field scales with the square of the magnetization for all three samples. Thus, the magnetodielectric coupling in this state appears to originate from the P{sup 2}M{sup 2} term in the free energy.

  5. Exchange Bias and Inverse Magnetocaloric Effect in Co and Mn Co-Doped Ni2MnGa Shape Memory Alloy

    Directory of Open Access Journals (Sweden)

    Yong Liu

    2013-01-01

    Full Text Available Exchange bias effect observed in the Ni1.68Co0.32Mn1.20Ga0.80 alloy confirms the coexistence of antiferromagnetic and ferromagnetic phases in the martensite phase. A large inverse magnetocaloric effect has been observed within the martensitic transformation temperature range, which is originated from modified magnetic order through magnetic-field-induced phase transformation from partially antiferromagnetic martensite to ferromagnetic austenite. The magnetic entropy change is 16.2 J kg−1 K−1 at 232 K under ΔH = 60 kOe, with the net refrigerant capacity of 68 J kg−1. These properties indicate Co and Mn co-doped Ni2MnGa alloy is a multifunctional material potentially suitable for magnetic refrigeration and spintronics applications.

  6. Structure and magnetic properties of the double-perovskites Ba2(B,Re)2O6 (B = Fe, Mn, Co and Ni)

    Science.gov (United States)

    Rammeh, N.; Ehrenberg, H.; Fuess, H.; Cheikkh-Rouhou, A.

    2006-09-01

    Structural and magnetic properties of Ba2(B,Re)2O6 (B = Fe, Mn, Co and Ni) double-perovskite oxides have been investigated. Rietveld analysis shows that all our synthesized samples are single phase and crystallize at room temperature in the cubic double-perovskite structure with Fm3m space group. Magnetization measurements versus temperature and versus magnetic applied field up to 5 T show that Ba2(Fe,Re)2O6, Ba2(Mn,Re)2O6 and Ba2(Ni,Re)2O6 are ferromagnetic at low temperature with TC = 318 K, 113 K and 32 K respectively while Ba2(Co,Re)2O6 is antiferromagnetic below TN = 25 K.

  7. Synthesis, structure, and magnetic properties of novel B-site ordered double perovskites, SrLaMReO6 (M = Mg, Mn, Co and Ni).

    Science.gov (United States)

    Thompson, Corey M; Chi, Lisheng; Hayes, John R; Hallas, Alannah M; Wilson, Murray N; Munsie, Timothy J S; Swainson, Ian P; Grosvenor, Andrew P; Luke, Graeme M; Greedan, John E

    2015-06-21

    Four new double perovskites, SrLaMReO(6) (M = Mg, Mn, Co, Ni) in which Re(5+) (5d(2)) is present, were prepared via conventional solid state reactions and characterized by X-ray and neutron powder diffraction, XANES, SQUID magnetometry, and muon spin relaxation (μSR). Synchrotron X-ray and neutron diffraction experiments confirmed that all compounds crystallize in the monoclinic P2(1)/n structure type, which consists of alternately corner-shared octahedra of MO(6) and ReO(6). Rietveld refinement results indicated anti-site mixing of less than 7% on the M/Re sites. Bond valence sum calculations (BVS) suggest all M and Re ions are 2+ and 5+, respectively, and for the Mn-containing phase this is also supported by XANES measurements. All of the materials are paramagnetic at room-temperature and their Curie-Weiss temperatures are positive (except for Mg) indicating net ferromagnetic interactions. No evidence for long-range magnetic order is evident in the dc magnetic susceptibility and μSR measurements for SrLaMgReO(6) to 2 K. The Mn-phase shows long-range order at T(C) = 190 K and neutron diffraction revealed a ferromagnetic structure with a refined net moment of ∼3.7μ(B). Both Co- and Ni-containing phases exhibit spin glass behavior at T(G) = 23 and 30 K, respectively, which is supported by neutron diffraction and a.c. susceptibility data. The structure and physical properties of these four new rhenium based ordered double perovskites are compared to the closely related "pillared perovskites", La(5)Re(3)MO(16), the isoelectronic Os(6+) (5d(2)) double perovskite Sr(2)CoOsO(6), and the Re(6+) (5d(1)) double perovskites, Sr(2)MReO(6), (M = Mg, Ca, Mn, Co, Ni).

  8. Magnetic annealing of the ion-beam sputtered IrMn/CoFeB bilayers - positive exchange bias and coercivity behaviour

    Science.gov (United States)

    Raju, M.; Chaudhary, Sujeet; Pandya, D. K.

    2013-12-01

    The effect of optimum dilution of antiferromagnetic (AF)/ferromagnetic (FM) interface necessary for observance of positive exchange bias in ion-beam sputtered Si/Ir22Mn78 ( t AF = 12, 18, 24 nm)/Co20Fe60B20( t FM = 6,9,15 nm) exchange coupled bilayers is investigated by magnetic annealing at 380, 420 and 460 °C for 1 h at 5 × 10-6 Torr in presence of 500 Oe magnetic field. While the coercivity of the exchange coupled FM layer decreases with the increase in annealing temperature irrespective of the value of t AF or t FM, the hysteresis loops however shift by ≈+ 10 Oe whenever the coercivity drops in the 10-15 Oe range. This is consistent with the phase diagram of exchange bias field and coercivity derived from Meiklejohn and Bean model. The X-ray diffraction and X-ray reflectivity measurements confirmed that the texture, grain size and interface roughness of IrMn/CoFeB bilayers are thickness dependent and are correlated to the observed magnetic response of the bilayers. The results establish that optimum dilution of the IrMn/CoFeB interface by thermally diffused Mn-spins is necessary in inducing the effective coupling between the IrMn domains and diluted CoFeB layer. It is further shown that the annealing temperature required for the optimum dilution of the CoFeB interface critically depends on the thickness of the layers.

  9. Shaped Ir-Ni bimetallic nanoparticles for minimizing Ir utilization in oxygen evolution reaction.

    Science.gov (United States)

    Lim, Jinkyu; Yang, Sungeun; Kim, Chanyeon; Roh, Chi-Woo; Kwon, Yongwoo; Kim, Yong-Tae; Lee, Hyunjoo

    2016-04-25

    Shaped Ir-Ni bimetallic nanoparticles were synthesized and used for electrocatalytic oxygen evolution reaction (OER). The obtained bimetallic nanoparticles showed significantly enhanced Ir mass activity and durability compared with Ir nanoparticles.

  10. 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...

  11. Ammonia Decomposition over Bimetallic Nitrides Supported on γ-Al2O3

    Institute of Scientific and Technical Information of China (English)

    Chun Shan LU; Xiao Nian LI; Yi Feng ZHU; Hua Zhang LIU; Chun Hui ZHOU

    2004-01-01

    A series of monometallic nitrides and bimetallic nitrides were prepared by temperature-programmed reaction with NH3. The effects of Co, Ni and Fe additives and the synergic action between Fe, Co, Ni and Mo on the ammonia decomposition activity were investigated. TPR-MS, XRD were also carried out to obtain better insight into the structure of the bimetallic nitride. The results of ammonia decomposition activity show that bimetallic nitrides are more active than monometallic nitrides or bimetallic oxides.

  12. Synthesis and Structural Characterization of Manganese Carbonyl Incorporated Polyoxomolybdate (n-Bu4N)2[Mo6O16(OCH3)2 {HOCH2C(CH2O)3}2{Mn(CO)3}2

    Institute of Scientific and Technical Information of China (English)

    WANG Jing-ping; LI Ji-li; NIU Jing-yang

    2008-01-01

    The polyoxoanion incorporated {Mn(CO)3+} complex,(n-Bu4N)2[Mo6O16(OCH3)2{HOCH2C(CH2O)3}2{Mn(CO)3}2](1),has been synthesized by the reaction of (n-Bu4N)4[MosO26] with Mn(CO)sBr in methanol,in the presence of C(CH2OH)4.The complex 1 has been characterized by IR UV-Vis,X-ray single crystal diffraction,and TG.Crystal data for the complex 1:C25H48MnMo3NO16 (1),Triclinic P1,a=0.9405(3) nm,b=1.3351 (4) nm,c=1.5455(4) nm,a=103.206(5)°,β=102.165(5)°,γ=100.784(5)°,V=1.7896(9) nm3,Z=2,R1=0.0703,wR2 = 0.1495.The structure analysis of complex 1 shows that the complex consists of two tetrabutylammonium cations and a polyoxomolybdate anion that incorporates two fac-Mn(CO)3+ units.The anion of complex 1 can be considered as the dimer of two rhomb-like anions by sharing of two comers.

  13. Nanocrystal and surface alloy properties of bimetallic Gold-Platinum nanoparticles

    Directory of Open Access Journals (Sweden)

    Mott Derrick

    2006-01-01

    Full Text Available AbstractWe report on the correlation between the nanocrystal and surface alloy properties with the bimetallic composition of gold-platinum(AuPt nanoparticles. The fundamental understanding of whether the AuPt nanocrystal core is alloyed or phase-segregated and how the surface binding properties are correlated with the nanoscale bimetallic properties is important not only for the exploitation of catalytic activity of the nanoscale bimetallic catalysts, but also to the general exploration of the surface or interfacial reactivities of bimetallic or multimetallic nanoparticles. The AuPt nanoparticles are shown to exhibit not only single-phase alloy character in the nanocrystal, but also bimetallic alloy property on the surface. The nanocrystal and surface alloy properties are directly correlated with the bimetallic composition. The FTIR probing of CO adsorption on the bimetallic nanoparticles supported on silica reveals that the surface binding sites are dependent on the bimetallic composition. The analysis of this dependence further led to the conclusion that the relative Au-atop and Pt-atop sites for the linear CO adsorption on the nanoparticle surface are not only correlated with the bimetallic composition, but also with the electronic effect as a result of the d-band shift of Pt in the bimetallic nanocrystals, which is the first demonstration of the nanoscale core-surface property correlation for the bimetallic nanoparticles over a wide range of bimetallic composition.

  14. Nanocrystal and surface alloy properties of bimetallic Gold-Platinum nanoparticles

    Science.gov (United States)

    Mott, Derrick; Luo, Jin; Smith, Andrew; Njoki, Peter N; Wang, Lingyan

    2007-01-01

    We report on the correlation between the nanocrystal and surface alloy properties with the bimetallic composition of gold-platinum(AuPt) nanoparticles. The fundamental understanding of whether the AuPt nanocrystal core is alloyed or phase-segregated and how the surface binding properties are correlated with the nanoscale bimetallic properties is important not only for the exploitation of catalytic activity of the nanoscale bimetallic catalysts, but also to the general exploration of the surface or interfacial reactivities of bimetallic or multimetallic nanoparticles. The AuPt nanoparticles are shown to exhibit not only single-phase alloy character in the nanocrystal, but also bimetallic alloy property on the surface. The nanocrystal and surface alloy properties are directly correlated with the bimetallic composition. The FTIR probing of CO adsorption on the bimetallic nanoparticles supported on silica reveals that the surface binding sites are dependent on the bimetallic composition. The analysis of this dependence further led to the conclusion that the relative Au-atop and Pt-atop sites for the linear CO adsorption on the nanoparticle surface are not only correlated with the bimetallic composition, but also with the electronic effect as a result of the d-band shift of Pt in the bimetallic nanocrystals, which is the first demonstration of the nanoscale core-surface property correlation for the bimetallic nanoparticles over a wide range of bimetallic composition.

  15. Insight into growth of Au-Pt bimetallic nanoparticles: an in situ XAS study.

    Science.gov (United States)

    Nayak, Chandrani; Bhattacharyya, D; Bhattacharyya, K; Tripathi, A K; Bapat, R D; Jha, S N; Sahoo, N K

    2017-07-01

    Au-Pt bimetallic nanoparticles have been synthesized through a one-pot synthesis route from their respective chloride precursors using block copolymer as a stabilizer. Growth of the nanoparticles has been studied by simultaneous in situ measurement of X-ray absorption spectroscopy (XAS) and UV-Vis spectroscopy at the energy-dispersive EXAFS beamline (BL-08) at Indus-2 SRS at RRCAT, Indore, India. In situ XAS spectra, comprising both X-ray near-edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) parts, have been measured simultaneously at the Au and Pt L3-edges. While the XANES spectra of the precursors provide real-time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed in the intermediate stages of growth. This insight into the formation process throws light on how the difference in the reduction potential of the two precursors could be used to obtain the core-shell-type configuration of a bimetallic alloy in a one-pot synthesis method. The core-shell-type structure of the nanoparticles has also been confirmed by ex situ energy-dispersive spectroscopy line-scan and X-ray photoelectron spectroscopy measurements with in situ ion etching on fully formed nanoparticles.

  16. Cluster-cluster clustering

    Science.gov (United States)

    Barnes, J.; Dekel, A.; Efstathiou, G.; Frenk, C. S.

    1985-01-01

    The cluster correlation function xi sub c(r) is compared with the particle correlation function, xi(r) in cosmological N-body simulations with a wide range of initial conditions. The experiments include scale-free initial conditions, pancake models with a coherence length in the initial density field, and hybrid models. Three N-body techniques and two cluster-finding algorithms are used. In scale-free models with white noise initial conditions, xi sub c and xi are essentially identical. In scale-free models with more power on large scales, it is found that the amplitude of xi sub c increases with cluster richness; in this case the clusters give a biased estimate of the particle correlations. In the pancake and hybrid models (with n = 0 or 1), xi sub c is steeper than xi, but the cluster correlation length exceeds that of the points by less than a factor of 2, independent of cluster richness. Thus the high amplitude of xi sub c found in studies of rich clusters of galaxies is inconsistent with white noise and pancake models and may indicate a primordial fluctuation spectrum with substantial power on large scales.

  17. Cluster-cluster clustering

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, J.; Dekel, A.; Efstathiou, G.; Frenk, C.S.

    1985-08-01

    The cluster correlation function xi sub c(r) is compared with the particle correlation function, xi(r) in cosmological N-body simulations with a wide range of initial conditions. The experiments include scale-free initial conditions, pancake models with a coherence length in the initial density field, and hybrid models. Three N-body techniques and two cluster-finding algorithms are used. In scale-free models with white noise initial conditions, xi sub c and xi are essentially identical. In scale-free models with more power on large scales, it is found that the amplitude of xi sub c increases with cluster richness; in this case the clusters give a biased estimate of the particle correlations. In the pancake and hybrid models (with n = 0 or 1), xi sub c is steeper than xi, but the cluster correlation length exceeds that of the points by less than a factor of 2, independent of cluster richness. Thus the high amplitude of xi sub c found in studies of rich clusters of galaxies is inconsistent with white noise and pancake models and may indicate a primordial fluctuation spectrum with substantial power on large scales. 30 references.

  18. Construction of three-dimensional models of bimetallic nanoparticles based on X-ray absorption spectroscopy data

    Science.gov (United States)

    Avakyan, L. A.; Srabionyan, V. V.; Pryadchenko, V. V.; Bulat, N. V.; Bugaev, L. A.

    2016-06-01

    A new method for constructing three-dimensional models of bimetallic nanoparticles is proposed. This method, which is based on X-ray absorption spectroscopy data on the number and type of nearest neighbors, provides information on the distribution of types of atoms over the nanoparticle volume. The application of the method to the study of the structures of platinum-copper and platinum-silver nanoparticles of metal-carbon electrocatalysts has allowed to distinguish the nanoparticles with a core-shell structure from the nanoparticles with structure of disordered alloy or clusterized solid solution.

  19. Structure-Property Relationship in Metal Carbides and Bimetallic Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jingguan [University of Delaware

    2014-03-04

    The primary objective of our DOE/BES sponsored research is to use carbide and bimetallic catalysts as model systems to demonstrate the feasibility of tuning the catalytic activity, selectivity and stability. Our efforts involve three parallel approaches, with the aim at studying single crystal model surfaces and bridging the “materials gap” and “pressure gap” between fundamental surface science studies and real world catalysis. The utilization of the three parallel approaches has led to the discovery of many intriguing catalytic properties of carbide and bimetallic surfaces and catalysts. During the past funding period we have utilized these combined research approaches to explore the possibility of predicting and verifying bimetallic and carbide combinations with enhanced catalytic activity, selectivity and stability.

  20. Recent Advances in Facile Synthesis of Bimetallic Nanostructures: An Overview

    Directory of Open Access Journals (Sweden)

    Arash Dehghan Banadaki

    2014-01-01

    Full Text Available Nobel metal nanomaterials with interesting physical and chemical properties are ideal building blocks for engineering and tailoring nanoscale structures for specific technological applications. Bimetallic nanomaterials consisting of magnetic metals and noble metals have attracted much interest for their promising potentials in many fields including magnetic sensors, catalysts, optical detection, and biomedical applications. Particularly, effective control of the size, shape, architecture, and compositional microstructure of metal nanomaterials plays an important role in enhancing their functionality and application potentials, for example, in fuel cells, optical and biomedical sensing. This paper focuses on recent advances in controllable synthesis of bimetallic nanostructured materials. Recent contributions in controllable synthesis of bimetallic nanomaterials with different architectures including nanoparticles, nanowires, nanosheets, or nanotubes and their assemblies are presented in this paper. A wide range of facile synthesis methods are covered herein with high emphasis on wet chemical methods owing to their facility of use, efficacy, and smaller environmental footprint.

  1. Bimetallic Nanoparticles in Alternative Solvents for Catalytic Purposes

    Directory of Open Access Journals (Sweden)

    Trung Dang-Bao

    2017-07-01

    Full Text Available Bimetallic nanoparticles represent attractive catalytic systems thanks to the synergy between both partners at the atomic level, mainly induced by electronic effects which in turn are associated with the corresponding structures (alloy, core-shell, hetero-dimer. This type of engineered material can trigger changes in the kinetics of catalyzed processes by variations on the electrophilicity/nucleophilicity of the metal centers involved and also promote cooperative effects to foster organic transformations, including multi-component and multi-step processes. Solvents become a crucial factor in the conception of catalytic processes, not only due to their environmental impact, but also because they can preserve the bimetallic structure during the catalytic reaction and therefore increase the catalyst life-time. In this frame, the present review focuses on the recent works described in the literature concerning the synthesis of bimetallic nanoparticles in non-conventional solvents, i.e., other than common volatile compounds, for catalytic applications.

  2. Bimetallic layered castings alloy steel – carbon cast steel

    Directory of Open Access Journals (Sweden)

    T. Wróbel

    2011-01-01

    Full Text Available In paper is presented technology of bimetallic layered castings based on founding method of layer coating directly in cast processso-called method of mould cavity preparation. Prepared castings consist two fundamental parts i.e. bearing part and working part (layer. The bearing part of bimetallic layered casting is typical foundry material i.e. ferritic-pearlitic carbon cast steel, whereas working part (layer is plate of austenitic alloy steel sort X10CrNi 18-8. The ratio of thickness between bearing and working part is 8:1. The quality of the bimetallic layered castings was evaluated on the basis of ultrasonic NDT (non-destructive testing, structure and macro- and microhardness researches.

  3. Examples of material solutions in bimetallic layered castings

    Directory of Open Access Journals (Sweden)

    S. Tenerowicz

    2011-07-01

    Full Text Available In paper is presented technology of bimetallic layered castings based on founding method of layer coating directly in cast process so-called method of mould cavity preparation. Prepared castings consist two fundamental parts i.e. bearing part and working part (layer. The bearing part of bimetallic layered casting is typical foundry material i.e. pearlitic grey cast iron, whereas working part (layer is depending on accepted variant plates of alloy steels sort X6Cr13, X12Cr13, X10CrNi18-8 and X2CrNiMoN22-5-3. The ratio of thickness between bearing and working part is 8:1. The verification of the bimetallic layered castings was evaluated on the basis of ultrasonic NDT (non-destructive testing, structure and macro- and microhardness researches.

  4. Magnetic field-induced phase transformation in NiMnCoIn magnetic shape-memory alloys - A new actuation mechanism with large work output

    Energy Technology Data Exchange (ETDEWEB)

    Karaca, Haluk E. [Department of Mechanical Engineering, Texas A and M University College Station, TX (United States); Department of Mechanical Engineering, University of Kentucky Lexington, KY 40506 (United States); Karaman, Ibrahim [Department of Mechanical Engineering, Texas A and M University College Station, TX (United States); Materials Science and Engineering Graduate Program, Texas A and M University College Station, TX 77843 (United States); Basaran, Burak [Materials Science and Engineering Graduate Program, Texas A and M University College Station, TX 77843 (United States); Ren, Yang [Advanced Photon Source Argonne National Laboratory Argonne, Illinois 60439 (United States); Chumlyakov, Yuny I. [Siberian Physical-Technical Institute Tomsk, 634050 (Russian Federation); Maier, Hans J. [Lehrstuhl fuer Werkstoffkunde, University of Paderborn 33095 Paderborn (Germany)

    2009-04-09

    Magnetic shape memory alloys (MSMAs) have recently been developed into a new class of functional materials that are capable of magnetic-field-induced actuation, mechanical sensing, magnetic refrigeration, and energy harvesting. In the present work, the magnetic and hyphen; field-induced martensitic phase transformation (FIPT) in Ni{sub 45}Mn{sub 36.5}Co{sub 5}In{sub 13.5} MSMA single crystals is characterized as a new actuation mechanism with potential to result in ultra-high actuation work outputs. The effects of the applied magnetic field on the transformation temperatures, magnetization, and superelastic response are investigated. The magnetic work output of NiMnCoIn alloys is determined to be more than 1 MJ m{sup -3} per Tesla, which is one order of magnitude higher than that of the most well-known MSMAs, i.e., NiMnGa alloys. In addition, the work output of NiMnCoIn alloys is orientation independent, potentially surpassing the need for single crystals, and not limited by a saturation magnetic field, as opposed to NiMnGa MSMAs. Experimental and theoretical transformation strains and magnetostress levels are determined as a function of crystal orientation. It is found that [111]-oriented crystals can demonstrate a magnetostress level of 140 MPa T{sup -1} with 1.2% axial strain under compression. These field-induced stress and strain levels are significantly higher than those from existing piezoelectric and magnetostrictive actuators. A thermodynamical framework is introduced to comprehend the magnetic energy contributions during FIPT. The present work reveals that the magnetic FIPT mechanism is promising for magnetic actuation applications and provides new opportunities for applications requiring high actuation work-outputs with relatively large actuation frequencies. One potential issue is the requirement for relatively high critical magnetic fields and field intervals (1.5-3 T) for the onset of FIPT and for reversible FIPT, respectively. (Abstract Copyright

  5. Structural, magnetic and electrical properties of La and Mn co-substituted BFO samples prepared by the sol–gel technique

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Prachi; Verma, Vivek, E-mail: vermavivek.neel@gmail.com

    2015-01-15

    We have examined the structural, magnetic and electrical properties of La and Mn co-substituted bismuth ferrite (BFO) samples prepared by the sol–gel technique. The XRD patterns confirm the formation of pure phase, rhombohedral structure in BFO. Manganese gave rise to spontaneous magnetization along with the clarity of magnetic hysteresis attributed to the mismatch of two magnetic ions Fe/Mn. The coercivity decreases with co substitution due to decrease in magneto crystalline anisotropy. It is observed that real part of dielectric constant (ε′) decreases with the increase in frequency. It is observed the modification in dielectric properties that may be due to La substitution which suppressed the transition of Fe{sup 3+} to Fe{sup 2+} ions, at room temperature. With La substitution in BFO there is an apparent increase in Ps, Pr and Ec values. In the case of the pristine sample BFO0, Ps reaches 0.043 μC/cm{sup 2} at the applied field (E) of 30 kV/cm with remnant polarization (Pr) 0.008 μC/cm{sup 2} and coercive field (Ec) 7.79 kV/cm. For the sample Bi{sub 0.80}La{sub 0.25}Fe{sub 0.95}Mn{sub 0.05}O{sub 3} (BFO6) Ps reaches 0.376 μC/cm{sup 2} at the applied field of 30 kV/cm with Pr 0.126 μC/cm{sup 2} and coercive field 10.3 kV/cm. - Highlights: • La and Mn co-substituted bismuth ferrite (BFO) samples were synthesized by the sol–gel technique. • Substitution of La and Mn in BFO is at Bi site and Fe site respectively. • Ferromagnetic, Ferroelectric and Dielectric properties enhanced with substitution. • Increase in the saturation magnetization, decrease in coercivity with co-substitution was found in the magnetic measurements. • The P–E loops show lossy behavior due to leakage current.

  6. Structures and electronic properties of Aun-1Cu and Aun (n≤9) clusters

    Institute of Scientific and Technical Information of China (English)

    Wang Hong-Yan; Li Xi-Bo; Tang Yong-Jian; R. Bruce King; Henry F. Schaefer III

    2007-01-01

    A systematic study on the structure and electronic properties of gold clusters doped each with one copper atom has been performed using the density functional theory. The average bond lengths in the Aun-1 Cu (n ≤ 9) bimetallic clusters are shorter than those in the corresponding pure gold clusters. The ionization potentials of the bimetallic clusters Aun-1 Cu (n ≤ 9) are larger than those of the corresponding homoatomic gold clusters except for Au5. The energy gaps of the Au-Cu binary clusters are narrower than those of the Aun clusters except AuCu and Au3Cu. No obvious even-odd effect exists in the variations of the electron affinities and ionization potentials for the Aun-1 Cu (n ≤ 9) clusters, which is in contrast to the case of gold clusters Aun.

  7. Distribution of platinum and cobalt atoms in a bimetallic nanoparticle

    Science.gov (United States)

    Chui, Yu Hang; Chan, Kwong-Yu

    2005-06-01

    Molecular dynamics simulations are performed to investigate the atomic distribution and the structure of platinum-cobalt nanoparticles. Heating and cooling techniques are applied before getting equilibrated structures at 298 K. Both crystalline (fcc) and amorphous structures are partly observed depending on cooling rates. The atomic distributions in different regions of a bimetallic nanoparticle are analyzed. Although platinum tends to occupy surface and near-surface sites of the bimetallic nanoparticle, a complete segregation to form a core-shell structure is not observed.

  8. 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.

  9. Influence of Cr, Mn, Co, Ni Substitution on Magnetic Properties and Magnetocaloric Effect in LaFe11.5Si1.5%Cr,Mn,Co,Ni替代对LaFe11.5Si1.5磁性与磁热效应的影响

    Institute of Scientific and Technical Information of China (English)

    胡义嘎; 松林; 王高峰; 李福安; 特古斯

    2011-01-01

    The effects of substitution of Fe by Cr, Mn, Co and Ni on the structure, magnetic and magnetocaloric properties of LaFe11.5Si1.5 were investigated by means of X-ray diffraction and magnetic measurements. The results showed that the compounds investigated mainly crystallized in NaZn13-type cubic structure. For Cr, Mn, Co and Ni substituted compounds, the impurity phases were mainly 1.3% α-Fe and 2.5% LaFeSi, both Curie temperature and saturation magnetization decreased with these impurity phases in LaFe11.5Si1.5, while increased for Co-substitution. The thermal hysteresis reduced for all substitution. The maximum value of magnetic entropy change ∣△Sm∣ for a magnetic field change of 0 ~5 T was about 23.8, 19.8, 26.4, 20.0 and 25.9 J·(kg·K) -1 for T = Cr, Mn, Fe, Co and Ni, respectively.%通过X射线衍射和磁性测量手段研究了由Cr,Mn,Co,Ni原子替代LaFe11.5Si1.5化合物中的Fe原子,对化合物结构、磁性与磁热效应的影响.结果表明:替代后的所有化合物的主相均为NaZn13型立方结构并存在杂相,衍射数据精修图表明杂相分别为1.3%的α-Fe相和2.5%的LaFeSi相.Cr,Mn和Ni的替代Fe使LaFe11.5 Si1.5化合物的居里温度与饱和磁化强度下降,而Co的替代化合物的居里温度与饱和磁化强度且增加.所有的替代均使化合物的热滞下降.对Cr,Mn,Fe,Co,Ni替代Fe的化合物在0~5.0T的磁场下最大磁熵变-△Sm分别为23.8,19.8,26.4,20.0和25.9 J·(kg·K)-1.

  10. New materials for Li-ion batteries: synthesis and spectroscopic characterization of Li2(FeMnCo)SiO4 cathode materials

    Science.gov (United States)

    Ferrari, Stefania; Mozzati, Maria Cristina; Lantieri, Marco; Spina, Gabriele; Capsoni, Doretta; Bini, Marcella

    2016-06-01

    Improving cathode materials is mandatory for next-generation Li-ion batteries. Exploring polyanion compounds with high theoretical capacity such as the lithium metal orthosilicates, Li2MSiO4 is of great importance. In particular, mixed silicates represent an advancement with practical applications. Here we present results on a rapid solid state synthesis of mixed Li2(FeMnCo)SiO4 samples in a wide compositional range. The solid solution in the P21/n space group was found to be stable for high iron concentration or for a cobalt content up to about 0.3 atom per formula unit. Other compositions led to a mixture of polymorphs, namely Pmn21 and Pbn21. All the samples contained a variable amount of Fe3+ ions that was quantified by Mössbauer spectroscopy and confirmed by the TN values of the paramagnetic to antiferromagnetic transition. Preliminary characterization by cyclic voltammetry revealed the effect of Fe3+ on the electrochemical response. Further work is required to determine the impact of these electrode materials on lithium batteries.

  11. Large single crystal diamond grown in FeNiMnCo-S-C system under high pressure and high temperature conditions

    Science.gov (United States)

    Zhang, He; Li, Shangsheng; Su, Taichao; Hu, Meihua; Li, Guanghui; Ma, Hongan; Jia, Xiaopeng

    2016-11-01

    Large diamonds have successfully been synthesized from FeNiMnCo-S-C system at temperatures of 1255-1393 °C and pressures of 5.3-5.5 GPa. Because of the presence of sulfur additive, the morphology and color of the large diamond crystals change obviously. The content and shape of inclusions change with increasing sulfur additive. It is found that the pressure and temperature conditions required for the synthesis decrease to some extent with the increase of S additive, which results in left down of the V-shape region. The Raman spectra show that the introduction of additive sulfur reduces the quality of the large diamond crystals. The x-ray photoelectron spectroscopy (XPS) spectra show the presence of S in the diamonds. Furthermore, the electrical properties of the large diamond crystals are tested by a four-point probe and the Hall effect method. When sulfur in the cell of diamond is up to 4.0 wt.%, the resistance of the diamond is 9.628×105 Ω·cm. It is shown that the large single crystal samples are n type semiconductors. This work is helpful for the further research and application of sulfur-doped semiconductor large diamond. Project supported by the National Natural Science Foundation of China (Grant No. 51172089), the Education Department of Henan Province, China (Grant No. 12A430010), and the Fundamental Research Funds for the Universities of Henan Province, China (Grant No. NSFRF140110).

  12. MnCo2O4 nanowires anchored on reduced graphene oxide sheets as effective bifunctional catalysts for Li-O2 battery cathodes.

    Science.gov (United States)

    Kim, Jong Guk; Kim, Youngmin; Noh, Yuseong; Kim, Won Bae

    2015-05-22

    A hybrid composite system of MnCo2 O4 nanowires (MCO NWs) anchored on reduced graphene oxide (RGO) nanosheets was prepared as the bifunctional catalyst of a Li-O2 battery cathode. The catalysts can be obtained from the hybridization of one-dimensional MCO NWs and two-dimensional RGO nanosheets. As O2 -cathode catalysts for Li-O2 cells, the MCO@RGO composites showed a high initial discharge capacity (ca. 11092.1 mAh gcarbon (-1) ) with a high rate performance. The Li-O2 cells could run for more than 35 cycles with high reversibility under a limited specific capacity of 1000 mAh gcarbon (-1) with a low potential polarization of 1.36 V, as compared with those of pure Ketjenblack and MCO NWs. The high cycling stability, low potential polarization, and rate capability suggest that the MCO@RGO composites prepared here are promising catalyst candidates for highly reversible Li-O2 battery cathodes.

  13. Abundances of Mn, Co and Eu in a sample of 20 F-G disk stars: the influence of hyperfine structure splitting

    CERN Document Server

    Peloso, E F; Silva, L; De Mello, G F P

    2005-01-01

    We present Mn, Co and Eu abundances for a sample of 20 disk F and G dwarfs and subgiants with metallicities in the range -0.8 <= [Fe/H] <= +0.3. We investigate the influence of hyperfine structure (HFS) on the derived abundances of Mn and Co by using HFS data from different sources in the literature, as well as calculated HFS from interaction factors A and B. Eu abundances were obtained from spectral synthesis of one Eu II line that takes into account HFS from a series of recent laboratory measurements. For the lines analyzed in this study, we find that for manganese, the differences between abundances obtained with different HFSs are no larger than 0.10 dex. Our cobalt abundances are even less sensitive to the choice of HFS than Mn, presenting a 0.07 dex maximum difference between determinations with different HFSs. However, the cobalt HFS data from different sources are significantly different. Our abundance results for Mn offer an independent confirmation of the results from Prochaska & McWilliam...

  14. Polymorphs of Li{sub 3}PO{sub 4} and Li{sub 2}MSiO{sub 4} (M = Mn, Co). The role of pressure

    Energy Technology Data Exchange (ETDEWEB)

    Arroyo y de Dompablo, M.E.; Gallardo-Amores, J.M.; Moran, E. [Dpto. de Quimica Inorganica, Facultad de CC. Quimicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Amador, U. [Dpto. de Quimica, Facultad de Farmacia, USP-CEU, 28668-Boadilla del Monte, Madrid (Spain); Ehrenberg, H. [IFW Dresden, Helmholtzstr. 20, D-01069 Dresden (Germany); Dupont, L. [LRCS, Universite de Picardie Jules-Verne, UMR 6007 CNRS, 33 rue Saint-Leu, 80039 Amiens (France); ALISTORE European Research Institute, Amiens (France); Dominko, R. [ALISTORE European Research Institute, Amiens (France); National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana (Slovenia)

    2009-04-01

    The behavior of Li{sub 3}PO{sub 4} and Li{sub 2}MSiO{sub 4} (M = Mn, Co) compounds under high pressure/high temperature is investigated. Pmn2{sub 1}-Li{sub 3}PO{sub 4} remains stable up to the higher experimental limit of 80 kbar (900 C). A sample of Li{sub 2}MnSiO{sub 4} consisting of a mixture of Pn2{sub 1} and Pmnb polymorphs converts upon high pressure/high temperature treatment into the Pmn2{sub 1} polymorph; the latter being stable at 80 kbar and 900 C. A sample of Li{sub 2}CoSiO{sub 4}-P2{sub 1}/n transforms to the denser Pmn2{sub 1} polymorph at 40 kbar/900 C, but decomposes at higher pressure (60 kbar/900 C). No evidence on any novel Li{sub 2}MSiO{sub 4} polymorph is detected in any of the high-pressure products. (author)

  15. Effect of (Li, Mn) co-doping on structural, optical and magnetic properties of chunk-shaped nano ZnO

    Energy Technology Data Exchange (ETDEWEB)

    Rajamanickam, N., E-mail: nrajamku@gmail.com; Mariammal, R.N.; Rajashabala, S.; Ramachandran, K.

    2014-11-25

    Highlights: • Chunk-shaped nano ZnO synthesized by varying Li and Mn doping concentrations. • The growth mechanism was discussed for chunk-shaped morphologies. • Undoped and Li doped CSNS ZnO exhibit weak ferromagnetic behavior with diamagnetism. • Room temperature ferromagnetism observed for Mn doped and Li/Mn co-doped CSNS ZnO. • Verdet constants and magneto-optic properties were measured from Faraday Effect method. - Abstract: Chunk shaped ZnO nanostructures (CSNS) simultaneously doped with Li and Mn for varying Li/Mn concentrations have been synthesized using wet-chemical method. Their crystal structural, optical and magnetic properties at room temperature (RT) were then investigated, which revealed that all the samples have a single phase with the wurtzite structure. Undoped and co-doped ZnO chunk-shape structures has been demonstrated by transmission electron microscope (TEM). The Mn/Li incorporation also creates more lattice defects and disorders, which influence directly characteristic photoluminescence (PL), FTIR and UV–vis spectra of Zn{sub 1−x−y}Mn{sub y}Li{sub x}O CSNS. Where green emission due to concentration of defects is seen. Magnetic measurements by VSM and the ferro fluid of synthesized nano ZnO by Faraday optical rotation for various concentration of Mn and Li in nano ZnO are done. Change of magnetic and magneto-optic (MO) properties due to Mn and Li ions are discussed in detail.

  16. A first-principles study of elastic, magnetic, and structural properties of PrX2 (X=Fe, Mn, Co) compounds

    Science.gov (United States)

    Shabara, Reham M.; Aly, Samy H.

    2017-02-01

    The elastic, magnetic, and structural properties of PrX2 (X=Fe, Mn, Co) alloys, of the cubic Laves structure (MgCu2), have been evaluated by first-principles density functional theory using both local spin density (LSDA) and generalized gradient (GGA) approximations. The lattice constant, magnetic moment, density of states, band structure, bulk modulus and its first pressure derivative are calculated. At zero pressure, the total magnetic moments of PrFe2, PrCo2, and PrMn2 using GGA are 4.515, 1.05, and 4.79 μB respectively. The bulk moduli using LSDA are higher than those using GGA approximation. The evaluated Bulk moduli of PrFe2, PrMn2 and PrCo2 using GGA approximation are 48.1, 42.98, and 72.23 GPa respectively. The lattice constant and magnetic moment of PrFe2 using GGA approximation are 7.2 Ǻ and 4.51 μB respectively in good agreement with experimental results.

  17. Synthesis of porous MnCo2O4microspheres with yolk–shell structure induced by concentration gradient and the effect on their performance in electrochemical energy storage

    DEFF Research Database (Denmark)

    Huang, Guoyong; Yang, Yue; Sun, Hongyu

    2016-01-01

    In this study, novel spherical yolk–shell MnCo2O4 powders with concentration gradient have been synthesized. The porous microspheres with yolk–shell structure (2.00–3.00 μm in average diameter, ∼200 nm in thickness of shell) are built up by irregular nanoparticles attached to each other. It is sh......In this study, novel spherical yolk–shell MnCo2O4 powders with concentration gradient have been synthesized. The porous microspheres with yolk–shell structure (2.00–3.00 μm in average diameter, ∼200 nm in thickness of shell) are built up by irregular nanoparticles attached to each other...

  18. Bimetallic Nanoparticles as Efficient Catalysts: Facile and Green Microwave Synthesis

    Directory of Open Access Journals (Sweden)

    Magda Blosi

    2016-07-01

    Full Text Available This work deals with the development of a green and versatile synthesis of stable mono- and bi-metallic colloids by means of microwave heating and exploiting ecofriendly reagents: water as the solvent, glucose as a mild and non-toxic reducer and polyvinylpirrolidone (PVP as the chelating agent. Particle size-control, total reaction yield and long-term stability of colloids were achieved with this method of preparation. All of the materials were tested as effective catalysts in the reduction of p-nitrophenol in the presence of NaBH4 as the probe reaction. A synergistic positive effect of the bimetallic phase was assessed for Au/Cu and Pd/Au alloy nanoparticles, the latter showing the highest catalytic performance. Moreover, monoand bi-metallic colloids were used to prepare TiO2- and CeO2-supported catalysts for the liquid phase oxidation of 5-hydroxymethylfufural (HMF to 2,5-furandicarboxylic acid (FDCA. The use of Au/Cu and Au/Pd bimetallic catalysts led to an increase in FDCA selectivity. Finally, preformed Pd/Cu nanoparticles were incorporated into the structure of MCM-41-silica. The resulting Pd/Cu MCM-41 catalysts were tested in the hydrodechlorination of CF3OCFClCF2Cl to CF3OCF=CF2. The effect of Cu on the hydrogenating properties of Pd was demonstrated.

  19. Photoluminescence of hollow gold-silver bimetallic nanoparticles

    OpenAIRE

    Weon-Sik Chae; Hee-Ok Lee; Seung-Lim Oh

    2011-01-01

    Hollow gold nanoparticles including silver were prepared by the galvanic replacement reaction of silver nanoparticles by gold. The resulting hollow gold-silver bimetallic nanoparticles show notable blue-green emissions, which are studied using steady-state and time-resolved spectroscopy.

  20. High pressure CO hydrogenation over bimetallic Pt-Co catalysts

    DEFF Research Database (Denmark)

    Christensen, Jakob Munkholt; Medford, Andrew James; Studt, Felix

    2014-01-01

    The potential of bimetallic Pt-Co catalysts for production of higher alcohols in high pressure CO hydrogenation has been assessed. Two catalysts (Pt3Co/SiO2 and PtCo/SiO2) were tested, and the existing literature on CO hydrogenation over Pt-Co catalysts was reviewed. It is found that the catalyst...

  1. Crystalline structure-dependent growth of bimetallic nanostructures.

    Science.gov (United States)

    Li, Qian; Jiang, Ruibin; Ming, Tian; Fang, Caihong; Wang, Jianfang

    2012-11-21

    Morphological control of multimetallic nanostructures is crucial for obtaining shape-dependent physical and chemical properties. Up to date, control of the shapes of multimetallic nanostructures has remained largely empirical. Multimetallic nanostructures have been produced mostly through seed-mediated growth. Understanding the role played by starting nanocrystal seeds can help in controlling the shape and in turn the plasmonic and catalytic properties of multimetallic nanostructures. In this work, we have studied the effect of the crystalline structure and shape of Au nanocrystal seeds on the morphology of the resultant bimetallic nanostructures. Single-crystalline Au nanorods, multiply twinned Au nanorods, and multiply twinned Au nanobipyramids were employed as the starting seeds. Both silver and palladium exhibit highly preferential growth on the side surfaces of the single-crystalline Au nanorods, giving rise to bimetallic cuboids, whereas they prefer to grow at the ends of the multiply twinned Au nanorods and nanobipyramids, giving rise to bimetallic nanorods. These results indicate that the morphology of the bimetallic nanostructures is highly dependent on the crystalline structure of the Au nanocrystal seeds. Our results will be useful for guiding the preparation of multimetallic nanostructures with desired shapes and therefore plasmonic properties for various plasmon-based applications.

  2. Photoluminescence of hollow gold-silver bimetallic nanoparticles

    Directory of Open Access Journals (Sweden)

    Weon-Sik Chae

    2011-12-01

    Full Text Available Hollow gold nanoparticles including silver were prepared by the galvanic replacement reaction of silver nanoparticles by gold. The resulting hollow gold-silver bimetallic nanoparticles show notable blue-green emissions, which are studied using steady-state and time-resolved spectroscopy.

  3. Charge distribution and Fermi level in bimetallic nanoparticles.

    Science.gov (United States)

    Holmberg, Nico; Laasonen, Kari; Peljo, Pekka

    2016-01-28

    Upon metal-metal contact, a transfer of electrons will occur between the metals until the Fermi levels in both phases are equal, resulting in a net charge difference across the metal-metal interface. Here, we have examined this contact electrification in bimetallic model systems composed of mixed Au-Ag nanoparticles containing ca. 600 atoms using density functional theory calculations. We present a new model to explain this charge transfer by considering the bimetallic system as a nanocapacitor with a potential difference equal to the work function difference, and with most of the transferred charge located directly at the contact interface. Identical results were obtained by considering surface contacts as well as by employing a continuum model, confirming that this model is general and can be applied to any multimetallic structure regardless of geometry or size (going from nano- to macroscale). Furthermore, the equilibrium Fermi level was found to be strongly dependent on the surface coverage of different metals, enabling the construction of scaling relations. We believe that the charge transfer due to Fermi level equilibration has a profound effect on the catalytic, electrocatalytic and other properties of bimetallic particles. Additionally, bimetallic nanoparticles are expected to have very interesting self-assembly for large superstructures due to the surface charge anisotropy between the two metals.

  4. Orderly packed anodes for high-power lithium-ion batteries with super-long cycle life: rational design of MnCO3/large-area graphene composites.

    Science.gov (United States)

    Zhong, Yiren; Yang, Mei; Zhou, Xianlong; Luo, Yuting; Wei, Jinping; Zhou, Zhen

    2015-02-01

    MnCO3 particles uniformly distributed on large-area graphene form 2D composites whose large-area character enables them to self-assemble face-to-face into orderly packed electrodes. Such regular structures form continuous and efficient transport networks, leading to outstanding lithium storage with high capacity, ultralong cycle life, and excellent rate capability--all characteristics that are required for high-power lithium-ion batteries.

  5. Remarkable effect of bimetallic nanocluster catalysts for aerobic oxidation of alcohols: combining metals changes the activities and the reaction pathways to aldehydes/carboxylic acids or esters.

    Science.gov (United States)

    Kaizuka, Kosuke; Miyamura, Hiroyuki; Kobayashi, Shū

    2010-11-01

    Selective oxidation of alcohols catalyzed by novel carbon-stabilized polymer-incarcerated bimetallic nanocluster catalysts using molecular oxygen has been developed. The reactivity and the selectivity were strongly dependent on the combination of metals and solvent systems; aldehydes and ketones were obtained by the gold/platinum catalyst in benzotrifluoride, and esters were formed by the gold/palladium catalyst in methanol. To the best of our knowledge, this is the first example that the reaction pathway has been changed dramatically in gold catalysis by combining with a second metal. The differences in the activity and the selectivity are considered to be derived from the difference in the structure of the bimetallic clusters.

  6. Structural and optical properties of the naked and passivated Al5Au5 bimetallic nanoclusters

    Science.gov (United States)

    Grande-Aztatzi, Rafael; Formoso, Elena; Mercero, Jose M.; Matxain, Jon M.; Grabowski, Slawomir J.; Ugalde, Jesus M.

    2016-03-01

    The structural and optical properties of both the naked and passivated bimetallic Al5Au5 nanoclusters have been analyzed based on data obtained from ab initio density functional theory and quantum molecular dynamics simulations. It has been found that the Al5Au5 nanocluster possesses a hollow shaped minimum energy structure with segregated Al and Au layered domains, the former representing the electrophilic domain and the latter the nucleophilic domain. In particular, it has been shown that alkali metal cations attach in the nucleophilic domain and hop from one Au site to the next one in the picoseconds time scale, while anions are bound tightly to the Al atoms of the electrophilic domain. Simulating annealing studies are very suggestive of the proneness of the nanocluster towards coalescence into large cluster units, when the cluster is left unprotected by appropriate ligands. Further passivation studies with NaF salt suggest, nonetheless, the possibility of the isolation of the Al5Au5 cluster in molten salts or ionic liquids.

  7. Structural, Transport and Electrochemical Properties of LiFePO4 Substituted in Lithium and Iron Sublattices (Al, Zr, W, Mn, Co and Ni

    Directory of Open Access Journals (Sweden)

    Konrad Świerczek

    2013-04-01

    Full Text Available LiFePO4 is considered to be one of the most promising cathode materials for lithium ion batteries for electric vehicle (EV application. However, there are still a number of unsolved issues regarding the influence of Li and Fe-site substitution on the physicochemical properties of LiFePO4. This is a review-type article, presenting results of our group, related to the possibility of the chemical modification of phosphoolivine by introduction of cation dopants in Li and Fe sublattices. Along with a synthetic review of previous papers, a large number of new results are included. The possibility of substitution of Li+ by Al3+, Zr4+, W6+ and its influence on the physicochemical properties of LiFePO4 was investigated by means of XRD, SEM/EDS, electrical conductivity and Seebeck coefficient measurements. The range of solid solution formation in Li1−3xAlxFePO4, Li1−4xZrxFePO4 and Li1−6xWxFePO4 materials was found to be very narrow. Transport properties of the synthesized materials were found to be rather weakly dependent on the chemical composition. The battery performance of selected olivines was tested by cyclic voltammetry (CV. In the case of LiFe1−yMyPO4 (M = Mn, Co and Ni, solid solution formation was observed over a large range of y (0 0.25 leads to considerably lower values of σ. The activated character of electrical conductivity with a rather weak temperature dependence of the Seebeck coefficient suggests a small polaron-type conduction mechanism. The electrochemical properties of LiFe1−yMyPO4 strongly depend on the Fe substitution level.

  8. Ionisation Potentials of Metal Carbide Clusters

    Science.gov (United States)

    Dryza, Viktoras; Addicoat, M.; Gascooke, Jason; Buntine, Mark; Metha, Gregory

    2006-03-01

    Photo-Ionisation Efficiency (PIE) experiments have been performed on gas phase niobium and tantalum carbide clusters to determine their ionisation potentials (IPs). For TanCm (n = 3-4, m = 0-4) clusters an oscillatory behaviour is observed such that clusters with an odd number of carbon atoms have higher IPs and clusters with an even number of carbons have lower IPs. Excellent agreement is found with relative IPs calculated using density functional theory for the lowest energy structures, which are consistent with the development of a 2x2x2 face-centred nanocrystal. For the niobium carbide clusters we observe the species Nb4C5 and Nb4C6. Initial calculations suggest that these clusters contain carbon-carbon bonding. Interestingly, the stoichiometry for Nb4C6 is half that of a metcar, M8C12. Preliminary data will also be shown on bimetallic-carbide clusters.

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

    OpenAIRE

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

    2014-01-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the s...

  10. Nanocrystal and surface alloy properties of bimetallic Gold-Platinum nanoparticles

    OpenAIRE

    Mott Derrick; Luo Jin; Smith Andrew; Njoki Peter; Wang Lingyan; Zhong Chuan-Jian

    2006-01-01

    AbstractWe report on the correlation between the nanocrystal and surface alloy properties with the bimetallic composition of gold-platinum(AuPt) nanoparticles. The fundamental understanding of whether the AuPt nanocrystal core is alloyed or phase-segregated and how the surface binding properties are correlated with the nanoscale bimetallic properties is important not only for the exploitation of catalytic activity of the nanoscale bimetallic catalysts, but also to the general exploration of t...

  11. Bimetallic dendrimer-encapsulated nanoparticles as catalysts: a review of the research advances

    OpenAIRE

    Peng, Xiaohong; Pan, Qinmin; Rempel, Garry L.

    2008-01-01

    Bimetallic dendrimer-encapsulated nanoparticles (DENs) are important materials, because they have demonstrated improvement in performance compared to the monometallic DENs in many systems when they are used as catalysts. This tutorial review focuses on the recent research advances in bimetallic DENs with respect to their synthesis, characterization, and applications as catalysts. Bimetallic DENs can be made mainly via three routes: co-complexation, sequential loading, and partial displacement...

  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 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

  13. Structural Characterization of Bimetallic Nanocrystal Electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cullen, David A [ORNL

    2016-01-01

    Late transition metal nanocrystals find applications in heterogeneous catalysis such as plasmon-enhanced catalysis and as electrode materials for fuel cells, a zero-emission and sustainable energy technology. Their commercial viability for automotive transportation has steadily increased in recent years, almost exclusively due to the discovery of more efficient bimetallic nanocatalysts for the oxygen reduction reaction (ORR) at the cathode. Despite improvements to catalyst design, achieving high activity while maintaining durability is essential to further enhance their performance for this and other important applications in catalysis. Electronic effects arising from the generation of metal-metal interfaces, from plasmonic metals, and from lattice distortions, can vastly improve sorption properties at catalytic surfaces, while increasing durability.[1] Multimetallic lattice-strained nanoparticles are thus an interesting opportunity for fundamental research.[2,3] A colloidal synthesis approach is demonstrated to produce AuPd alloy and Pd@Au core-shell nanoicosahedra as catalysts for electro-oxidations. The nanoparticles are characterized using aberration-corrected scanning transmission electron microscopy (ac-STEM) and large solid angle energy dispersive X-ray spectroscopy (EDS) on an FEI Talos 4-detector STEM/EDS system. Figure 1 shows bright-field (BF) and high-angle annular dark-field (HAADF) ac-STEM images of the alloy and core-shell nanoicosahedra together with EDS line-scans and elemental maps. These structures are unique in that the presence of twin boundaries, alloying, and core-shell morphology could create highly strained surfaces and interfaces. The shell thickness of the core-shell structures observed in HAADF-STEM images is tuned by adjusting the ratio between metal precursors (Figure 2a-f) to produce shells ranging from a few to several monolayers. Specific activity was measured in ethanol electro-oxidation to examine the effect of shell thickness on

  14. Tuning structural motifs and alloying of bulk immiscible Mo-Cu bimetallic nanoparticles by gas-phase synthesis

    NARCIS (Netherlands)

    Krishnan, Gopi; Verheijen, Marcel A.; ten Brink, Gert; Palasantzas, George; Kooi, Bart J.

    2013-01-01

    Nowadays bimetallic nanoparticles (NPs) have emerged as key materials for important modern applications in nanoplasmonics, catalysis, biodiagnostics, and nanomagnetics. Consequently the control of bimetallic structural motifs with specific shapes provides increasing functionality and selectivity for

  15. Tuning structural motifs and alloying of bulk immiscible Mo-Cu bimetallic nanoparticles by gas-phase synthesis

    NARCIS (Netherlands)

    Krishnan, Gopi; Verheijen, Marcel A.; ten Brink, Gert; Palasantzas, George; Kooi, Bart J.

    2013-01-01

    Nowadays bimetallic nanoparticles (NPs) have emerged as key materials for important modern applications in nanoplasmonics, catalysis, biodiagnostics, and nanomagnetics. Consequently the control of bimetallic structural motifs with specific shapes provides increasing functionality and selectivity for

  16. Nanosegregated bimetallic oxide anode catalyst for proton exchange membrane electrolyzer

    Science.gov (United States)

    Danilovic, Nemanja; Kang, Yijin; Markovic, Nenad; Stamenkovic, Vojislav; Myers, Deborah J.; Subbaraman, Ram

    2016-08-23

    A surface segregated bimetallic composition of the formula Ru.sub.1-xIr.sub.x wherein 0.1.ltoreq.x.ltoreq.0.75, wherein a surface of the material has an Ir concentration that is greater than an Ir concentration of the material as a whole is provided. The surface segregated material may be produced by a method including heating a bimetallic composition of the formula Ru.sub.1-xIr.sub.x, wherein 0.1.ltoreq.x.ltoreq.0.75, at a first temperature in a reducing environment, and heating the composition at a second temperature in an oxidizing environment. The surface segregated material may be utilized in electrochemical devices.

  17. Extended X-ray absorption fine structure of bimetallic nanoparticles

    Directory of Open Access Journals (Sweden)

    Carolin Antoniak

    2011-05-01

    Full Text Available Electronic and magnetic properties strongly depend on the structure of the material, especially on the crystal symmetry and chemical environment. In nanoparticles, the break of symmetry at the surface may yield different physical properties with respect to the corresponding bulk material. A useful tool to investigate the electronic structure, magnetic behaviour and local crystallographic structure is X-ray absorption spectroscopy. In this review, recent developments in the field of extended X-ray absorption fine structure measurements and in the analysis methods for structural investigations of bimetallic nanoparticles are highlighted. The standard analysis based on Fourier transforms is compared to the relatively new field of wavelet transforms that have the potential to outperform traditional analysis, especially in bimetallic alloys. As an example, the lattice expansion and inhomogeneous alloying found in FePt nanoparticles is presented, and this is discussed below in terms of the influence of employed density functional theory calculations on the magnetic properties.

  18. Bimetallic Thermal Resists for Photomask, Micromachining and Microfabrication

    OpenAIRE

    Tu, Richard Yuqiang

    2004-01-01

    Photoresists and photomasks are two of the most critical materials in microfabrication and micromachining industries. As the shift towards shorter wavelength exposure continues, conventional organic photoresists and chromelquartz photomasks start to encounter problems. This thesis investigates and presents an alternative to organic photoresists and chromium photomasks which overcomes their intrinsic problems. A bimetallic thin film, such as BilIn and SnIIn, creates an inorganic thermal resist...

  19. Antibacterial activity of graphene supported FeAg bimetallic nanocomposites.

    Science.gov (United States)

    Ahmad, Ayyaz; Qureshi, Abdul Sattar; Li, Li; Bao, Jie; Jia, Xin; Xu, Yisheng; Guo, Xuhong

    2016-07-01

    We report the simple one pot synthesis of iron-silver (FeAg) bimetallic nanoparticles with different compositions on graphene support. The nanoparticles are well dispersed on the graphene sheet as revealed by the TEM, XRD, and Raman spectra. The antibacterial activity of graphene-FeAg nanocomposite (NC) towards Bacillus subtilis, Escherichia coli, and Staphylococcus aureus was investigated by colony counting method. Graphene-FeAg NC demonstrates excellent antibacterial activity as compared to FeAg bimetallic without graphene. To understand the antibacterial mechanism of the NC, oxidative stress caused by reactive oxygen species (ROS) and the glutathione (GSH) oxidation were investigated in the system. It has been observed that ROS production and GSH oxidation are concentration dependent while the increase in silver content up to 50% generally enhances the ROS production while ROS decreases on further increase in silver content. Graphene loaded FeAg NC demonstrates higher GSH oxidation capacity than bare FeAg bimetallic nanocomposite. The mechanism study suggests that the antibacterial activity is probably due to membrane and oxidative stress produced by the nanocomposites. The possible antibacterial pathway mainly includes the non-ROS oxidative stress (GSH oxidation) while ROS play minor role.

  20. Reduction of nitrate by bimetallic Fe/Ni nanoparticles.

    Science.gov (United States)

    Kang, Haiyan; Xiu, Zongming; Chen, Jiawei; Cao, Wenping; Guo, Yifei; Li, Tielong; Jin, Zhaohui

    2012-09-01

    Bimetallic Fe/Ni nanoparticles were synthesized and their nitrate reduction capacity was studied. Nitrate (354 mg L(-1), equal to 5.71 mmol L(-1)) reduction was performed using Fe/Ni nanoparticles with various Ni contents (1.0, 5.0, 10 and 20%) in an unbuffered condition. Optimum nitrate reduction rate (1.03 +/- 0.087 x 10(-4) mol x min(-1) x greduc(-1)) was obtained with 5.0% nano-scale Fe/Ni, while only 25% nitrate (1.05 +/- 0.091 x 10(-5) mol x min(-1) x greduc(-1)) was transformed by nano-scale Fe(0) within the same reaction time, which means that these bimetallic nanoparticles are obviously more reactive than monometallic nano-scale Fe(0). For this bimetallic system a near-neutral initial pH (6.5) is more favourable than an acidic condition (2.0 and 4.0). Relatively air-stable nano-scale Fe/Ni particles were developed by slowly aging them for 22 h and exhibited similar reactivity to freshly synthesized nano-scale Fe(0). Although undesirable transformation of nitrate (91.0 +/- 0.37%) to ammonium was observed in this study, Fe/Ni particles showed a much higher nitrate reduction rate and an optimum reduction rate at near-neutral pH, which may have important implications for nitrate-contaminated site remediation.

  1. Facile synthesis of bimetallic nanoparticles by femtosecond laser irradiation method

    Directory of Open Access Journals (Sweden)

    Joseph Lik Hang Chau

    2017-02-01

    Full Text Available Bimetallic Pt–Au and Fe–Pt nanoparticles are successfully fabricated by high-intensity laser irradiation of aqueous solution without any chemical reducing agent. The mechanism of the formation of bimetallic nanoalloys by laser irradiation of the solution without using any reducing agent was mainly attributed to the optically induced decomposition of water molecule. When an intense femtosecond laser field is focused in an aqueous solution containing metal ions, the free electrons will be produced by the dissociation of water molecules, these free electrons and hydrogen radicals contained in the plasma might be caught by H+ or OH− ions to form the bubbles of H2 and O2 gases or they can be trapped by metal ions, resulting in the formation of metal atoms during the femtosecond laser irradiation process. The average size of the bimetallic nanoparticles increases with irradiation time. This technique is simple and ‘green’ process without using any chemicals except for metal salt and dispersing agent.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-08-30

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

  3. Designed synthesis of MOx (M = Zn, Fe, Sn, Ni, Mn, Co, Ce, Mg, Ag), Pt, and Au nanoparticles supported on hierarchical CuO hollow structures.

    Science.gov (United States)

    Zhang, Zailei; Jung, Ji Chul; Yan, Ning

    2016-12-01

    Despite intensive research into support substrates for the dispersal of nanoparticles and their applications, there has been a lack of general methods to produce metal oxide hollow substrates supporting a wide range of metal and metal oxides. Herein, a synthetic protocol for the preparation of CuO hollow structure-supported MOx (M = Zn, Fe, Ni, Sn, Mn, Co, Ce, Mg, and Ag) and noble metals (Pt and Au) with the desired properties and shell structure, such as CuO/Fe2O3, CuO/ZnO, CuO/SnO2, CuO/MgO, CuO/NiO, CuO/Mn2O3, CuO/CoO, CuO/CeO2, CuO/Ag2O, CuO/Pt, CuO/Au hollow cubes, CuO/ZnO double-shell hollow cubes, CuO/SnO2 double-shell hollow octahedra, CuO/SnO2/Fe2O3 and CuO/Mn2O3/NiO double-shell hollow cubes, was developed based on controlled calcination and etching. These hybrid hollow structures were employed not only as support substrates but also as active constituents for catalytic reactions. As an example, we demonstrated that CuO/ZnO hollow cubes are remarkably efficient in converting solid chitin biomass to liquid chemicals in methanol. In addition, CuO/ZnO double-shell hollow cubes were highly effective in the oxidation of benzyl alcohol in the presence of H2O2, whereas CuO/Pt and CuO/Au hollow cubes promoted the oxidation of benzyl alcohol in pure O2. The strategy developed in this work extends the controllable fabrication of high-quality CuO hollow structure-supported nanoparticles using various compositions and shell structures, paving the way to the exploration and systematic comparison of these materials in a wider range of applications.

  4. Investigating the effect of Cd-Mn co-doped nano-sized BiFeO3 on its physical properties

    Science.gov (United States)

    Ishaq, B.; Murtaza, G.; Sharif, S.; Azhar Khan, M.; Akhtar, Naeem; Will, I. G.; Saleem, Murtaza; Ramay, Shahid M.

    This work deals with the investigation of different effects on the structural, magnetic, electronic and dielectric properties of Cd and Mn doped Bi0.75Cd0.25Fe1-xMnxO3 multiferroic samples by taking fixed ratios of Cd and varying the Mn ratio with values of x = 0.0, 0.5, 0.10 and 0.15. Cd-Mn doped samples were synthesized chemically using a microemulsion method. All the samples were finally sintered at 700 °C for 2 h to obtain the single phase perovskites structure of BiFeO3 materials. The synthesized samples were characterized by different techniques, such as X-ray diffractometry (XRD), Scanning Electron Microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), LCR meter and magnetic properties using VSM. XRD results confirm BFO is a perovskite structure having crystallite size in the range of 24-54 nm. XRD results also reveal observed structural distortion due to doping of Cd at the A-site and Mn at the B-site of BFO. SEM results depict that, as the substitution of Cd-Mn increases in BFO, grain size decreases up to 30 nm. FTIR spectra showed prominent absorption bands at 555 cm-1 and 445 cm-1 corresponding to the stretching vibrations of the metal ions complexes at site A and site B, respectively. Variation of dielectric constant (ɛ‧) and loss tangent (tan δ) at room temperature in the range of 1 MHz to 3 GHz have been investigated. Results reveal that with Cd-Mn co doping a slight decrease in dielectric constant have been observed. Magnetic properties of Cd-Mn doped pure BFO samples have been studied at 300 K. Results reveal that undoped BiFeO3 exhibits weak ferromagnetic ordering due to the canting of its spin. Increase in magnetization and decrease in coercivity is a clear indication that a material can be used in high density recording media and memory devices.

  5. Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO3, –MnO2, and –Mn2O3 Nanocomposites for Aerial Oxidation of Alcohols

    Directory of Open Access Journals (Sweden)

    Mohamed E. Assal

    2017-01-01

    Full Text Available Zinc oxide nanoparticles doped manganese carbonate catalysts [X% ZnOx–MnCO3] (where X = 0–7 were prepared via a facile and straightforward coprecipitation procedure, which upon different calcination treatments yields different manganese oxides, that is, [X% ZnOx–MnO2] and [X% ZnOx–Mn2O3]. A comparative catalytic study was conducted to evaluate the catalytic efficiency between carbonates and oxides for the selective oxidation of secondary alcohols to corresponding ketones using molecular oxygen as a green oxidizing agent without using any additives or bases. The prepared catalysts were characterized by different techniques such as SEM, EDX, XRD, TEM, TGA, BET, and FTIR spectroscopy. The 1% ZnOx–MnCO3 calcined at 300°C exhibited the best catalytic performance and possessed highest surface area, suggesting that the calcination temperature and surface area play a significant role in the alcohol oxidation. The 1% ZnOx–MnCO3 catalyst exhibited superior catalytic performance and selectivity in the aerial oxidation of 1-phenylethanol, where 100% alcohol conversion and more than 99% product selectivity were obtained in only 5 min with superior specific activity (48 mmol·g−1·h−1 and 390.6 turnover frequency (TOF. The specific activity obtained is the highest so far (to the best of our knowledge compared to the catalysts already reported in the literatures used for the oxidation of 1-phenylethanol. It was found that ZnOx nanoparticles play an essential role in enhancing the catalytic efficiency for the selective oxidation of alcohols. The scope of the oxidation process is extended to different types of alcohols. A variety of primary, benzylic, aliphatic, allylic, and heteroaromatic alcohols were selectively oxidized into their corresponding carbonyls with 100% convertibility without overoxidation to the carboxylic acids under base-free conditions.

  6. CO methanation over supported bimetallic Ni-Fe catalysts: From computational studies towards catalyst optimization

    DEFF Research Database (Denmark)

    Kustov, Arkadii; Frey, Anne Mette; Larsen, Kasper Emil

    2007-01-01

    DFT calculations combined with a computational screening method have previously shown that bimetallic Ni-Fe alloys should be more active than the traditional Ni-based catalyst for CO methanation. That was confirmed experimentally for a number of bimetallic Ni-Fe catalysts supported on MgAl2O4. He...

  7. PREPARATION OF NOVEL METALLIC AND BIMETALLIC CROSS-LINKED POLY (VINYL ALCOHOL) NANOCOMPOSITES UNDER MICROWAVE IRRADIATION

    Science.gov (United States)

    A facile method utilizing microwave irradiation is described that accomplishes the cross-linking reaction of PVA with metallic and bimetallic systems. Nanocomposites of PVA-cross-linked metallic systems such as Pt, Cu, and In and bimetallic systems such as Pt-In, Ag-Pt, Pt-Fe, Cu...

  8. NOVEL METALLIC AND BIMETALLIC CROSS-LINKED POLY (VINYL ALCOHOL) NANOCOMPOSITES PREPARED UNDER MICROWAVE IRRADIATION

    Science.gov (United States)

    A facile microwave irradiation approach that results in a cross-linking reaction of poly (vinyl alcohol) (PVA) with metallic and bimetallic systems is described. Nanocomposites of PVA cross-linked metallic systems such as Pt, Cu, and In and bimetallic systems such as Pt-In, Ag-P...

  9. Strategies to initiate and control the nucleation behavior of bimetallic nanoparticles

    NARCIS (Netherlands)

    Krishnan, Gopi; de Graaf, Sytze; Brink, ten Gert; Persson, Per O. A.; Kooi, Bart J.; Palasantzas, Georgios

    2017-01-01

    In this work we report strategies to nucleate bimetallic nanoparticles (NPs) made by gas phase synthesis of elements showing difficulty in homogeneous nucleation. It is shown that the nucleation assisted problem of bimetallic NP synthesis can be solved via the following pathways: (i) selecting an

  10. Catalytic reforming of glycerol in supercritical water over bimetallic Pt-Ni catalyst

    NARCIS (Netherlands)

    Chakinala, Anand G.; Swaaij, van Wim P.M.; Kersten, Sascha R.A.; Vlieger, de Dennis; Seshan, Kulathuiyer; Brilman, D.W.F. (Wim)

    2013-01-01

    Catalytic reforming of pure glycerol for the production of hydrogen at low temperature and short residence times in supercritical water was investigated using a bimetallic Pt–Ni catalyst supported on alumina. Initial tests were carried out to study the reforming activity of bimetallic Pt–Ni catalyst

  11. Magnetic property and thermal analysis of a Mn(II) complex with [Mn(CO2)]n chains based on 4,4‧-bis(1H-imidazol-1-yl-methyl)biphenyl

    Science.gov (United States)

    Zhang, Ming-Dao; Zheng, Bao-Hui; Wang, Zhe; Jiao, Yan; Chen, Min-Dong

    2014-11-01

    Magnetic coordination polymers have attracted considerable interest due to their novel structures and potential applications. In this paper, one new 2D magnetic manganese coordination polymer {[Mn(bimb)(OBA)]}n (1) was synthesized under solvothermal conditions based on 4,4‧-bis(1H-imidazol-1-yl-methyl)biphenyl (bimb) and 4,4‧-oxybis(benzoate) (H2OBA). Complex 1 contains [Mn(CO2)]n 1D chains and magnetic susceptibility measurements indicate that compound 1 exhibits an antiferromagnetic coupling interaction. In addition, complex 1 exhibits solid-state photoluminescence and high thermal stability.

  12. Bimetallic ruthenium-copper nanoparticles embedded in mesoporous carbon as an effective hydrogenation catalyst.

    Science.gov (United States)

    Liu, Jiajia; Zhang, Li Li; Zhang, Jiatao; Liu, Tao; Zhao, X S

    2013-11-21

    Bimetallic ruthenium-copper nanoparticles embedded in the pore walls of mesoporous carbon were prepared via a template route and evaluated in terms of catalytic properties in D-glucose hydrogenation. The existence of bimetallic entities was supported by Ru L3-edge and Cu K-edge X-ray absorption results. The hydrogen spillover effect of the bimetallic catalyst on the hydrogenation reaction was evidenced by the results of both hydrogen and carbon monoxide chemisorptions. The bimetallic catalyst displayed a higher catalytic activity than the single-metal catalysts prepared using the same approach, namely ruthenium or copper nanoparticles embedded in the pore walls of mesoporous carbon. This improvement was due to the changes in the geometric and electronic structures of the bimetallic catalyst because of the presence of the second metal.

  13. Preparation of bimetallic nanoparticles using a facile green synthesis method and their application.

    Science.gov (United States)

    Xia, Bihua; He, Fang; Li, Lidong

    2013-04-16

    A straightforward, economically viable, and green approach for the synthesis of well-stabilized Au/Ag bimetallic nanoparticles is described; this method uses nontoxic and renewable degraded pueraria starch (DPS) as a matrix and mild reaction conditions. The DPS acted as both a reducing agent and a capping agent for the bimetallic nanoparticles. Au/Ag bimetallic nanoparticles were successfully grown within the DPS matrixes, and the bimetallic structures were characterized using various methods, including high-resolution transmission electron microscopy, energy-dispersive X-ray, and X-ray diffraction. Moreover, it was shown that these DPS-capped Au/Ag bimetallic nanoparticles could function as catalysts for the reduction of 4-nitrophenol in the presence of NaBH4 and were more effective than Au or Ag monometallic nanoparticles.

  14. Characterization of Bimetallic Fe-Ru Oxide Nanoparticles Prepared by Liquid-Phase Plasma Method

    Science.gov (United States)

    Lee, Sung-Jin; Lee, Heon; Jeon, Ki-Joon; Park, Hyunwoong; Park, Young-Kwon; Jung, Sang-Chul

    2016-07-01

    The bimetallic Fe-Ru oxide nanoparticles were synthesized in the liquid-phase plasma (LPP) method which employed iron chloride and ruthenium chloride as precursors. The active species (OH·, Hα, Hβ, and OI) and the iron and ruthenium ions were observed in the plasma field created by the LPP process. The spherical-shaped bimetallic Fe-Ru oxide nanoparticles were synthesized by the LPP reaction, and the size of the particles was growing along with the progression of the LPP reaction. The synthesized bimetallic Fe-Ru oxide nanoparticles were comprised of Fe2O3, Fe3O4, RuO, and RuO2. Ruthenium had a higher reduction potential than iron and resulted in higher ruthenium composition in the synthesized bimetallic nanoparticles. The control of the molar ratio of the precursors in the reactant solution was found to be employed as a means to control the composition of the elements in bimetallic nanoparticles.

  15. An in-depth understanding of the bimetallic effects and coked carbon species on an active bimetallic Ni(Co)/Al2O3 dry reforming catalyst.

    Science.gov (United States)

    Liao, Xin; Gerdts, Rihards; Parker, Stewart F; Chi, Lina; Zhao, Yongxiang; Hill, Martyn; Guo, Junqiu; Jones, Martin O; Jiang, Zheng

    2016-06-29

    Ni/Al2O3, Co/Al2O3 and bimetallic Ni(Co)/Al2O3 catalysts were prepared using an impregnation method and employed in CO2 dry reforming of methane under coking-favored conditions. The spent catalysts were carefully characterized using typical characterization technologies and inelastic neutron scattering spectroscopy. The bimetallic catalyst exhibited a superior activity and anti-coking performance compared to Ni/Al2O3, while the most resistant to coking behavior was Co/Al2O3. The enhanced activity of the Ni(Co)/Al2O3 bimetallic catalyst is attributed to the reduced particle size of metallic species and resistance to forming stable filamentous carbon. The overall carbon deposition on the spent bimetallic catalyst is comparable to that of the spent Ni/Al2O3 catalyst, whereas the carbon deposited on the bimetallic catalyst is mainly less-stable carbonaceous species as confirmed by SEM, TPO, Raman and INS characterization. This study provides an in depth understanding of alloy effects in catalysts, the chemical nature of coked carbon on spent Ni-based catalysts and, hopefully, inspires the creative design of a new bimetallic catalyst for dry reforming reactions.

  16. XPS study of the electron structure of heterometallic trinuclear complexes Fe{sub 2}M(μ{sub 3}-O)(μ-Piv){sub 6}(HPiv){sub 3} (M=Mn, Co, Ni)

    Energy Technology Data Exchange (ETDEWEB)

    Ivanova, T.M. [Kurnakov Institute of General and Inorganic Chemistry of RAS, Moscow (Russian Federation); Kochur, A.G., E-mail: agk@rgups.ru [Rostov State Transport University, Rostov-na-Donu (Russian Federation); Maslakov, K.I. [Lomonosov Moskow State University, Moscow (Russian Federation); Kiskin, M.A. [Kurnakov Institute of General and Inorganic Chemistry of RAS, Moscow (Russian Federation); Savilov, S.V.; Lunin, V.V. [Lomonosov Moskow State University, Moscow (Russian Federation); Novotortsev, V.M.; Eremenko, I.L. [Kurnakov Institute of General and Inorganic Chemistry of RAS, Moscow (Russian Federation)

    2015-11-15

    Highlights: • Electron structure of pivalate trinuclear heterometallic complexes is studied by XPS. • C1s-, O1s-, M2p, and M3s-spectra are measured (M=Fe, Mn, Co, Ni). • Redistribution of electron density upon complex formation is studied. - Abstract: Electron structure of pivalate heterometallic trinuclear complexes with a triangular structure and varying ligands environment is studied by the XPS method. An effect of substitution of one of the Fe atoms by M=Mn, Co, Ni on Fe2p and M2p spectra is studied. Redistribution of electron density in an OCO group upon formation of complexes and introduction of donor ligands is discovered. Correlation of the characteristics of photoelectron spectra with the variation of ligands environment is studied. The complexes are assigned to high-spin ones with Fe in oxidation state III, and M, II. A relation is established between Fe2p-spectra characteristics and electron affinity of M ions.

  17. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, July--September 1993

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, E.; Song, C.; Schobert, H.H.

    1994-01-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts can be superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. The primary objective of this research is to explore novel bimetallic dispersed catalysts from heterometallic molecular precursors, that can be used in low concentrations but exhibit high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. This quarterly report describes the preparation of two precursors. The first is a heterometallic complex consisting of two transition metals, Mo and Ni, and sulfur in a single molecule synthesized. The second is a thiocubane type cluster consisting of iron and sulfur.

  18. Atomic Structure of Au−Pd Bimetallic Alloyed Nanoparticles

    KAUST Repository

    Ding, Yong

    2010-09-08

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

  19. Exploration of Nanotube Structure Selectivity Using Bimetallic Catalysts

    Science.gov (United States)

    Pfefferle, Lisa

    2007-10-01

    Achieving selectivity for nanotube chirality is one of the holy grails for single-walled carbon nanotube research. One approach we are following is based on the ability to engineer the size and state of the initiating metal particle to constrain the type of cap formed. The chirality/structure of a nanotube is controlled by carbon cap formation on the metal particle during the nucleation step. It has been proposed that varying the carbon-metal catalyst binding energy could help lead to structure selectivity. One reason theoretically proposed for the favoring of armchair nanotubes, for example, is the proximity of low energy binding locations for two carbon atoms. Thus blocking sites or perturbing the binding energy on adjacent sites could in theory affect the structure of the carbon cap formed in the nucleation step. Our goal is to demonstrate structure selectivity in the growth of single wall carbon nanotubes (SWNT) using a bimetallic catalyst. The catalyst used was a bimetallic CoCr-MCM 41 and the effect of different molecular ratios between the two metals on the SWNT diameter distribution was studied. We have found that by adding Cr to the Co-MCM 41 monometallic catalyst the diameter distribution shifted in a systematic manner correlated to the development of a bimetallic phase as characterized by X-Ray absorption spectroscopy (XAS). We have also found that the shift is accompanied by suppression of metallic SWNT, particularly those with diameter over 0.9 nm. We are also currently exploring the possibility of a further narrowing of the distribution by lowering the reaction temperatures.

  20. Controllable Catalysis with Nanoparticles: Bimetallic Alloy Systems and Surface Adsorbates

    KAUST Repository

    Chen, Tianyou

    2016-05-16

    Transition metal nanoparticles are privileged materials in catalysis due to their high specific surface areas and abundance of active catalytic sites. While many of these catalysts are quite useful, we are only beginning to understand the underlying catalytic mechanisms. Opening the “black box” of nanoparticle catalysis is essential to achieve the ultimate goal of catalysis by design. In this Perspective we highlight recent work addressing the topic of controlled catalysis with bimetallic alloy and “designer” adsorbate-stabilized metal nanoparticles.

  1. Enhanced plasmonic behavior of bimetallic (Ag-Au multilayered spheres

    Directory of Open Access Journals (Sweden)

    Pal Umapada

    2011-01-01

    Full Text Available Abstract In this article we study the plasmonic behavior of some stable, highly biocompatible bimetallic metal-dielectric-metal (MDM and double concentric nanoshell (DCN structures. By simply switching the material of the inner structure from Au to Ag, the intensity of their surface plasmon resonance could be increased in the optical transparency region of the human tissues up to 20 and 60 percent for the MDM and DCN, respectively, while the biocompatibility is retained. The obtained results indicate that these novel structures could be highly suitable for surface enhanced Raman scattering and photothermal cancer therapy.

  2. Progress, Challenge, and Perspective of Bimetallic TiO2-Based Photocatalysts

    Directory of Open Access Journals (Sweden)

    Anna Zielińska-Jurek

    2014-01-01

    Full Text Available Bimetallic TiO2-based photocatalysts have attracted considerable attention in recent years as a class of highly active catalysts and photocatalysts under both UV and Vis light irradiation. Bimetallic noble metal structures deposited on TiO2 possess the ability to absorb visible light, in a wide wavelength range (broad LSPR peak, and therefore reveal the highest level of activity as a result of utilization of a large amount of incident photons. On the other hand they can enhance the rate of trapping photoexcited electrons and inhibit the recombination process due to the capability of the storage of photoexcited electrons. Based on literature two groups of bimetallic photocatalysts were distinguished. The first group includes bimetallic TiO2 photocatalysts (BMOX, highly active under UV and Vis light irradiation in a variety of oxidation reactions, and the second group presents bimetallic photocatalysts (BMRED exceptionally active in hydrogenation reactions. This review summarizes recent advances in the preparation and environmental application of bimetallic TiO2-based photocatalysts. Moreover, the effects of various parameters such as particle shape, size, amount of metals, and calcination on the photocatalytic activity of bimetallic TiO2-based photocatalysts are also discussed.

  3. Strategies to initiate and control the nucleation behavior of bimetallic nanoparticles.

    Science.gov (United States)

    Krishnan, Gopi; de Graaf, Sytze; Ten Brink, Gert H; Persson, Per O Å; Kooi, Bart J; Palasantzas, George

    2017-06-22

    In this work we report strategies to nucleate bimetallic nanoparticles (NPs) made by gas phase synthesis of elements showing difficulty in homogeneous nucleation. It is shown that the nucleation assisted problem of bimetallic NP synthesis can be solved via the following pathways: (i) selecting an element which can itself nucleate and act as a nucleation center for the synthesis of bimetallic NPs; (ii) introducing H2 or CH4 as an impurity/trace gas to initiate nucleation during the synthesis of bimetallic NPs. The latter can solve the problem if none of the elements in a bimetallic NP can initiate nucleation. We illustrate the abovementioned strategies for the case of Mg based bimetallic NPs, which are interesting as hydrogen storage materials and exhibit both nucleation and oxidation issues even under ultra-high vacuum conditions. In particular, it is shown that adding H2 in small proportions favors the formation of a solid solution/alloy structure even in the case of immiscible Mg and Ti, where normally phase separation occurs during synthesis. In addition, we illustrate the possibility of improving the nucleation rate, and controlling the structure and size distribution of bimetallic NPs using H2/CH4 as a reactive/nucleating gas. This is shown to be associated with the dimer bond energies of the various formed species and the vapor pressures of the metals, which are key factors for NP nucleation.

  4. Colloidal synthesis and structural control of PtSn bimetallic nanoparticles.

    Science.gov (United States)

    Wang, Xiaodong; Stöver, Jörg; Zielasek, Volkmar; Altmann, Lena; Thiel, Karsten; Al-Shamery, Katharina; Bäumer, Marcus; Borchert, Holger; Parisi, Jürgen; Kolny-Olesiak, Joanna

    2011-09-06

    PtSn bimetallic nanoparticles with different particle sizes (1-9 nm), metal compositions (Sn content of 10-80 mol %), and organic capping agents (e.g., amine, thiol, carboxylic acid and polymer) were synthesized by colloidal chemistry methods. Transmission electron microscopy (TEM) measurements show that, depending on the particle size, the as-prepared bimetallic nanocrystals have quasi-spherical or faceted shapes. Energy-dispersive X-ray (EDX) analyses indicate that for all samples the signals of both Pt and Sn can be detected from single nanoparticles, confirming that the products are actually bimetallic but not only a physical mixture of pure Pt and Sn metal nanoparticles. X-ray diffraction (XRD) measurements were also conducted on the bimetallic particle systems. When compared with the diffraction patterns of monometallic Pt nanoparticles, the bimetallic samples show distinct shifts of the Bragg reflections to lower degrees, which gives clear proof of the alloying of Pt with Sn. However, a quantitative analysis of the lattice parameter shifts indicates that only part of the Sn atoms are incorporated into the alloy nanocrystals. This is consistent with X-ray photoelectron spectroscopy (XPS) measurements that reveal the segregation of Sn at the surfaces of the nanocrystals. Moreover, short PtSn bimetallic nanowires were synthesized by a seed-mediated growth method with amine-capped bimetallic particles as precursors. The resulting nanowires have an average width of 2.3 nm and lengths ranging from 5 to 20 nm. © 2011 American Chemical Society

  5. Physical and Numerical Analysis of Extrusion Process for Production of Bimetallic Tubes

    Energy Technology Data Exchange (ETDEWEB)

    Misiolek, W.Z.; Sikka, V.K.

    2006-08-10

    Bimetallic tubes are used for very specific applications where one of the two metals provides strength and the other provides specific properties such as aqueous corrosion and carburization, coking resistance, and special electrical and thermal properties. Bimetallic tubes have application in pulp and paper industry for heat-recovery boilers, in the chemical industry for ethylene production, and in the petrochemical industry for deep oil well explorations. Although bimetallic tubes have major applications in energy-intensive industry, they often are not used because of their cost and manufacturing sources in the United States. This project was intended to address both of these issues.

  6. Bimetallic Catalysts Containing Gold and Palladium for Environmentally Important Reactions

    Directory of Open Access Journals (Sweden)

    Ahmad Alshammari

    2016-07-01

    Full Text Available Supported bimetallic nanoparticles (SBN are extensively used as efficient redox catalysts. This kind of catalysis particularly using SBN has attracted immense research interest compared to their parent metals due to their unique physico-chemical properties. The primary objective of this contribution is to provide comprehensive overview about SBN and their application as promising catalysts. The present review contains four sections in total. Section 1 starts with a general introduction, recent progress, and brief summary of the application of SBN as promising catalysts for different applications. Section 2 reviews the preparation and characterization methods of SBN for a wide range of catalytic reactions. Section 3 concentrates on our own results related to the application of SBN in heterogeneous catalysis. In this section, the oxidation of cyclohexane to adipic acid (an eco-friendly and novel approach will be discussed. In addition, the application of bimetallic Pd catalysts for vapor phase toluene acetoxylation in a fixed bed reactor will also be highlighted. Acetoxylation of toluene to benzyl acetate is another green route to synthesize benzyl acetate in one step. Finally, Section 4 describes the summary of the main points and also presents an outlook on the application of SBN as promising catalysts for the production of valuable products.

  7. Mechanical properties of bimetallic one-dimensional structures

    Science.gov (United States)

    Smelova, Ekaterina M.; Sitnikov, Ivan I.; Zelensky, Vladimir S.; Tsysar, Kseniya M.; Andreev, Valery G.; Vdovin, Vladimir A.; Saletsky, Alexander M.

    2016-12-01

    Mechanical properties of freestanding Au-Mn nanowires and Au-Mn nanowire on a Cu (110) substrate are studied with ab initio theoretical approach. The calculations were carried out using the software package Vienna Ab-initio Simulation Package (VASP), which is based on the density functional theory (DFT). It was shown that the breaking force (0.45nN) as well as the interatomic distance at a breaking point in bimetallic nanowire (3.0 Å) are higher than in one component Au wire (0.4 nN and 2.6Å respectively). Relative elongation of 15 % results in a fracture of bimetallic nanowire. We studied the mechanical response of the nanojunction in a form of three-atomic Au chain aligned vertically between two pyramidal gold electrodes and demonstrated that the breaking of nanocontact depends only the interaction between Au atoms in the chain and dependents slightly on the structure and properties of the atomic structure of the electrodes.

  8. Optical properties and sensing applications of stellated and bimetallic nanoparticles

    Science.gov (United States)

    Smith, Alison F.

    This dissertation focuses on developing guidelines to aid in the design of new bimetallic platforms for sensing applications. Stellated metal nanostructures are a class of plasmonic colloids in which large electric field enhancements can occur at sharp features, making them excellent candidates for surface enhanced Raman spectroscopy (SERS) and surface enhanced infrared spectroscopy (SE-IRS) platforms. Shape-dependent rules for convex polyhedra such as cubes or octahedra exist, which describe far-field scattering and near-field enhancements. However, such rules are lacking for their concave (stellated) counterparts. This dissertation presents the optical response of stellated Au nanocrystals with Oh, D4h, D3h, C2v, and T d symmetry, which were modeled to systematically investigate the role of symmetry, branching, and particle orientation with respect to excitation source using finite difference time domain (FDTD) calculations. Expanding on stellated nanostructures, bimetallic compositions introduce an interplay between overall architecture and composition to provide tunable optical properties and the potential of new functionality. However, decoupling the complex compositional and structural contributions to the localized surface plasmon resonance (LSPR) remains a challenge, especially when the monometallic counterparts are not synthetically accessible for comparison and the theoretical tools for capturing gradient compositions are lacking. This dissertation explores a stellated Au-Pd nanocrystal model system with Oh symmetry to decouple structural and complex compositional effects on LSPR. (Abstract shortened by ProQuest.).

  9. CO2 activation on bimetallic CuNi nanoparticles☆

    Institute of Scientific and Technical Information of China (English)

    Natalie Austin; Brandon Butina; Giannis Mpourmpakis⁎

    2016-01-01

    Density functional theory calculations have been performed to investigate the structural, electronic, and CO2 adsorption properties of 55-atom bimetallic CuNi nanoparticles (NPs) in core-shell and decorated architectures, as well as of their monometallic counterparts. Our results revealed that with respect to the monometallic Cu55 and Ni55 parents, the formation of decorated Cu12Ni43 and core-shell Cu42Ni13 are energetically favorable. We found that CO2 chemisorbs on monometallic Ni55, core-shell Cu13Ni42, and decorated Cu12Ni43 and Cu43Ni12, whereas, it physisorbs on monometallic Cu55 and core-shell Cu42Ni13. The presence of surface Ni on the NPs is key in strongly adsorbing and activating the CO2 molecule (linear to bent transition and elongation of C˭O bonds). This activation occurs through a charge transfer from the NPs to the CO2 molecule, where the local metal d-orbital density localization on surface Ni plays a pivotal role. This work identifies insightful structure-property relationships for CO2 activation and highlights the importance of keeping a balance between NP stability and CO2 adsorption behavior in designing catalytic bimetallic NPs that activate CO2.

  10. CO2 activation on bimetallic CuNi nanoparticles

    Directory of Open Access Journals (Sweden)

    Natalie Austin

    2016-10-01

    Full Text Available Density functional theory calculations have been performed to investigate the structural, electronic, and CO2 adsorption properties of 55-atom bimetallic CuNi nanoparticles (NPs in core-shell and decorated architectures, as well as of their monometallic counterparts. Our results revealed that with respect to the monometallic Cu55 and Ni55 parents, the formation of decorated Cu12Ni43 and core-shell Cu42Ni13 are energetically favorable. We found that CO2 chemisorbs on monometallic Ni55, core-shell Cu13Ni42, and decorated Cu12Ni43 and Cu43Ni12, whereas, it physisorbs on monometallic Cu55 and core-shell Cu42Ni13. The presence of surface Ni on the NPs is key in strongly adsorbing and activating the CO2 molecule (linear to bent transition and elongation of C˭O bonds. This activation occurs through a charge transfer from the NPs to the CO2 molecule, where the local metal d-orbital density localization on surface Ni plays a pivotal role. This work identifies insightful structure-property relationships for CO2 activation and highlights the importance of keeping a balance between NP stability and CO2 adsorption behavior in designing catalytic bimetallic NPs that activate CO2.

  11. Improved catalytic activity of laser generated bimetallic and trimetallic nanoparticles.

    Science.gov (United States)

    Singh, Rina; Soni, R K

    2014-09-01

    We report synthesis of silver nanoparticles, bimetallic (Al2O3@Ag) nanoparticles and trimetallic (Al2O3@AgAu) nanoparticles by nanosecond pulse laser ablation (PLA) in deionized water. Two-step laser ablation methodologies were adopted for the synthesis of bi- and tri-metallic nanoparticles. In this method a silver or gold target was ablated in colloidal solution of γ-alumina nanoparticles prepared by PLA. The TEM image analysis of bimetallic and trimetallic particles reveals deposition of fine silver particles and Ag-Au alloy particles, respectively, on large alumina particles. The laser generated nanoparticles were tested for catalytic reduction of 4-nitrophenol to 4-aminophenol and showed excellent catalytic behaviour. The catalytic rate was greatly improved by incorporation of additional metal in silver nanoparticles. The catalytic efficiency of trimetallic Al2O3@AgAu for reduction of 4-nitrophenol to 4-aminophenol was remarkably enhanced and the catalytic reaction was completed in just 5 sec. Even at very low concentration, both Al2O3@Ag nanoparticles and Al2O3@AgAu nanoparticles showed improved rate of catalytic reduction than monometallic silver nanoparticles. Our results demonstrate that alumina particles in the solution not only provide the active sites for particle dispersion but also improve the catalytic activity.

  12. Versatile Optimization of Chemical Ordering in Bimetallic Nanoparticles

    KAUST Repository

    Kovács, Gábor

    2017-01-05

    Chemical ordering in bimetallic nanocrystallites can now be efficiently determined by density-functional calculations with the help of topological energy expressions. Herein, we deal with extending the usage of that computational scheme. We show that it enables one to structurally characterize bimetallic nanoparticles of less regular shapes than previously studied magic-type particles. In fcc Pd–Au particles of different shapes (cuboctahedral Pd58Au58, C3v Pd61Au61, cubic Pd68Au67, and truncated octahedral Pd70Au70), we identify the surface segregation of gold as the driving force to the lowest-energy chemical ordering. We applied the calculated descriptor values quantifying the segregation propensity of Au and energies of Pd–Au bonds in these ∼1.5 nm large particles to optimize and analyze the chemical ordering in 3.7–6 nm large Pd–Au particles. We also discuss how to predict the chemical ordering in nanoalloys at elevated temperatures. The present study paves the way to advanced structural investigations of nanoalloys to substantially accelerate their knowledge-driven engineering and manufacturing.

  13. Supported bimetallic Pt-Au nanoparticles: Structural features predicted by molecular dynamics simulations

    Science.gov (United States)

    Morrow, Brian H.; Striolo, Alberto

    2010-04-01

    We have utilized all-atom molecular dynamics simulations to study bimetallic Pt-Au nanoparticles supported by carbonaceous materials at 700 K. Nanoparticles containing 250 atoms with 25%, 50%, and 75% Pt ( Pt62Au188 , Pt125Au125 , and Pt188Au62 , respectively) were considered. A single graphite sheet and bundles of seven (10,10), (13,13), and (20,20) single-walled carbon nanotubes were used as supports. It was found that Pt125Au125 forms a well-defined Pt core covered by an Au shell, regardless of the support. Pt62Au188 exhibits a mixed Pt-Au core with an Au shell. Pt188Au62 has a Pt core with a mixed Pt-Au shell. The support affects the atomic distribution. We investigated the percentage of nanoparticle surface atoms that are Pt. Our results show that for Pt62Au188 and Pt125Pt125 , this percentage is lowest when there is no support and highest when carbon nanotubes are supports. We studied the size of clusters of Pt atoms on the nanoparticle surface, finding that the geometry of the support influences the distribution of cluster sizes. Finally, we found that the coordination states of the atoms on the nanoparticle surface are affected by the support structure. These results suggest that it is possible to tailor the distribution of atoms in Pt-Au nanoparticles by controlling the nanoparticle composition and the support geometry. Such level of control is desirable for improving selectivity of catalysts.

  14. Molecular Dynamics Simulation of Icosahedral Transformations in Solid Cu-Co Clusters

    Institute of Scientific and Technical Information of China (English)

    LI Guo-Jian; WANG Qiang; LIU Tie; LI Dong-Gang; LU Xiao; HE Ji-Cheng

    2009-01-01

    We study the icosahedral transformations of solid Cu-Co clusters with different initial configurations by using molecular dynamics with the embedded atom method.It is found that the formation of symmetric icosahedral cluster is strongly related to the atomic number and initial configuration.The transformation originates from the surface into the interior of the cluster and is a structural change which is rapid and diffusionless.The icosahedral clusters with any composition and configuration,such as core-shell or three-shell cluster,can be prepared by the means of solid-solid phase transition in bimetallic dusters.

  15. Bimetallic structure fabricated by laser interference lithography for tuning surface plasmon resonance.

    Science.gov (United States)

    Liu, C H; Hong, M H; Cheung, H W; Zhang, F; Huang, Z Q; Tan, L S; Hor, T S A

    2008-07-07

    Tuning of surface plasmon resonance by gold and silver bimetallic thin film and bimetallic dot array is investigated. Laser interference lithography is applied to fabricate the nanostructures. A bimetallic dot structure is obtained by a lift-off procedure after gold and silver thin film deposition by an electron beam evaporator. Surface plasmon behaviors of these films and nanostructures are studied using UV-Vis spectroscopy. It is observed that for gold thin film on quartz substrate, the optical spectral peak is blue shifted when a silver thin film is coated over it. Compared to the plasmon band in single metal gold dot array, the bimetallic nanodot array shows a similar blue shift in its spectral peak. These shifts are both attributed to the interaction between gold and silver atoms. Electromagnetic interaction between gold and silver nanostructures is discussed using a simplified spring model.

  16. Fabrication of bimetallic nanostructures via aerosol-assisted electroless silver deposition for catalytic CO conversion.

    Science.gov (United States)

    Byeon, Jeong Hoon; Kim, Jang-Woo

    2014-03-12

    Bimetallic nanostructures were fabricated via aerosol-assisted electroless silver deposition for catalytic CO conversion. An ambient spark discharge was employed to produce nanocatalysts, and the particles were directly deposited on a polytetrafluoroethylene substrate for initiating silver deposition to form Pd-Ag, Pt-Ag, Au-Ag bimetallic nanostructures as well as a pure Ag nanostructure. Kinetics and morphological evolutions in the silver deposition with different nanocatalysts were comparatively studied. The Pt catalyst displayed the highest catalytic activity for electroless silver deposition, followed by the order Pd > Au > Ag. Another catalytic activity of the fabricated bimetallic structures in the carbon monoxide conversion was further evaluated at low-temperature conditions. The bimetallic systems showed significantly higher catalytic activity than that from a pure Ag system.

  17. Analysis of Al-Cu Bimetallic Bars Properties After Explosive Welding and Rolling in Modified Passes

    Directory of Open Access Journals (Sweden)

    Mróz S.

    2015-04-01

    Full Text Available The paper presents the results of the experimental tests of Al-Cu bimetallic bars rolling process in multi-radial modified passes. The bimetallic bars consist of aluminium core, grade 1050A and copper outer layer, grade M1E. The stocks were round bars with diameter 22 mm with a copper layer share of 15 and 30%. As a result of rolling in four passes, bars of a diameter of about 16.0 mm were obtained. A bimetallic stock was manufactured using an explosive welding method. The use of the designed arrangement of multi-radial modified stretching passes resulted in obtaining Al-Cu bimetallic bars with the required lateral dimensions, an uniform distribution of the cladding layer over the bar perimeter and high quality of shear strength between individual layers.

  18. Toward atomically-precise synthesis of supported bimetallic nanoparticles using atomic layer deposition.

    Science.gov (United States)

    Lu, Junling; Low, Ke-Bin; Lei, Yu; Libera, Joseph A; Nicholls, Alan; Stair, Peter C; Elam, Jeffrey W

    2014-01-01

    Multi-metallic nanoparticles constitute a new class of materials offering the opportunity to tune the properties via the composition, atomic ordering and size. In particular, supported bimetallic nanoparticles have generated intense interest in catalysis and electrocatalysis. However, traditional synthesis methods often lack precise control, yielding a mixture of monometallic and bimetallic particles with various compositions. Here we report a general strategy for synthesizing supported bimetallic nanoparticles by atomic layer deposition, where monometallic nanoparticle formation is avoided by selectively growing the secondary metal on the primary metal nanoparticle but not on the support; meanwhile, the size, composition and structure of the bimetallic nanoparticles are precisely controlled by tailoring the precursor pulse sequence. Such exquisite control is clearly demonstrated through in situ Fourier transform infrared spectroscopy of CO chemisorption by mapping the gradual atomic-scale evolution in the surface composition, and further confirmed using aberration-corrected scanning transmission electron microscopy.

  19. Levelling the playing field: screening for synergistic effects in coalesced bimetallic nanoparticles.

    Science.gov (United States)

    Tan, Rachel Lee Siew; Song, Xiaohui; Chen, Bo; Chong, Wen Han; Fang, Yin; Zhang, Hua; Wei, Jun; Chen, Hongyu

    2016-02-14

    Depending on the synthetic methods, bimetallic nanoparticles can have either core-shell, phase segregated, alloy, or partially coalesced structures, presenting different degrees of atomic mixing on their surface. Along with the variations of size and morphology, the structural differences make it difficult to compare the catalytic activity of bimetallic nanoparticles. In this article, we developed a facile screening method that can focus on the synergistic effects rather than structural differences. Prefabricated nanoparticles are mixed together to form linear aggregates and coalesced to form bimetallic junctions. Their hollow silica shells allow materials transport but prevent further aggregation. With a level playing field, this screening platform can identify the best bimetallic combination for a catalytic reaction, before optimizing the synthesis. This approach is more advantageous than the conventional approaches where structural difference may have dominant effects on the catalytic performance.

  20. Biosynthetic trends and future aspects of bimetallic nanoparticles and its medicinal applications.

    Science.gov (United States)

    Roopan, Selvaraj Mohana; Surendra, Tammineni Venkata; Elango, Ganesh; Kumar, Subramanian Hari Subbish

    2014-06-01

    Recently, in all over the world, nanotechnology plays a major role in various applications. Most of the researchers focused their work on bimetallic nanoparticles due to their several modes or mechanisms of synthesis such as chemical, physical, and biosynthesis methods. These nanoparticles are of great interest due to their enormous applications and catalytic activities. Currently, syntheses of bimetallic nanoparticles using different sources of natural products are focused due to their advantage of being nontoxic to human and environment. To our knowledge, there is no report on the review of bimetallic nanoparticles and their medicinal applications. Taking this fact into account, we discussed the various synthesizing methods of bimetallic nanoparticles and their application related to biology.

  1. Automated electrodeposition of bimetallic noble-metal nanoclusters via redox-replacement reactions for electrocatalysis

    CSIR Research Space (South Africa)

    Mkwizu, TS

    2009-01-01

    Full Text Available Nanoclusters of bimetallic composition involving platinum with gold or ruthenium were sequentially deposited via redoxreplacement of electrodeposited sacrificial Cu adlayers for controlling the deposition of the noble metals. These steps were...

  2. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-30

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

  4. Sonogashira and "Click" reactions for the N-terminal and side-chain functionalization of peptides with [Mn(CO)3(tpm)]+-based CO releasing molecules (tpm = tris(pyrazolyl)methane).

    Science.gov (United States)

    Pfeiffer, Hendrik; Rojas, Alfonso; Niesel, Johanna; Schatzschneider, Ulrich

    2009-06-14

    A recently identified photoactivatable CO releasing molecule (CORM) based on [Mn(CO)(3)(tpm)](+) was conjugated to functionalized amino acids and model peptides using the Pd-catalyzed Sonogashira cross-coupling and the alkyne-azide 1,3-dipolar cycloaddition ("Click reaction"). Both were found to be fully compatible with all functional groups present. The CORM-peptide conjugates were isolated in reasonable yield and high purity, as indicated by IR spectroscopy, ESI mass spectrometry and RP-HPLC. The myoglobin assay was used to demonstrate that they have CO release properties identical those of the parent compound. This work thus opens the way for a targeted delivery of CORMs to cellular systems.

  5. Gas-Phase Growth of Heterostructures of Carbon Nanotubes and Bimetallic Nanowires

    Directory of Open Access Journals (Sweden)

    Whi Dong Kim

    2011-01-01

    Full Text Available A simple, inexpensive, and viable method for growing multiple heterostructured carbon nanotubes (CNTs over the entire surface of Ni-Al bimetallic nanowires (NWs in the gas phase was developed. Polymer-templated bimetallic nitrate NWs were produced by electrospinning in the first step, and subsequent calcination resulted in the formation of bimetallic oxide NWs by thermal decomposition. In the second step, free-floating bimetallic NWs were produced by spray pyrolysis in an environment containing hydrogen gas as a reducing gas. These NWs were continuously introduced into a thermal CVD reactor in order to grow CNTs in the gas phase. Scanning electron microscopy (SEM, transmission electron microscopy (TEM, and Raman spectrometry analyses revealed that the catalytic Ni sites exposed in the non-catalytic Al matrix over the entire surface of the bimetallic NWs were seeded to radially grow highly graphitized CNTs, which resembled “foxtail” structures. The grown CNTs were found to have a relatively uniform diameter of approximately 10±2 nm and 10 to 15 walls with a hollow core. The average length of the gas-phase-grown CNTs can be controlled between 100 and 1000 nm by adjusting the residence time of the free-floating bimetallic NWs in the thermal CVD reactor.

  6. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold-copper bimetallic nanoparticles

    National Research Council Canada - National Science Library

    Kim, Dohyung; Resasco, Joaquin; Yu, Yi; Asiri, Abdullah Mohamed; Yang, Peidong

    2014-01-01

    .... Here we assemble uniform gold-copper bimetallic nanoparticles with different compositions into ordered monolayers, which serve as a well-defined platform to understand their fundamental catalytic...

  7. Green synthesis and applications of Au-Ag bimetallic nanoparticles.

    Science.gov (United States)

    Meena Kumari, M; Jacob, John; Philip, Daizy

    2015-02-25

    This paper reports for the first time the synthesis of bimetallic nanoparticles at room temperature using the fruit juice of pomegranate. Simultaneous reduction of gold and silver ions in different molar ratios leads to the formation of alloy as well as core-shell nanostructures. The nanoparticles have been characterized using UV-vis spectroscopy, transmission electron microscopy, Fourier Transform Infrared Spectroscopy and X-ray diffraction. The synthesized alloy particles are used as catalysts in the reduction of 2-, 3-, 4-nitrophenols to the corresponding amines and in the degradation of methyl orange. The reduction kinetics for all the reactions follows pseudo-first order. The rate constants follow the order k4-nitrophenolnanoparticles enhances the thermal conductivity of the base fluid (water) showing nanofluid application. The nitric oxide and hydroxyl radical scavenging activity shown by the nanoparticles promise the potential application in biomedical field.

  8. Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

    KAUST Repository

    Thomas, Renee M.

    2010-11-24

    A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.

  9. Lanthanide bimetallic helicates for in vitro imaging and sensing.

    Science.gov (United States)

    Bünzli, Jean-Claude G; Chauvin, Anne-Sophie; Vandevyver, Caroline D B; Bo, Song; Comby, Steve

    2008-01-01

    As the need for targeting luminescent biolabels increases, for mapping selected analytes, imaging of cells and organs, and tracking in cellulo processes, lanthanide bimetallic helicates are emerging as versatile bioprobes. The wrapping of three ligand strands around two metallic centers by self-assembly affords robust molecular edifices with tunable chemical and photophysical properties. In addition, heterometallic helical chelates can be assembled leading to bioprobes with inherent chiral properties. In this paper, we review the literature demonstrating that neutral [Ln(2)(L(CX))(3)] (x=1-3) helicates represent a viable alternative to existing chelating agents for bio-analyses, while featuring specific enhanced properties. These bimetallic chelates self-assemble in water, and at physiological pH the 2:3 (Ln:L(CX)) complex is by far the dominant species, conditional stability constants logbeta(23) being in the range 23-30. The metal ions are 9-coordinate and lie in sites with slightly distorted D(3) symmetry. Efficient protection from water interaction by the tightly wrapped ligand strands results in sizeable photophysical properties, with quantum yields up to 24% for Eu(III) and 11% for Tb(III), while the luminescence of several other visible and/or near-infrared emitting Ln(III) ions is also sensitized. Noncytotoxicity for all the helicates is established for several living cell lines including HeLa, HaCat, MCF-7, 5D10, and Jurkat. We present new data pertaining to the live cell imaging ability of [Eu(2)(L(C1))(3)] and compare the three systems with x=1-3 with respect to thermodynamic stability, photophysics, cell-permeation ability, and targeting capability for sensing in cellulo processes. Prospects of derivatization for characterizing specific biological interactions are discussed.

  10. The selective hydrogenation of crotonaldehyde over bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Schoeb, Ann M. [Iowa State Univ., Ames, IA (United States)

    1997-10-17

    The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO2 catalyst and platinum bimetallic catalysts where the second metal was either silver, copper, or tin. The effects of addition of a second metal to the Pt/SiO2 system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, 1H NMR and microcalorimetry. The Pt-Ag/SiO2 and Pt-Cu/SiO2 catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO2 catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO2 catalysts for the hydrogenation of crotonaldehyde to crotyl alcohol were those in which the Sn precursor was dissolved in a HCl solution. Sn increased both the rate of formation of butyraldehyde and the rate of formation of crotyl alcohol. The Pt/SiO2, Pt-Ag/SiO2 and Pt-Cu/SiO2 catalysts produced only butyraldehyde. Initial heats of adsorption (~90 kJ/mol) measured using microcalorimetry were not affected by the presence of Sn on Pt. We can conclude that there is no through metal electronic interaction between Pt and Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn had similar initial heats of adsorption coupled with the invariance of the 1H NMR Knight shift.

  11. Dopant-induced 2D-3D transition in small Au-containing clusters: DFT-global optimisation of 8-atom Au-Ag nanoalloys.

    Science.gov (United States)

    Heiles, Sven; Logsdail, Andrew J; Schäfer, Rolf; Johnston, Roy L

    2012-02-21

    A genetic algorithm (GA) coupled with density functional theory (DFT) calculations is used to perform global optimisations for all compositions of 8-atom Au-Ag bimetallic clusters. The performance of this novel GA-DFT approach for bimetallic nanoparticles is tested for structures reported in the literature. New global minimum structures for various compositions are predicted and the 2D-3D transition is located. Results are explained with the aid of an analysis of the electronic density of states. The chemical ordering of the predicted lowest energy isomers are explained via a detailed analysis of the charge separation and mixing energies of the bimetallic clusters. Finally, dielectric properties are computed and the composition and dimensionality dependence of the electronic polarizability and dipole moment is discussed, enabling predictions to be made for future electric beam deflection experiments.

  12. Dielectric, piezoelectric, and ferroelectric properties of MnCO3-added 74(Bi(1/2)Na(1/2)) TiO3-20.8(Bi(1/2)K(1/2))TiO3-5.2BaTiO3 lead-free piezoelectric ceramics.

    Science.gov (United States)

    Hu, Hanchen; Zhu, Mankang; Hou, Yudong; Yan, Hui

    2009-05-01

    74(Bi(1/2)Na(1/2))TiO3-20.8(Bi(1/2)K(1/2))TiO3-5.2BaTiO3-x MnCO3 lead-free piezoelectric ceramics were synthesized by conventional solid oxide routine. The tetragonal 74(Bi(1/2)Na(1/2))TiO3-20.8(Bi(1/2)K(1/2))TiO3-5.2 BaTiO3 (BNKB) exhibits high depolarization temperature T(d) of 195 degrees C; however, its properties are far from satisfactory for practical application and need to be improved. The experiments show that the addition of MnCO3 reduces the tetragonality c/a and increases the cell volume. In addition, it revealed that the suitable addition of MnCO3 promotes the sintering and increases the densities of BNKB ceramics. The addition of MnCO3 also enhances the relaxor behavior of BNKB ceramics due to the reconstruct of the disorder arrays. Due to the effect of the crystal lattice, grain growth, and relaxor behavior, the optimal electric properties were realized at MnCO3 addition x of 0.16: the dielectric permittivity epsilon(r) = 1047, dielectric dissipation tandelta = 0.022, piezoelectric strain d33 = 140 pC/N, mechanical coupling k(p) = 0.18, mechanical quality Q(m) = 89 while the depolarization temperature T(d) stays relatively high at 175 degrees C. The effect and mechanism of Mn doping on the electrical properties were discussed in detail.

  13. Peptide-Directed PdAu Nanoscale Surface Segregation: Toward Controlled Bimetallic Architecture for Catalytic Materials.

    Science.gov (United States)

    Bedford, Nicholas M; Showalter, Allison R; Woehl, Taylor J; Hughes, Zak E; Lee, Sungsik; Reinhart, Benjamin; Ertem, S Piril; Coughlin, E Bryan; Ren, Yang; Walsh, Tiffany R; Bunker, Bruce A

    2016-09-27

    Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when two different metallic species are mixed at the nanoscale. This is particularly prevalent in catalysis, where bimetallic nanoparticles often exhibit improved catalytic activity and durability over their monometallic counterparts. Yet despite intense research efforts, little is understood regarding how to optimize bimetallic surface composition and structure synthetically using rational design principles. Recently, it has been demonstrated that peptide-enabled routes for nanoparticle synthesis result in materials with sequence-dependent catalytic properties, providing an opportunity for rational design through sequence manipulation. In this study, bimetallic PdAu nanoparticles are synthesized with a small set of peptides containing known Pd and Au binding motifs. The resulting nanoparticles were extensively characterized using high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy, and high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Structural information obtained from synchrotron radiation methods was then used to generate model nanoparticle configurations using reverse Monte Carlo simulations, which illustrate sequence dependence in both surface structure and surface composition. Replica exchange with solute tempering molecular dynamics simulations were also used to predict the modes of peptide binding on monometallic surfaces, indicating that different sequences bind to the metal interfaces via different mechanisms. As a testbed reaction, electrocatalytic methanol oxidation experiments were performed, wherein differences in catalytic activity are clearly observed in materials with identical bimetallic composition. Taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be leveraged

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

    Science.gov (United States)

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

    2016-11-01

    Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N2 adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H2 chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d5/2 shifted to higher positions while that of Au 4f7/2 had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest catalytic activity. For the bimetallic catalysts, a disproportional increase of turnover frequency (TOF) was observed with increasing Au content due to the enhanced cationization of Pd particles. Moreover, the dechlorination of 2,4-DCP over the supported monometallic and bimetallic catalysts proceeded via both the stepwise and concerted pathway, and the concerted pathway became predominant with Au decoration amount in the catalyst.

  15. Structures of 38-atom gold-platinum nanoalloy clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ong, Yee Pin; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    Bimetallic nanoclusters, such as gold-platinum nanoclusters, are nanomaterials promising wide range of applications. We perform a numerical study of 38-atom gold-platinum nanoalloy clusters, Au{sub n}Pt{sub 38−n} (0 ≤ n ≤ 38), to elucidate the geometrical structures of these clusters. The lowest-energy structures of these bimetallic nanoclusters at the semi-empirical level are obtained via a global-minimum search algorithm known as parallel tempering multi-canonical basin hopping plus genetic algorithm (PTMBHGA), in which empirical Gupta many-body potential is used to describe the inter-atomic interactions among the constituent atoms. The structures of gold-platinum nanoalloy clusters are predicted to be core-shell segregated nanoclusters. Gold atoms are observed to preferentially occupy the surface of the clusters, while platinum atoms tend to occupy the core due to the slightly smaller atomic radius of platinum as compared to gold’s. The evolution of the geometrical structure of 38-atom Au-Pt clusters displays striking similarity with that of 38-atom Au-Cu nanoalloy clusters as reported in the literature.

  16. Direct decomposition of methane over SBA-15 supported Ni, Co and Fe based bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Pudukudy, Manoj, E-mail: manojpudukudy@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, UKM, Bangi 43600, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, UKM, Bangi 43600, Selangor (Malaysia); Yaakob, Zahira, E-mail: zahirayaakob65@gmail.com [Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, UKM, Bangi 43600, Selangor (Malaysia); Akmal, Zubair Shamsul [Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, UKM, Bangi 43600, Selangor (Malaysia)

    2015-03-01

    Graphical abstract: - Highlights: • Synthesis and characterization of Ni, Co and Fe based bimetallic catalysts supported over SBA-15. • Thermocatalytic decomposition of methane over the SBA-15 supported bimetallic catalysts. • Enhanced catalytic efficiency of the bimetallic catalysts for the production of CO{sub x} free hydrogen and nanocarbon. • Production of value added open tip hollow multi-walled carbon nanotubes. • Crystalline characterization of carbon nanotubes by XRD, Raman and thermogravimetric analysis. - Abstract: Thermocatalytic decomposition of methane is an alternative route for the production of CO{sub x}-free hydrogen and carbon nanomaterials. In this work, a set of novel Ni, Co and Fe based bimetallic catalysts supported over mesoporous SBA-15 was synthesized by a facile wet impregnation route, characterized for their structural, textural and reduction properties and were successfully used for the methane decomposition. The fine dispersion of metal oxide particles on the surface of SBA-15, without affecting its mesoporous texture was clearly shown in the low angle X-ray diffraction patterns and the transmission electron microscopy (TEM) images. The nitrogen sorption analysis showed the reduced specific surface area and pore volume of SBA-15, after metal loading due to the partial filling of hexagonal mesopores by metal species. The results of methane decomposition experiments indicated that all of the bimetallic catalysts were highly active and stable for the reaction at 700 °C even after 300 min of time on stream (TOS). However, a maximum hydrogen yield of ∼56% was observed for the NiCo/SBA-15 catalyst within 30 min of TOS. A high catalytic stability was shown by the CoFe/SBA-15 catalyst with 51% of hydrogen yield during the course of reaction. The catalytic stability of the bimetallic catalysts was attributed to the formation of bimetallic alloys. Moreover, the deposited carbons were found to be in the form of a new set of hollow

  17. Facile Synthesis of Highly Active and Robust Ni-Mo Bimetallic Electrocatalyst for Hydrocarbon Oxidation in Solid Oxide Fuel Cells

    NARCIS (Netherlands)

    Hua, B.; Li, M.; Zhang, Y.-Q.; Chen, J.; Sun, Y.-F.; Yan, N.; Li, J.; Luo, J.L.

    2016-01-01

    We report a novel Ni–Mo bimetallic alloy decorated with multimicrocrystals as an efficient anode catalyst for hydrocarbon-fueled solid oxide fuel cells (SOFCs). We show that these Ni–Mo bimetallic alloys are highly active, thermally stable, and sulfur/coke tolerant electrocatalysts for hydrocarbon o

  18. Enhanced dechlorination of trichloroethylene using electrospun polymer nanofibrous mats immobilized with iron/palladium bimetallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Hui [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620 (China); College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620 (China); Huang, Yunpeng; Shen, Mingwu; Guo, Rui; Cao, Xueyan [College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620 (China); Shi, Xiangyang, E-mail: xshi@dhu.edu.cn [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620 (China); College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620 (China); CQM - Centro de Quimica da Madeira, Universidade da Madeira, Campus da Penteada, 9000-390 Funchal (Portugal)

    2012-04-15

    Fe/Pd bimetallic nanoparticles (NPs) have held great promise for treating trichloroethylene (TCE)-contaminated groundwater, without the accumulation of chlorinated intermediates. However, the conventionally used colloidal Fe/Pd NPs usually aggregate rapidly, resulting in a reduced reactivity. To reduce the particle aggregation, we employed electrospun polyacrylic acid (PAA)/polyvinyl alcohol (PVA) polymer nanofibers as a nanoreactor to immobilize Fe/Pd bimetallic NPs. In the study, the water-stable PAA/PVA nanofibrous mats were complexed with Fe (III) ions via the binding with the free carboxyl groups of PAA for subsequent formation and immobilization of zero-valent iron (ZVI) NPs. Fe/Pd bimetallic NPs were then formed by the partial reduction of Pd(II) ions with ZVI NPs. The formed electrospun nanofibrous mats containing Fe/Pd bimetallic NPs with a diameter of 2.8 nm were characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, thermogravimetric analysis, and inductively coupled plasma-atomic emission spectroscopy. The Fe/Pd NP-containing electrospun PAA/PVA nanofibrous mats exhibited higher reactivity than that of the ZVI NP-containing mats or colloidal Fe/Pd NPs in the dechlorination of trichloroethylene (TCE), which was used as a model contaminant. With the high surface area to volume ratio, high porosity, and great reusability of the fibrous mats immobilized with the bimetallic NPs, the composite nanofibrous mats should be amenable for applications in remediation of various environmental contaminants.

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

    Science.gov (United States)

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

    2012-10-05

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

  20. Cr(VI) reduction in wastewater using a bimetallic galvanic reactor

    Energy Technology Data Exchange (ETDEWEB)

    Lugo-Lugo, Violeta [Centro Conjunto de Investigacion en Quimica Sustentable UAEM-UNAM, Universidad Autonoma del Estado de Mexico, Facultad de Quimica. Paseo Colon interseccion Paseo Tollocan S/N. C.P. 50120, Toluca (Mexico); Barrera-Diaz, Carlos, E-mail: cbarrera@uaemex.mx [Centro Conjunto de Investigacion en Quimica Sustentable UAEM-UNAM, Universidad Autonoma del Estado de Mexico, Facultad de Quimica. Paseo Colon interseccion Paseo Tollocan S/N. C.P. 50120, Toluca (Mexico); Bilyeu, Bryan [Xavier University of Louisiana, Department of Chemistry, 1 Drexel Drive, New Orleans, LA 70125 (United States); Balderas-Hernandez, Patricia [Centro Conjunto de Investigacion en Quimica Sustentable UAEM-UNAM, Universidad Autonoma del Estado de Mexico, Facultad de Quimica. Paseo Colon interseccion Paseo Tollocan S/N. C.P. 50120, Toluca (Mexico); Urena-Nunez, Fernando [Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, Col. Escandon, Delegacion Miguel Hidalgo, C.P. 11801, Mexico, D.F. (Mexico); Sanchez-Mendieta, Victor [Centro Conjunto de Investigacion en Quimica Sustentable UAEM-UNAM, Universidad Autonoma del Estado de Mexico, Facultad de Quimica. Paseo Colon interseccion Paseo Tollocan S/N. C.P. 50120, Toluca (Mexico)

    2010-04-15

    The electrochemical reduction of Cr(VI)-Cr(III) in wastewater by iron and copper-iron bimetallic plates was evaluated and optimized. Iron has been used as a reducing agent, but in this work a copper-iron galvanic system in the form of bimetallic plates is applied to reducing hexavalent chromium. The optimal pH (2) and ratio of copper to iron surface areas (3.5:1) were determined in batch studies, achieving a 100% reduction in about 25 min. The Cr(VI) reduction kinetics for the bimetallic system fit a first order mechanism with a correlation of 0.9935. Thermodynamic analysis shows that the Cr(VI) reduction is possible at any pH value. However, at pH values above 3.0 for iron and 5.5 for chromium insoluble species appear, indicating that the reaction will be hindered. Continuous column studies indicate that the bimetallic copper-iron galvanic system has a reduction capacity of 9.5890 mg Cr(VI) cm{sup -2} iron, whereas iron alone only has a capacity of 0.1269 mg Cr(VI) cm{sup -2}. The bimetallic copper-iron galvanic system is much more effective in reducing hexavalent chromium than iron alone. The exhausted plates were analyzed by SEM, EDS, and XRD to determine the mechanism and the surface effects, especially surface fouling.

  1. Magnetic properties of bimetallic Au/Co nanoparticles prepared by thermal laser treatment

    Science.gov (United States)

    Sosunov, A. V.; Spivak, L. V.

    2016-07-01

    The irradiation of metallic films by a nanosecond pulsed laser leads to a self-assembly of nanoparticle arrays. This method has been used to prepare bimetallic Au/Co nanoparticles on a SiO2 substrate. The microstructure and morphology of the bimetallic nanoparticles have been investigated using scanning electron microscopy and transmission electron microscopy. It has been shown that the bimetallic nanoparticles have a hemispherical shape with a single-crystal structure and an average size of ~50 nm. The magnetic properties of these nanoparticles have been examined using a vibrating-sample magnetometer in the transverse and longitudinal directions. It has been found that the direction of the magnetization of the bimetallic nanoparticles lies in the plane of the substrate, and the coercive forces in the transverse and longitudinal directions differ by 25%. The use of the vibrating-sample magnetometer method makes it possible to investigate the differences in the magnetic saturations and the coercive forces of an array of bimetallic nanoparticles on a large surface area. The performed investigations have demonstrated that the anisotropic nanomagnetic materials with the desired magnetic orientation can be easily and quickly prepared by means of thermal laser treatment.

  2. Supported Pd-Cu bimetallic nanoparticles that have high activity for the electrochemical oxidation of methanol.

    Science.gov (United States)

    Yin, Zhen; Zhou, Wu; Gao, Yongjun; Ma, Ding; Kiely, Christopher J; Bao, Xinhe

    2012-04-16

    Monodisperse bimetallic Pd-Cu nanoparticles with controllable size and composition were synthesized by a one-step multiphase ethylene glycol (EG) method. Adjusting the stoichiometric ratio of the Pd and Cu precursors afforded nanoparticles with different compositions, such as Pd(85)-Cu(15), Pd(56)-Cu(44), and Pd(39)-Cu(61). The nanoparticles were separated from the solution mixture by extraction with non-polar solvents, such as n-hexane. Monodisperse bimetallic Pd-Cu nanoparticles with narrow size-distribution were obtained without the need for a size-selection process. Capping ligands that were bound to the surface of the particles were removed through heat treatment when the as-prepared nanoparticles were loaded onto a Vulcan XC-72 carbon support. Supported bimetallic Pd-Cu nanoparticles showed enhanced electrocatalytic activity towards methanol oxidation compared with supported Pd nanoparticles that were fabricated according to the same EG method. For a bimetallic Pd-Cu catalyst that contained 15 % Cu, the activity was even comparable to the state-of-the-art commercially available Pt/C catalysts. A STEM-HAADF study indicated that the formation of random solid-solution alloy structures in the bimetallic Pd(85)-Cu(15)/C catalysts played a key role in improving the electrochemical activity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Synthesis of hollow Ag-Au bimetallic nanoparticles in polyelectrolyte multilayers.

    Science.gov (United States)

    Zhang, Xin; Zhang, Guangyu; Zhang, Bodong; Su, Zhaohui

    2013-06-04

    Ag nanoparticles of ~20 nm size and rather uniform size distribution were synthesized in polyelectrolyte multilayers (PEMs) via an ion-exchange/reduction process in two stages (seeding and growth), which were used as sacrificial templates to fabricate Ag-Au bimetallic hollow nanoparticles via galvanic replacement reaction. The reaction process was monitored by UV-vis spectroscopy. The morphology and structure of the nanoparticles were characterized by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy, which confirmed the formation of hollow Ag-Au bimetallic nanoparticles. UV-vis absorbance spectroscopy and TEM results indicated that both size and optical properties of the Ag nanoparticles in the PEM can be controlled by manipulating ion content in the PEM and the number of the ion-exchange/reduction cycle, whereas that of Ag-Au bimetallic nanoparticles were dependent on size of the Ag templates and the replacement reaction kinetics. The hollow Ag-Au bimetallic nanoparticles exhibited a significant red shift in the surface plasmon resonance to the near-infrared region. The strategy enables facile preparation of hollow bimetallic nanoparticles in situ in polymer matrixes.

  4. Ordered macroporous bimetallic nanostructures: design, characterization, and applications.

    Science.gov (United States)

    Lu, Lehui; Eychmüller, Alexander

    2008-02-01

    Ordered porous metal nanomaterials have current and future potential applications, for example, as catalysts, as photonic crystals, as sensors, as porous electrodes, as substrates for surface-enhanced Raman scattering (SERS), in separation technology, and in other emerging nanotechnologies. Methods for creating such materials are commonly characterized as "templating", a technique that involves first the creation of a sacrificial template with a specific porous structure, followed by the filling of these pores with desired metal materials and finally the removal of the starting template, leaving behind a metal replica of the original template. From the viewpoint of practical applications, ordered metal nanostructures with hierarchical porosity, namely, macropores in combination with micropores or mesopores, are of particular interest because macropores allow large guest molecules to access and an efficient mass transport through the porous structures is enabled while the micropores or mesopores enhance the selectivity and the surface area of the metal nanostructures. For this objective, colloidal crystals (or artificial opals) consisting of three-dimensional (3D) long-range ordered arrays of silica or polymer microspheres are ideal starting templates. However, with respect to the colloidal crystal templating strategies for production of ordered porous metal nanostructures, there are two challenging questions for materials scientists: (1) how to uniformly and controllably fill the interstitial space of the colloidal crystal templates and (2) how to generate ordered composite metal nanostructures with hierarchical porosity. This Account reports on recent work in the development and applications of ordered macroporous bimetallic nanostructures in our laboratories. A series of strategies have been explored to address the challenges in colloidal crystal template techniques. By rationally tailoring experimental parameters, we could readily and selectively design

  5. Formate--the analogue of azide: structural and magnetic properties of M(HCOO)2(4,4'-bpy).nH2O (M = Mn, Co, Ni; n = 0, 5).

    Science.gov (United States)

    Wang, Xin-Yi; Wei, Hai-Yan; Wang, Zhe-Ming; Chen, Zhi-Da; Gao, Song

    2005-02-07

    Reaction of transition metal formate M(HCOO)(2).2H2O (M = Mn, Co, Ni) with 4,4'-bpy (4,4-bipyridine) has led to four new compounds with the formula M(HCOO)2(4,4'-bpy).nH2O (M = Mn, Co (1.Mn, 2.Co), n = 0; M = Co, Ni (3.Co, 4.Ni), n = 5). Compounds 1.Mn and 2.Co are isomorphous and crystallized in the tetragonal crystal system with the chiral space group P4(1)2(1)2. They are of three-dimensional diamondoid structure connected by anti-anti formate with 4,4'-bpy in the cavities of the framework reinforcing the intermetallic connections; the diamond-like net was observed also in their azide analogue (Mn(N3)2(4,4'-bpy)). Compounds 3.Co and 4.Ni are isomorphous also but crystallized in the monoclinic crystal system with the space group Cc. Both structures are uninterpenetrated 3D "CdSO4" type with big channels, constructed by anti-anti formate and 4,4'-bpy. This type of net was not observed in their azide analogue. Residing in the channels, water molecules form a new type of 1D tape constructed by vertex-sharing cyclic pentamers. Magnetic measurements were performed on all of these four compounds. 1.Mn and 2.Co are weak ferromagnets with the critical temperature Tc = 5.3 and 7.4 K, respectively. 3.Co is an antiferromagnet with Neel temperature TN = 3.0 K, and 4.Ni is a weak ferromagnet below 20 K. Hysteresis loop can be observed for 2.Co and 4.Ni at 1.8 K. As an analogue of azide, formate can be used to construct molecular architectures, which structurally and magnetically have great similarities to and also differences from those of azide. This offers a promising method for the design of new molecular architectures with formate.

  6. Ligand-controlled Co-reduction versus electroless Co-deposition: synthesis of nanodendrites with spatially defined bimetallic distributions.

    Science.gov (United States)

    Ortiz, Nancy; Weiner, Rebecca G; Skrabalak, Sara E

    2014-12-23

    The predictable synthesis of bimetallic nanostructures via co-reduction of two metal precursors is challenging due to our limited understanding of precursor ligand effects. Here, the influence of different metal-ligand environments is systematically examined in the synthesis of Pd-Pt nanostructures as a model bimetallic system. Nanodendrites with different spatially defined Pd-Pt compositions are achieved, where the local ligand environments of metal precursors dictate if temporally separated co-reduction dominates to achieve core-shell nanostructures or whether electroless co-deposition proceeds to facilitate alloyed nanostructure formation. As the properties of bimetallic nanomaterials depend on crystal ordering and composition, chemical routes to structurally defined bimetallic nanomaterials are critically needed. The approaches reported here should be applicable to other bimetallic compositions given the established reactivity of coordination complexes available for use as precursors.

  7. Aqueous synthesis of Ag and Mn co-doped In2S3/ZnS quantum dots with tunable emission for dual-modal targeted imaging.

    Science.gov (United States)

    Lai, Pei-Yu; Huang, Chih-Ching; Chou, Tzung-Han; Ou, Keng-Liang; Chang, Jia-Yaw

    2017-03-01

    Here, we present the microwave-assisted synthesis of In2S3/ZnS core/shell quantum dots (QDs) co-doped with Ag(+) and Mn(2+) (referred to as AgMn:In2S3/ZnS). Ag(+) altered the optical properties of the host QDs, whereas the spin magnetic moment (S=5/2) of Mn(2+) efficiently induced the longitudinal relaxation of water protons. To the best of our knowledge, this is the first report of the aqueous synthesis of color-tunable AgMn:In2S3/ZnS core/shell QDs with magnetic properties. The synthetic procedure is rapid, facile, reproducible, and scalable. The obtained QDs offered a satisfactory quantum yield (45%), high longitudinal relaxivity (6.84s(-1)mM(-1)), and robust photostability. In addition, they exhibited excellent stability over a wide pH range (5-12) and high ionic strength (0.15-2.0M NaCl). As seen by confocal microscopy and magnetic resonance imaging, AgMn:In2S3/ZnS conjugated to hyaluronic acid (referred to as AgMn:In2S3/ZnS@HA) efficiently and specifically targeted cluster determinant 44, a receptor overexpressed on cancer cells. Moreover, AgMn:In2S3/ZnS@HA showed negligible cytotoxicity in vitro and in vivo, rendering it a promising diagnostic probe for dual-modal imaging in clinical applications.

  8. Formation of Cu/Pd bimetallic crystals by electrochemical deposition

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez, A.E. [Instituto de Ingenieria Electroquimica y Corrosion (INIEC), Departamento de Ingenieria Quimica, Universidad Nacional del Sur, Avda. Alem 1253, 8000 Bahia Blanca (Argentina); Salinas, D.R., E-mail: dsalinas@uns.edu.a [Instituto de Ingenieria Electroquimica y Corrosion (INIEC), Departamento de Ingenieria Quimica, Universidad Nacional del Sur, Avda. Alem 1253, 8000 Bahia Blanca (Argentina)

    2010-04-15

    The early stages of the palladium electrodeposition process onto a vitreous carbon (VC) substrate as well as the deposition of Cu on such Pd/VC modified surface were investigated using classical electrochemical techniques, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Within the potential range considered the kinetics of the Pd electrodeposition from a PdCl{sub 2} acid solution can be described by a model involving progressive nucleation on active sites and diffusion-controlled 3D growth. The nucleation rate constant, A{sub 0}, and the number of active sites of the substrate, N{sub 0}, were determined from the analysis of potentiostatic current transients on the basis of an existing theoretical model. The AFM images corroborated the progressive nucleation mechanism showing irregular palladium crystals randomly distributed over the VC surface, with different sizes and 3D morphological characteristics. The electrodeposition of Cu was carried out onto the characterized Pd/VC modified surface from a Cu{sup 2+} containing solution using a well defined polarization routine. The SEM/EDX images confirmed the formation of Cu/Pd bimetallic crystals uniformly distributed on the VC surface and the in situ AFM images obtained during this process corroborated that Cu formed a core-shell structure with the Pd crystals. Nevertheless, the subsequent anodic stripping produced only a partial dissolution of the Cu deposits, and therefore, the formation of a Cu/Pd alloy could be inferred.

  9. Regeneration of sulfur-fouled bimetallic Pd-based catalysts.

    Science.gov (United States)

    Chaplin, Brian P; Shapley, John R; Werth, Charles J

    2007-08-01

    Pd-based catalysts provide efficient and selective reduction of several drinking water contaminants, but their long-term application requires effective treatments for catalyst regeneration following fouling by constituents in natural waters. This studytested alumina-supported Pd-Cu and Pd-In bimetallic catalysts for nitrate reduction with H2 after sulfide fouling and oxidative regeneration procedures. Both catalysts were severely deactivated after treatment with microM levels of sulfide. Regeneration was attempted with dissolved oxygen, hydrogen peroxide, sodium hypochlorite, and heated air. Only sodium hypochlorite and heated air were effective regenerants, specifically restoring nitrate reduction rates for a Pd-In/gamma-Al2O3 catalyst from 20% to between 39 and 60% of original levels. Results from ICP-MS revealed that sodium hypochlorite caused dissolution of Cu from the Pd-Cu catalyst but that the Pd-In catalyst was chemically stable over a range of sulfide fouling and oxidative regenerative conditions. Analysis byXPS indicated that PdS and In2S3 complexes form during sulfide fouling, where sulfur is present as S2-, and that regeneration with sodium hypochlorite converts a portion of the S2- to S6+, with a corresponding increase in reduction rates. These results indicate that Pd-In catalysts show exceptional promise for being robust under fouling and regeneration conditions that may occur when treating natural waters.

  10. Salt flux synthesis of single and bimetallic carbide nanowires

    Science.gov (United States)

    Leonard, Brian M.; Waetzig, Gregory R.; Clouser, Dale A.; Schmuecker, Samantha M.; Harris, Daniel P.; Stacy, John M.; Duffee, Kyle D.; Wan, Cheng

    2016-07-01

    Metal carbide compounds have a broad range of interesting properties and are some of the hardest and highest melting point compounds known. However, their high melting points force very high reaction temperatures and thus limit the formation of high surface area nanomaterials. To avoid the extreme synthesis temperatures commonly associated with these materials, a new salt flux technique has been employed to reduce reaction temperatures and form these materials in the nanometer regime. Additionally, the use of multiwall carbon nanotubes as a reactant further reduces the diffusion distance and provides a template for the final carbide materials. The metal carbide compounds produced through this low temperature salt flux technique maintain the nanowire morphology of the carbon nanotubes but increase in size to ˜15-20 nm diameter due to the incorporation of metal in the carbon lattice. These nano-carbides not only have nanowire like shape but also have much higher surface areas than traditionally prepared metal carbides. Finally, bimetallic carbides with composition control can be produced with this method by simply using two metal precursors in the reaction. This method provides the ability to produce nano sized metal carbide materials with size, morphology, and composition control and will allow for these compounds to be synthesized and studied in a whole new size and temperature regime.

  11. STEM-EDX tomography of bimetallic nanoparticles: A methodological investigation

    Energy Technology Data Exchange (ETDEWEB)

    Slater, Thomas J.A.; Janssen, Arne [School of Materials, University of Manchester, Manchester M13 9PL (United Kingdom); Camargo, Pedro H.C. [Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo (Brazil); Burke, M. Grace [School of Materials, University of Manchester, Manchester M13 9PL (United Kingdom); Zaluzec, Nestor J. [School of Materials, University of Manchester, Manchester M13 9PL (United Kingdom); Nanoscience and Technology Division, Argonne National Laboratory, Argonne, IL 60439, US (United States); Haigh, Sarah J., E-mail: sarah.haigh@manchester.ac.uk [School of Materials, University of Manchester, Manchester M13 9PL (United Kingdom)

    2016-03-15

    This paper presents an investigation of the limitations and optimisation of energy dispersive X-ray (EDX) tomography within the scanning transmission electron microscope, focussing on application of the technique to characterising the 3D elemental distribution of bimetallic AgAu nanoparticles. The detector collection efficiency when using a standard tomography holder is characterised using a tomographic data set from a single nanoparticle and compared to a standard low background double tilt holder. Optical depth profiling is used to investigate the angles and origin of detector shadowing as a function of specimen field of view. A novel time-varied acquisition scheme is described to compensate for variations in the intensity of spectrum images at each sample tilt. Finally, the ability of EDX spectrum images to satisfy the projection requirement for nanoparticle samples is discussed, with consideration of the effect of absorption and shadowing variations. - Highlights: • We investigate the methodology of STEM-EDX tomography of nanoparticles. • We present a time-varied acquisition scheme to compensate for detector shadowing. • The ability of STEM-EDX tomography to meet the projection requirement is discussed.

  12. Sulfentrazone dechlorination by iron-nickel bimetallic nanoparticles.

    Science.gov (United States)

    Nascimento, Mayra A; Lopes, Renata P; Cruz, Jean C; Silva, Antônio A; Lima, Claudio F

    2016-04-01

    The sulfentrazone dechlorination using bimetallic nanoparticles of Fe/Ni was studied. Different variables that could influence the sulfentrazone conversion were investigated, such as nitrogen atmosphere, pH and dosage of the nanoparticles and initial concentration of sulfentrazone. The best results were obtained using controlled pH (pH 4.0) and 1.0 g L(-1) of nanomaterials, resulting in 100 % conversion in only 30 min. Kinetic studies were also conducted, evaluating the influence of different nanoparticle dosages (1.0 to 4.0 g L(-1)), system temperatures (20 to 35 °C) and nickel levels in the composition of the nanomaterials (0.025 to 0.10 gNi/gFe). The mechanism of sulfentrazone conversion has changed due a direct reduction on the catalytic activity sites and indirect reduction by atomic hydrogen. Both mechanisms have followed pseudo-first order models. The conversion rate improved when the dosage of the nanomaterials, system temperature and nickel content in the composition of the nanocomposites were increased. Finally, the conversion products were elucidated by mass spectrometry and toxicity assays were performed using Daphnia Similis. The results showed that the dechlorination product is less toxic than sulfentrazone. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Titania-supported silver-based bimetallic nanoparticles as photocatalysts.

    Science.gov (United States)

    Barakat, M A; Al-Hutailah, R I; Hashim, M H; Qayyum, E; Kuhn, J N

    2013-06-01

    Photocatalytic process has shown recently a great potential as an environmental friendly and clean remediation technology for organic pollutants in wastewater. This work described the synthesis of silver-based bimetallic nanoparticles using colloid chemistry and the subsequent immobilization onto titania to form composite photocatalytic materials (titania-supported Ag-Pt nanoparticles). The photocatalysts were characterized by X-ray diffraction, electron microscopy, and nitrogen physisorption. The catalytic activity of the photocatalysts was evaluated by photocatalytic degradation of phenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The photocatalytic processes were conducted in a batch photoreactor containing appropriate solutions of phenol and 2-CP with UV irradiation of 450 W. UV-visible spectrophotometer was used for analyzing the concentration of phenol and 2-CP in solutions. Parameters affecting the photocatalytic process such as the solution pH, phenol and 2-CP concentrations, and catalyst concentration were investigated. The results obtained revealed that TiO(2)-supported Ag/Pt nanoparticles showed a higher activity for UV-photocatalytic degradation of both phenol and 2-CP pollutants in the solution (as compared to the plain rutile TiO(2)). The photodegradation processes were optimized by the 0.5-g/L catalyst with a pollutant concentration of 50 mg/L for all the samples. Complete degradation for both phenol and 2-CP was achieved after 120 min.

  14. Synthesis of supported bimetallic nanoparticles with controlled size and composition distributions for active site elucidation

    Energy Technology Data Exchange (ETDEWEB)

    Hakim, Sikander H.; Sener, Canan; Alba Rubio, Ana C.; Gostanian, Thomas M.; O' neill, Brandon J; Ribeiro, Fabio H.; Miller, Jeffrey T.; Dumesic, James A

    2015-08-01

    Elucidation of active sites in supported bimetallic catalysts is complicated by the high level of dispersity in the nanoparticle size and composition that is inherent in conventional methods of catalyst preparation. We present a synthesis strategy that leads to highly dispersed, bimetallic nanoparticles with uniform particle size and composition by means of controlled surface reactions. We demonstrate the synthesis of three systems, RhMo, PtMo, and RhRe, consisting of a highly reducible metal with an oxophilic promoter. These catalysts are characterized by FTIR, CO chemisorption, STEM/EDS, TPR, and XAS analysis. The catalytic properties of these bimetallic nanoparticles were probed for the selective CO hydrogenolysis of (hydroxymethyl)tetrahydropyran to produce 1,6 hexanediol. Based on the characterization results and reactivity trends, the active sites in the hydrogenolysis reaction are identified to be small ensembles of the more noble metal (Rh, Pt) adjacent to highly reduced moieties of the more oxophilic metal (Mo, Re).

  15. Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons

    Science.gov (United States)

    Tang, Jing; Salunkhe, Rahul R.; Zhang, Huabin; Malgras, Victor; Ahamad, Tansir; Alshehri, Saad M.; Kobayashi, Naoya; Tominaka, Satoshi; Ide, Yusuke; Kim, Jung Ho; Yamauchi, Yusuke

    2016-07-01

    Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications.

  16. Effects of different additives on bimetallic Au-Pt nanoparticles electrodeposited onto indium tin oxide electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Ballarin, Barbara, E-mail: ballarin@ms.fci.unibo.i [Dipartimento di Chimica Fisica ed Inorganica, Universita di Bologna, V.le Risorgimento, 4, 40136-Bologna (Italy)] [INSTM, UdR Bologna (Italy); Gazzano, Massimo [ISOF-CNR, V. Selmi, 40126-Bologna (Italy); Tonelli, Domenica [Dipartimento di Chimica Fisica ed Inorganica, Universita di Bologna, V.le Risorgimento, 4, 40136-Bologna (Italy)] [INSTM, UdR Bologna (Italy)

    2010-09-01

    Bimetallic Au-Pt nanoparticles (Au-Pt{sub NPs}) have been synthesized using an electrochemical reduction approach. The effects of the addition of different additives in the electrodeposition bath namely KI, 1-nonanesulfonic acid sodium salt and Triton X-100 have been investigated. The structural characterization of the bimetallic nanoparticles has been carried out using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), UV-vis spectroscopy, X-ray diffraction (XRD) and cyclic voltammetry (CV). The Au-Pt{sub NPs} prepared in the presence of KI and Triton X-100 characterized by a relatively narrow size distribution as well as a higher particle density and surface coverage whereas no changes in the morphology were observed. These results suggest a dependence of the size and distribution of the bimetallic nanoparticles from the type and concentration of the additives employed.

  17. Description of the performances of a thermo-mechanical energy harvester using bimetallic beams

    Science.gov (United States)

    Arnaud, A.; Boughaleb, J.; Monfray, S.; Boeuf, F.; Cugat, O.; Skotnicki, T.

    2016-06-01

    Many recent researches have been focused on the development of thermal energy harvesters using thermo-mechanical or thermo-electrical coupling phenomena associated to a first-order thermodynamic transition. In the case of the bimetallic strip heat engine, the exploitation of the thermo-mechanical instability of bimetallic membranes placed in a thermal gradient enables to convert heat into kinetic energy. This paper is a contribution to the modeling and the comprehension of these heat engines. By restraining the study to the simply-supported bimetallic beams and using a Ritz approximation of the beam shape, this paper aims to give an analytical solution to the first mode of the composite beams and then to evaluate the efficiency of the harvesters exploiting these kinds of instability.

  18. Design and performance benchmark of various architectures of a piezoelectric bimetallic strip heat engine

    Science.gov (United States)

    Boughaleb, J.; Arnaud, A.; Monfray, S.; Cottinet, P. J.; Quenard, S.; Boeuf, F.; Guyomar, D.; Skotnicki, T.

    2016-06-01

    This paper deals with an investigation of a thermal energy harvester based on the coupling of a piezoelectric membrane and a bimetallic strip heat engine. The general working principle of the device consists of a double conversion mechanism: the thermal energy is first converted into mechanical energy by means of a bimetallic strip, then the mechanical energy is converted into electricity with a piezoelectric membrane. This paper deals with the study and optimization of the harvester's design. First, the piezoelectric membrane configuration is studied to find the most efficient way to convert mechanical energy into electricity. A benchmark of various piezoelectric materials is then presented to point out the most efficient materials. Finally, our study focuses on the bimetallic strip's properties: the effect of its dimensions of its thermal hysteresis on the harvester's performances are studied and compared. Thanks to these different steps, we were able to point out the best configuration to convert efficiently thermal heat flux into electricity.

  19. Silver-gold bimetallic nanoparticles and their applications as optical materials.

    Science.gov (United States)

    Boote, Brett W; Byun, Hongsik; Kim, Jun-Hyun

    2014-02-01

    Recently, nanoscale metallic particles have been studied extensively due to their tunable and strong optical properties that are well beyond those of organic chromophores. As monometallic nanoparticles have shown strong but narrow absorption bands within the ultraviolet and visible wavelengths, the preparation of bimetallic core-shell structures can give rise to strong, wide, and tunable absorption bands across the visible to near infrared areas. The silver-gold bimetallic nanoparticles with core-shell structures can offer unique physical and optical properties inaccessible to monometallic systems. These nanoparticles have been utilized in many areas of research including chemical catalysis, surface-enhanced Raman spectroscopy, and photothermal therapy. This review article is a comprehensive overview of bimetallic nanoparticle systems consisting of gold and silver; it is based on the recent advances in wet-chemical synthetic methodologies, the characterization of size and shape-dependent optical properties, and various optically driven applications including catalysis, signal-enhancing devices, and biomedical purposes.

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

    Science.gov (United States)

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

    2014-01-01

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

  1. The quality of the joint between alloy steel and unalloyed cast steel in bimetallic layered castings

    Directory of Open Access Journals (Sweden)

    T. Wróbel

    2012-01-01

    Full Text Available In paper is presented technology of bimetallic layered castings based on founding method of layer coating directly in cast process so-called method of mould cavity preparation. Prepared castings consist two fundamental parts i.e. bearing part and working part (layer. The bearing part of bimetallic layered casting is typical foundry material i.e. ferritic-pearlitic unalloyed cast steel, whereas working part (layer is plate of austenitic alloy steel sort X2CrNi 18-9. The ratio of thickness between bearing and working part is 8:1. The aim of paper was assessed the quality of the joint between bearing and working part in dependence of pouring temperature and carbon concentration in cast steel. The quality of the joint in bimetallic layered castings was evaluated on the basis of ultrasonic non-destructive testing, structure and microhardness researches.

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

    Science.gov (United States)

    Hosseinkhani, Baharak; Søbjerg, Lina Sveidal; Rotaru, Amelia-Elena; Emtiazi, Giti; Skrydstrup, Troels; Meyer, Rikke Louise

    2012-01-01

    Bimetallic nanoparticles are considered the next generation of nanocatalysts with increased stability and catalytic activity. Bio-supported synthesis of monometallic nanoparticles has been proposed as an environmentally friendly alternative to the conventional chemical and physical protocols. In this study we synthesize bimetallic bio-supported Pd-Au nanoparticles for the first time using microorganisms as support material. The synthesis involved two steps: (1) Formation of monometallic bio-supported Pd(0) and Au(0) nanoparticles on the surface of Cupriavidus necator cells, and (2) formation of bimetallic bio-supported nanoparticles by reduction of either Au(III) or Pd(II) on to the nanoparticles prepared in step one. Bio-supported monometallic Pd(0) or Au(0) nanoparticles were formed on the surface of C. necator by reduction of Pd(II) or Au(III) with formate. Addition of Au(III) or Pd(II) to the bio-supported particles resulted in increased particle size. UV-Vis spectrophotometry and HR-TEM analyses indicated that the previously monometallic nanoparticles had become fully or partially covered by Au(0) or Pd(0), respectively. Furthermore, Energy Dispersive Spectrometry (EDS) and Fast Fourier Transformation (FFT) analyses confirmed that the nanoparticles indeed were bimetallic. The bimetallic nanoparticles did not have a core-shell structure, but were superior to monometallic particles at reducing p-nitrophenol to p-aminophenol. Hence, formation of microbially supported nanoparticles may be a cheap and environmentally friendly approach for production of bimetallic nanocatalysts. Copyright © 2011 Wiley Periodicals, Inc.

  3. Direct decomposition of methane over SBA-15 supported Ni, Co and Fe based bimetallic catalysts

    Science.gov (United States)

    Pudukudy, Manoj; Yaakob, Zahira; Akmal, Zubair Shamsul

    2015-03-01

    Thermocatalytic decomposition of methane is an alternative route for the production of COx-free hydrogen and carbon nanomaterials. In this work, a set of novel Ni, Co and Fe based bimetallic catalysts supported over mesoporous SBA-15 was synthesized by a facile wet impregnation route, characterized for their structural, textural and reduction properties and were successfully used for the methane decomposition. The fine dispersion of metal oxide particles on the surface of SBA-15, without affecting its mesoporous texture was clearly shown in the low angle X-ray diffraction patterns and the transmission electron microscopy (TEM) images. The nitrogen sorption analysis showed the reduced specific surface area and pore volume of SBA-15, after metal loading due to the partial filling of hexagonal mesopores by metal species. The results of methane decomposition experiments indicated that all of the bimetallic catalysts were highly active and stable for the reaction at 700 °C even after 300 min of time on stream (TOS). However, a maximum hydrogen yield of ∼56% was observed for the NiCo/SBA-15 catalyst within 30 min of TOS. A high catalytic stability was shown by the CoFe/SBA-15 catalyst with 51% of hydrogen yield during the course of reaction. The catalytic stability of the bimetallic catalysts was attributed to the formation of bimetallic alloys. Moreover, the deposited carbons were found to be in the form of a new set of hollow multi-walled nanotubes with open tips, indicating a base growth mechanism, which confirm the selectivity of SBA-15 supported bimetallic catalysts for the formation of open tip carbon nanotubes. The Raman spectroscopic and thermogravimetric analysis of the deposited carbon nanotubes over the bimetallic catalysts indicated their higher graphitization degree and oxidation stability.

  4. Synthesis and characterization of one-dimensional and molecular M(tren)InAsS4 (M = Mn, Co, and Zn) compounds with a noncondensed AsS3(3-) unit.

    Science.gov (United States)

    Wang, Zhenqing; Zhang, Hongjie; Wang, Cheng

    2009-09-07

    Four transition-metal-amine complexes incorporating indium thioarsenates with the general formula M(tren)InAsS(4) (M = Mn, Co, and Zn) and a noncondensed AsS(3)(3-) unit have been prepared and characterized. Single-crystal X-ray diffraction analyses show that compound 1 (M = Mn) crystallizes in the triclinic crystal system (space group: P1) and consists of a one-dimensional (1D) inorganic (1)(infinity){[InAsS(4)](2-)} chain and [Mn(tren)](2+) groups bonded to the opposite sides of an eight-membered In(2)As(2)S(4) ring along the backbone of the infinite inorganic chains. Compounds 2 (M = Mn), 3 (M = Zn), and 4 (M = Co) are isomorphous molecular compounds. They all crystallize in the monoclinic crystal system (space group: P2(1)/c). The Mn(2+) cation of [Mn(tren)](2+) in 1 has a distorted octahedral environment, while the transition-metal cations of [M(tren)](2+) in the other three compounds locate in trigonal-bipyramidal environments. This difference results in different bonding modes of [M(tren)](2+) to indium thioarsenates between compound 1 and the other three compounds.

  5. Beyond organic chemistry: aromaticity in atomic clusters.

    Science.gov (United States)

    Boldyrev, Alexander I; Wang, Lai-Sheng

    2016-04-28

    We describe joint experimental and theoretical studies carried out collaboratively in the authors' labs for understanding the structures and chemical bonding of novel atomic clusters, which exhibit aromaticity. The concept of aromaticity was first discovered to be useful in understanding the square-planar unit of Al4 in a series of MAl4(-) bimetallic clusters that led to discoveries of aromaticity in many metal cluster systems, including transition metals and similar cluster motifs in solid compounds. The concept of aromaticity has been found to be particularly powerful in understanding the stability and bonding in planar boron clusters, many of which have been shown to be analogous to polycyclic aromatic hydrocarbons in their π bonding. Stimulated by the multiple aromaticity in planar boron clusters, a design principle has been proposed for stable metal-cerntered aromatic molecular wheels of the general formula, M@Bn(k-). A series of such borometallic aromatic wheel complexes have been produced in supersonic cluster beams and characterized experimentally and theoretically, including Ta@B10(-) and Nb@B10(-), which exhibit the highest coordination number in two dimensions.

  6. INTERACTION OF SULPHUR WITH BIMETALLIC SURFACES: EFFECTS OF STRUCTURAL, ELECTRONIC AND CHEMICAL PROPERTIES.

    Energy Technology Data Exchange (ETDEWEB)

    RODRIGUEZ,J.A.; HRBEK,J.

    2001-10-04

    In recent years, several new interesting phenomena have been discovered when studying the interaction of sulphur with bimetallic surfaces using the modern techniques of surface science. Very small amounts of sulphur can induce dramatic changes in the morphology of bimetallic surfaces. The electronic perturbations associated with the formation of a heteronuclear metal-metal bond affect the reactivity of the bonded metals toward sulphur. This can be a very important issue to consider when trying to minimize the negative effects of sulphur poisoning or dealing with the design of desulfurization catalysts.

  7. Polyfunctional two- (2D) and three- (3D) dimensional oxalate bridged bimetallic magnets

    CERN Document Server

    Clément, R; Gruselle, M; Train, C

    2003-01-01

    We report major results concerning polyfunctional two- (2D) and three- (3D) dimensional oxalate bridged bimetallic magnets. As a consequence of their specific organization they are composed of an anionic sub-lattice and a cationic counter-part. These bimetallic polymers can accommodate various counter-cations possessing specific physical properties in addition to the magnetic ones resulting from the interactions between the metallic ions in the anionic sub-lattice. Thus, molecular magnets possessing paramagnetic, conductive and optical properties are presented in this review. Refs. 60 (author)

  8. Structure analysis of bimetallic Co-Au nanoparticles formed by sequential ion implantation

    Science.gov (United States)

    Chen, Hua-jian; Wang, Yu-hua; Zhang, Xiao-jian; Song, Shu-peng; chen, Hong; Zhang, Ke; Xiong, Zu-zhao; Ji, Ling-ling; Dai, Hou-mei; Wang, Deng-jing; Lu, Jian-duo; Wang, Ru-wu; Zheng, Li-rong

    2016-08-01

    Co-Au alloy Metallic nanoparticles (MNPs) are formed by sequential ion implantation of Co and Au into silica glass at room temperature. The ion ranges of Au ions implantation process have been displayed to show the ion distribution. We have used the atomic force microscopy (AFM) and transmission electron microscopy (TEM) to investigate the formation of bimetallic nanoparticles. The extended X-ray absorption fine structure (EXAFS) has been used to study the local structural information of bimetallic nanoparticles. With the increase of Au ion implantation, the local environments of Co ions are changed enormously. Hence, three oscillations, respectively, Co-O, Co-Co and Co-Au coordination are determined.

  9. A theoretical approach for estimation of ultimate size of bimetallic nanocomposites synthesized in microemulsion systems

    Science.gov (United States)

    Salabat, Alireza; Saydi, Hassan

    2012-12-01

    In this research a new idea for prediction of ultimate sizes of bimetallic nanocomposites synthesized in water-in-oil microemulsion system is proposed. In this method, by modifying Tabor Winterton approximation equation, an effective Hamaker constant was introduced. This effective Hamaker constant was applied in the van der Waals attractive interaction energy. The obtained effective van der Waals interaction energy was used as attractive contribution in the total interaction energy. The modified interaction energy was applied successfully to predict some bimetallic nanoparticles, at different mass fraction, synthesized in microemulsion system of dioctyl sodium sulfosuccinate (AOT)/isooctane.

  10. Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

    KAUST Repository

    Li, Lidong

    2015-02-03

    Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core-shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. These catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure. The reform of reforming: A series of alumina-supported Ni/Pt bimetallic nanoparticles (NPs) with controlled surface composition and structure are prepared. Remarkable surface segregation for these bimetallic NPs is observed upon thermal treatment. These bimetallic NPs are active catalysts for CO2 reforming of CH4, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

  11. Phytogenic silver, gold, and bimetallic nanoparticles as novel antitubercular agents.

    Science.gov (United States)

    Singh, Richa; Nawale, Laxman; Arkile, Manisha; Wadhwani, Sweety; Shedbalkar, Utkarsha; Chopade, Snehal; Sarkar, Dhiman; Chopade, Balu Ananda

    2016-01-01

    Multi- and extensively drug-resistant tuberculosis (TB) is a global threat to human health. It requires immediate action to seek new antitubercular compounds and devise alternate strategies. Nanomaterials, in the present scenario, have opened new avenues in medicine, diagnosis, and therapeutics. In view of this, the current study aims to determine the efficacy of phytogenic metal nanoparticles to inhibit mycobacteria. Silver (AgNPs), gold (AuNPs), and gold-silver bimetallic (Au-AgNPs) nanoparticles synthesized from medicinal plants, such as Barleria prionitis, Plumbago zeylanica, and Syzygium cumini, were tested against Mycobacterium tuberculosis and M. bovis BCG. In vitro and ex vivo macrophage infection model assays were designed to determine minimum inhibitory concentration (MIC) and half maximal inhibitory concentration of nanoparticles. Microscopic analyses were carried out to demonstrate intracellular uptake of nanoparticles in macrophages. Besides this, biocompatibility, specificity, and selectivity of nanoparticles were also established with respect to human cell lines. Au-AgNPs exhibited highest antitubercular activity, with MIC of nanoparticles were capable of entering macrophage cells and exhibited up to 45% cytotoxicity at 30 μg/mL (ten times MIC concentration) after 48 hours. Among these, Au-AgNPs synthesized from S. cumini were found to be more specific toward mycobacteria, with their selectivity index in the range of 94-108. This is the first study to report the antimycobacterial activity of AuNPs, AgNPs, and Au-AgNPs synthesized from medicinal plants. Among these, Au-AgNPs from S. cumini showed profound efficiency, specificity, and selectivity to kill mycobacteria. These should be investigated further to develop novel TB nanoantibiotics.

  12. ELECTRONIC AND CHEMICAL PROPERTIES OF PD IN BIMETALLIC SYSTEMS: HOW MUCH DO WE KNOW ABOUT HETERONUCLEAR METAL-METAL BONDING?

    Energy Technology Data Exchange (ETDEWEB)

    RODRIGUEZ,J.A.

    2001-09-27

    The experimental and theoretical studies described above illustrate the complex nature of the heteronuclear metal-metal bond. In many cases, bimetallic bonding induces a significant redistribution of charge around the bonded metals. This redistribution of charge is usually linked to the strength of the bimetallic bond, affects the position of the core and valence levels of the metals, and can determine the chemical reactivity of the system under study. New concepts are emerging [22,23,34,36] and eventually the coupling of experiment and theory can be useful for designing more efficient bimetallic catalysts [98,106,107].

  13. Synthesis of bimetallic gold-silver alloy nanoclusters by simple mortar grinding.

    Science.gov (United States)

    Murugadoss, Arumugam; Kai, Noriko; Sakurai, Hidehiro

    2012-02-21

    A macroscale quantity of bimetallic Au-Ag alloy nanoclusters was achieved through sequential reduction by simple mortar grinding. The chitosan biopolymer was used as both a stabilizing and reducing agent. These nanoclusters exhibit excellent catalytic activity toward the reduction of 4-nitrophenol.

  14. Antisymmetric Magnetic Interactions in Oxo-Bridged Copper(II) Bimetallic Systems

    NARCIS (Netherlands)

    Maurice, R.; Pradipto, A. M.; Guihery, N.; Broer, R; de Graaf, C.

    2010-01-01

    The antisymmetric magnetic interaction is studied using correlated wave-function-based calculations in oxo-bridged copper bimetallic complexes. All of the anisotropic multispin Hamiltonian parameters are extracted using spin orbit state interaction and effective Hamiltonian theory. It is shown that

  15. Synthesis and exceptional thermal stability of Mg-based bimetallic nanoparticles during hydrogenation

    NARCIS (Netherlands)

    Krishnan, Gopi; Negrea, Raluca F.; Ghica, Corneliu; ten Brink, Gert H.; Kooi, Bart J.; Palasantzas, Georgios

    2014-01-01

    Here we report the extraordinary thermal stability of Mg rich bimetallic nanoparticles (NPs), which is important for hydrogen storage technology. The enhanced NP stability is accomplished because of two critical improvements: (i) no void development within NPs (nanoscale Kirkendall effect) during

  16. Non-Precious Bimetallic Catalysts for Selective Dehydrogenation of an Organic Chemical Hydride System

    KAUST Repository

    Shaikh Ali, Anaam

    2015-07-06

    Methylcyclohexane (MCH)-Toluene (TOL) chemical hydride cycles as a hydrogen carrier system is successful with the selective dehydrogenation reaction of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report improved selectivity using non-precious metal nickel-based bimetallic catalysts, where the second metal occupies the unselective step sites.

  17. Optical properties of multilayer bimetallic films obtained by laser deposition of colloidal particles

    Science.gov (United States)

    Antipov, A.; Arakelian, S.; Vartanyan, T.; Gerke, M.; Istratov, A.; Kutrovskaya, S.; Kucherik, A.; Osipov, A.

    2016-11-01

    The optical properties of multilayer bimetallic films composed of silver and gold nanoparticles have been investigated. The dependence of the transmission spectra of the films on their morphology is demonstrated. A finite-difference time-domain (FDTD) simulation has confirmed that there is a dependence of the transmission spectra on the average distance between particles and the number of deposited layers.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Zhao-Bin; Wu, Feng; Wang, Yue-Chao; Jiang, Hong, E-mail: jianghchem@pku.edu.cn [Beijing National Laboratory of Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China)

    2015-06-07

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

  19. Fundamental studies of hydrogen interaction with supported meta and bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Bhatia, S.

    1993-12-07

    The thesis is divided into 3 parts: interaction of H with silica supported Ru catalysts (high pressure in situ NMR), in situ NMR study of H interaction with supported Ru-group IB bimetallic catalysts, and in-situ NMR study of H effects on silica-supported Pt, Rh and Ru catalysts.

  20. Synthesis and exceptional thermal stability of Mg-based bimetallic nanoparticles during hydrogenation

    NARCIS (Netherlands)

    Krishnan, Gopi; Negrea, Raluca F.; Ghica, Corneliu; ten Brink, Gert H.; Kooi, Bart J.; Palasantzas, Georgios

    2014-01-01

    Here we report the extraordinary thermal stability of Mg rich bimetallic nanoparticles (NPs), which is important for hydrogen storage technology. The enhanced NP stability is accomplished because of two critical improvements: (i) no void development within NPs (nanoscale Kirkendall effect) during th

  1. Surface Segregation in Bimetallic Nanoparticles: A Critical Issue in Electrocatalyst Engineering.

    Science.gov (United States)

    Liao, Hanbin; Fisher, Adrian; Xu, Zhichuan J

    2015-07-15

    Bimetallic nanoparticles are a class of important electrocatalyst. They exhibit a synergistic effect that critically depends on the surface composition, which determines the surface properties and the adsorption/desorption behavior of the reactants and intermediates during catalysis. The surface composition can be varied, as nanoparticles are exposed to certain environments through surface segregation. Thermodynamically, this is caused by a difference in surface energy between the two metals. It may lead to the enrichment of one metal on the surface and the other in the core. The external conditions that influence the surface energy may lead to the variation of the thermodynamic steady state of the particle surface and, thus, offer a chance to vary the surface composition. In this review, the most recent and important progress in surface segregation of bimetallic nanoparticles and its impact in electrocatalysis are introduced. Typical segregation inducements and surface characterization techniques are discussed in detail. It is concluded that surface segregation is a critical issue when designing bimetallic catalysts. It is necessary to explore methods to control it and utilize it as a way towards producing robust, bimetallic electrocatalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. EXAFS as a tool to interrogate the size and shape of mono and bimetallic catalyst nanoparticles

    NARCIS (Netherlands)

    Beale, A.M.|info:eu-repo/dai/nl/325802068; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2013-01-01

    The influence of atom packing and the geometric arrangement of atoms on the coordination number(s) and resultant simulated EXAFS spectra for face centrered cubic (fcc), hexagonal close packed (hcp) and body centered cubic (bcc) monometallic structures and fcc bimetallic structures, has been examined

  3. A Systematic Investigation of p-Nitrophenol Reduction by Bimetallic Dendrimer Encapsulated Nanoparticles

    Science.gov (United States)

    2013-01-01

    We demonstrate that the reduction of p-nitrophenol to p-aminophenol by NaBH4 is catalyzed by both monometallic and bimetallic nanoparticles (NPs). We also demonstrate a straightforward and precise method for the synthesis of bimetallic nanoparticles using poly(amido)amine dendrimers. The resulting dendrimer encapsulated nanoparticles (DENs) are monodisperse, and the size distribution does not vary with different elemental combinations. Random alloys of Pt/Cu, Pd/Cu, Pd/Au, Pt/Au, and Au/Cu DENs were synthesized and evaluated as catalysts for p-nitrophenol reduction. These combinations are chosen in order to selectively tune the binding energy of the p-nitrophenol adsorbate to the nanoparticle surface. Following the Brønsted–Evans–Polanyi (BEP) relation, we show that the binding energy can reasonably predict the reaction rates of p-nitrophenol reduction. We demonstrate that the measured reaction rate constants of the bimetallic DENs is not always a simple average of the properties of the constituent metals. In particular, DENs containing metals with similar lattice constants produce a binding energy close to the average of the two constituents, whereas DENs containing metals with a lattice mismatch show a bimodal distribution of binding energies. Overall, in this work we present a uniform method for synthesizing pure and bimetallic DENs and demonstrate that their catalytic properties are dependent on the adsorbate’s binding energy. PMID:23616909

  4. The formation mechanism of bimetallic PtRu alloy nanoparticles in solvothermal synthesis.

    Science.gov (United States)

    Mi, Jian-Li; Nørby, Peter; Bremholm, Martin; Becker, Jacob; Iversen, Bo B

    2015-10-21

    An understanding of the nucleation and growth mechanism of bimetallic nanoparticles in solvothermal synthesis is important for further development of nanoparticles with tailored nanostructures and properties. Here the formation of PtRu alloy nanoparticles in a solvothermal synthesis using metal acetylacetonate salts as precursors and ethanol as both the solvent and reducing agent has been studied by in situ synchrotron radiation powder X-ray diffraction (SR-PXRD). Unlike the classical mechanism for the synthesis of monodisperse sols, the nucleation and growth processes of bimetallic PtRu nanoparticles occur simultaneously under solvothermal conditions. In the literature co-reduction of Pt and Ru is often assumed to be required to form PtRu bimetallic nanocrystals, but it is shown that monometallic Pt nanocrystals nucleate first and rapidly grow to an average size of 5 nm. Subsequently, the PtRu bimetallic alloy is formed in the second nucleation stage through a surface nucleation mechanism related to the reduction of Ru. The calculated average crystallite size of the resulting PtRu nanocrystals is smaller than that of the primary Pt nanocrystals due to the large disorder in the PtRu alloyed structure.

  5. VAPOR PHASE MERCURY SORPTION BY ORGANIC SULFIDE MODIFIED BIMETALLIC IRON-COPPER NANOPARTICLE AGGREGATES

    Science.gov (United States)

    Novel organic sulfide modified bimetallic iron-copper nanoparticle aggregate sorbent materials have been synthesized for removing elemental mercury from vapor streams at elevated temperatures (120-140 °C). Silane based (disulfide silane and tetrasulfide silane) and alkyl sulfide ...

  6. EXAFS as a tool to interrogate the size and shape of mono and bimetallic catalyst nanoparticles

    NARCIS (Netherlands)

    Beale, A.M.; Weckhuysen, B.M.

    2013-01-01

    The influence of atom packing and the geometric arrangement of atoms on the coordination number(s) and resultant simulated EXAFS spectra for face centrered cubic (fcc), hexagonal close packed (hcp) and body centered cubic (bcc) monometallic structures and fcc bimetallic structures, has been examined

  7. Exceptional methanol electro-oxidation activity by bimetallic concave and dendritic Pt-Cu nanocrystals catalysts

    Science.gov (United States)

    Wang, Ying-Xia; Zhou, Hui-Jing; Sun, Ping-Chuan; Chen, Tie-Hong

    2014-01-01

    PtCux (x = 1, 2 and 3) bimetallic nanocrystals with concave surface and dendritic morphology were prepared and used as electrocatalysts in methanol oxidation reaction (MOR) for polymer electrolyte membrane fuel cells. The bimetallic nanocrystals were synthesized via one-pot co-reduction of H2PtCl6 and Cu(acac)2 by oleylamine and polyvinyl pyrrolidone (PVP) in an autoclave at 180 °C. The concave dendritic bimetallic nanostructure consisted of a core rich in Cu and nanodendrites rich in Pt, which was formed via galvanic replacement of Cu by Pt. It was found that PVP played an important role in initiating, facilitating, and directing the replacement reaction. The electrochemical properties of the PtCux were characterized by cyclic voltammetry (CV) and chronoamperometry (CA). The concave dendritic PtCu2/C nanocrystals exhibited exceptionally high activity and strong poisoning resistance in MOR. At 0.75 V (vs. reversible hydrogen electrode, RHE) the mass activity and specific activity of PtCu2/C were 3.3 and 4.1 times higher than those of the commercial Pt/C catalysts, respectively. The enhanced catalytic activity could be attributed to the unique concave dendritic morphology of the bimetallic nanocrystals.

  8. Enhanced dechlorination of trichloroethylene using electrospun polymer nanofibrous mats immobilized with iron/palladium bimetallic nanoparticles.

    Science.gov (United States)

    Ma, Hui; Huang, Yunpeng; Shen, Mingwu; Guo, Rui; Cao, Xueyan; Shi, Xiangyang

    2012-04-15

    Fe/Pd bimetallic nanoparticles (NPs) have held great promise for treating trichloroethylene (TCE)-contaminated groundwater, without the accumulation of chlorinated intermediates. However, the conventionally used colloidal Fe/Pd NPs usually aggregate rapidly, resulting in a reduced reactivity. To reduce the particle aggregation, we employed electrospun polyacrylic acid (PAA)/polyvinyl alcohol (PVA) polymer nanofibers as a nanoreactor to immobilize Fe/Pd bimetallic NPs. In the study, the water-stable PAA/PVA nanofibrous mats were complexed with Fe (III) ions via the binding with the free carboxyl groups of PAA for subsequent formation and immobilization of zero-valent iron (ZVI) NPs. Fe/Pd bimetallic NPs were then formed by the partial reduction of Pd(II) ions with ZVI NPs. The formed electrospun nanofibrous mats containing Fe/Pd bimetallic NPs with a diameter of 2.8 nm were characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, thermogravimetric analysis, and inductively coupled plasma-atomic emission spectroscopy. The Fe/Pd NP-containing electrospun PAA/PVA nanofibrous mats exhibited higher reactivity than that of the ZVI NP-containing mats or colloidal Fe/Pd NPs in the dechlorination of trichloroethylene (TCE), which was used as a model contaminant. With the high surface area to volume ratio, high porosity, and great reusability of the fibrous mats immobilized with the bimetallic NPs, the composite nanofibrous mats should be amenable for applications in remediation of various environmental contaminants. Copyright © 2011 Elsevier B.V. All rights reserved.

  9. Cluster headache

    Science.gov (United States)

    Histamine headache; Headache - histamine; Migrainous neuralgia; Headache - cluster; Horton's headache; Vascular headache - cluster ... A cluster headache begins as a severe, sudden headache. The headache commonly strikes 2 to 3 hours after you fall ...

  10. Cluster Forests

    CERN Document Server

    Yan, Donghui; Jordan, Michael I

    2011-01-01

    Inspired by Random Forests (RF) in the context of classification, we propose a new clustering ensemble method---Cluster Forests (CF). Geometrically, CF randomly probes a high-dimensional data cloud to obtain "good local clusterings" and then aggregates via spectral clustering to obtain cluster assignments for the whole dataset. The search for good local clusterings is guided by a cluster quality measure $\\kappa$. CF progressively improves each local clustering in a fashion that resembles the tree growth in RF. Empirical studies on several real-world datasets under two different performance metrics show that CF compares favorably to its competitors. Theoretical analysis shows that the $\\kappa$ criterion is shown to grow each local clustering in a desirable way---it is "noise-resistant." A closed-form expression is obtained for the mis-clustering rate of spectral clustering under a perturbation model, which yields new insights into some aspects of spectral clustering.

  11. On the performance of surface plasmon resonance based fibre optic sensor with different bimetallic nanoparticle alloy combinations

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Anuj K; Mohr, Gerhard J [Institute of Physical Chemistry, Friedrich-Schiller University, Lessingstrasse 10, 07743 Jena (Germany)], E-mail: anuj.sharma@uni-jena.de

    2008-03-07

    In this work, we have investigated the capability of different bimetallic nanoparticle alloy combinations to be used in fibre optic sensors based on the technique of surface plasmon resonance. The metals considered for this analysis are silver, gold, copper and aluminium. The performance of the sensor with different bimetallic nanoparticle alloy combinations is evaluated and compared numerically. The performance is analysed in terms of three parameters: sensitivity, signal-to-noise ratio (SNR) and operating range for the sensing layer refractive index values. On the basis of the comparison and some logistic criteria, the best possible bimetallic alloy combinations along with a requisite alloy composition ratio are predicted. The bimetallic nanoparticle alloy combination is capable of simultaneously providing larger values of sensitivity, SNR and operating range, which is not possible with any single metallic nanoparticle layer.

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

    Science.gov (United States)

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

    2015-04-14

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

  13. Thermal decomposition of mono- and bimetallic magnesium amidoborane complexes.

    Science.gov (United States)

    Spielmann, Jan; Piesik, Dirk F-J; Harder, Sjoerd

    2010-07-26

    Complexes of the type [(DIPPnacnac)MgNH(R)BH(3)] have been prepared (DIPPnacnac=CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)). The following substituents R have been used: H, Me, iPr, DIPP (DIPP=2,6-diisopropylphenyl). Complexes [(DIPPnac- nac)MgNH(2)BH(3)].THF, [{(DIPPnac- nac)MgNH(iPr)BH(3)}(2)] and [(DIPPnacnac)MgNH(DIPP)BH(3)] were structurally characterised. The Mg amidoborane complexes decompose at a significantly higher temperature (90-110 degrees C) than the corresponding Ca amidoborane complexes (20-110 degrees C). The complexes with the smaller R substituents (H, Me) gave a mixture of decomposition products of which one could be structurally characterised as [{(DIPPnacnac)Mg}(2)(H(3)B-NMe-BH-NMe)].THF. [{(DIPP- nacnac)MgNH(iPr)BH(3)}(2)] cleanly decomposed to [(DIPPnacnac)MgH], which was characterised as a dimeric THF adduct. The amidoborane complex with the larger DIPP-substituent decomposed into a borylamide complex [(DIPPnacnac)MgN(DIPP)BH(2)], which was structurally characterised as its THF adduct. Bimetallic Mg amidoborane complexes decompose at lower temperatures (60-90 degrees C) and show a different decomposition pathway. The dinuclear Mg amidoborane complexes presented here are based on DIPPnacnac units that are either directly coupled through N-N bonding (abbreviated NN) or through a 2,6-pyridylene bridge (abbreviated PYR). Crystal structures of [PYR-{Mg(nBu)}(2)], [PYR-{MgNH(iPr)BH(3)}(2)], [NN-{MgNH(iPr)BH(3)}(2)]THF and the decomposition products [PYR-Mg(2)(iPrN-BH-iPrN-BH(3))] and [NN-Mg(2)(iPrN-BH-iPrN-BH(3))].THF are presented. The following conclusions can be drawn from these studies: i) The first step in the decomposition of a metal amidoborane complex is beta-hydride elimination, which results in formation of a metal hydride complex and R(H)N=BH(2), ii) depending on the nature of the metal, the metal hydride is either stable and can be isolated or it reacts further, iii) amidoborane anions with small R substituents decompose into the dianionic

  14. Phytogenic silver, gold, and bimetallic nanoparticles as novel antitubercular agents

    Directory of Open Access Journals (Sweden)

    Singh R

    2016-05-01

    Full Text Available Richa Singh,1 Laxman Nawale,2 Manisha Arkile,2 Sweety Wadhwani,1 Utkarsha Shedbalkar,1 Snehal Chopade,1 Dhiman Sarkar,2 Balu Ananda Chopade1,3 1Department of Microbiology, Savitribai Phule Pune University, 2Combichem-Bioresource Center, Organic Chemistry Division, National Chemical Laboratory, Pune, 3Dr Babasaheb Ambedkar Marathwada University, Aurangabad, Maharashtra, India Purpose: Multi- and extensively drug-resistant tuberculosis (TB is a global threat to human health. It requires immediate action to seek new antitubercular compounds and devise alternate strategies. Nanomaterials, in the present scenario, have opened new avenues in medicine, diagnosis, and therapeutics. In view of this, the current study aims to determine the efficacy of phytogenic metal nanoparticles to inhibit mycobacteria. Methods: Silver (AgNPs, gold (AuNPs, and gold–silver bimetallic (Au–AgNPs nanoparticles synthesized from medicinal plants, such as Barleria prionitis, Plumbago zeylanica, and Syzygium cumini, were tested against Mycobacterium tuberculosis and M. bovis BCG. In vitro and ex vivo macrophage infection model assays were designed to determine minimum inhibitory concentration (MIC and half maximal inhibitory concentration of nanoparticles. Microscopic analyses were carried out to demonstrate intracellular uptake of nanoparticles in macrophages. Besides this, biocompatibility, specificity, and selectivity of nanoparticles were also established with respect to human cell lines. Results: Au–AgNPs exhibited highest antitubercular activity, with MIC of <2.56 µg/mL, followed by AgNPs. AuNPs did not show such activity at concentrations of up to 100 µg/mL. In vitro and ex vivo macrophage infection model assays revealed the inhibition of both active and dormant stage mycobacteria on exposure to Au–AgNPs. These nanoparticles were capable of entering macrophage cells and exhibited up to 45% cytotoxicity at 30 µg/mL (ten times MIC concentration after 48 hours

  15. Star Clusters

    OpenAIRE

    Gieles, M.

    1993-01-01

    Star clusters are observed in almost every galaxy. In this thesis we address several fundamental problems concerning the formation, evolution and disruption of star clusters. From observations of (young) star clusters in the interacting galaxy M51, we found that clusters are formed in complexes of stars and star clusters. These complexes share similar properties with giant molecular clouds, from which they are formed. Many (70%) of the young clusters will not survive the fist 10 Myr, due to t...

  16. Ligand-protected gold clusters: the structure, synthesis and applications

    Science.gov (United States)

    Pichugina, D. A.; Kuz'menko, N. E.; Shestakov, A. F.

    2015-11-01

    Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Aun with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au15 and Au25) and on anchorage to a support surface (Au25/SiO2, Au20/C, Au10/FeOx) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR)n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters MxAunLm (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR)x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active sites. The bibliography includes 345 references.

  17. Dechlorination of disinfection by-product monochloroacetic acid in drinking water by nanoscale palladized iron bimetallic particle

    Institute of Scientific and Technical Information of China (English)

    CHEN Chao; WANG Xiangyu; CHANG Ying; LIU Huiling

    2008-01-01

    Nanoscale palladized iron (Pd/Fe) bimetallic particles were prepared by reductive deposition method. The particles were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscope (SEM), transmission electron microscope (TEM), and Brunauer-Emmett-Teller-nitrogen (BET-N2) method. Data obtained from those methods indicated that nanoscale Pd/Fe bimetallic particles contained α-Fe0. Detected Pd to Fe ratio by weight (PFRW) was close to theoretical PFRW. Spherical granules with diameter of 47±11.5 nm connected with one another to form chains and the chains composed nanoscale Pd/Fe bimetallic particles. Specific surface area of particles was 51 m2/g. Factors, such as species of reductants, PFRW, dose of nanoscale Pd/Fe bimetallic particles added into solutions, solution initial pH, and a variety of solvents were studied. Dechlorination effect of monochloroacetic acid (MCAA) by different reductants followed the trend: nanoscale Pd/Fe bimetallic particles of 0.182% PFRW > nanoscale Fe > reductive Fe. When PFRW was lower than 0.083%, increasing PFRW would increase dechlorination efficiency (DE) of MCAA. But when the PFRW was higher than 0.083%, increasing PFRW caused decrease in DE. Adding more nanoscale Pd/Fe bimetallic particles to solution would enhance DE. The DE of MCAA decreased as initial pH of solution increased.

  18. Surface plasmon resonance sensing of a biomarker of Alzheimer disease in an intensity measurement mode with a bimetallic chip

    Science.gov (United States)

    Kim, Hyung Jin; Sohn, Young-Soo; Kim, Chang-duk; Jang, Dae-ho

    2016-09-01

    A surface plasmon resonance (SPR) sensor system with a bimetallic chip has been utilized to sense the very low concentration of amyloid-beta (A β)(1-42) by measurement of the reflectance variation. The bimetallic chip was comprised of Au (10 nm) and Ag (40 nm) on Cr (2 nm)-coated BK-7 glass substrate. Protein A was used to efficiently immobilize the antibody of A β(1-42) on the surface of the bimetallic chip. The reflectance curve of the bimetallic chip represented a narrower linewidth compared to that of the conventional gold (Au) chip. The SPR sensor using the bimetallic chip in the intensity interrogation mode acquired the response of A β(1-42) at concentrations of 250, 500, 750 and 1,000 pg/ml. The calibration plot showed a linear relationship between the mean reflectance variation and the A β(1-42) concentration. The results proved that the SPR sensor system with the bimetallic chip in the intensity interrogation mode can successfully detect various concentrations of A β(1-42), including critical concentration, to help diagnose Alzheimer's disease.

  19. Bimetallic gold-silver nanoplate array as a highly active SERS substrate for detection of streptavidin/biotin assemblies.

    Science.gov (United States)

    Bi, Liyan; Dong, Jian; Xie, Wei; Lu, Wenbo; Tong, Wei; Tao, Lin; Qian, Weiping

    2013-12-17

    The silver-modified gold nanoplate arrays as bimetallic surface-enhanced Raman scattering (SERS) substrates were optimized for the surface-enhanced Raman detection of streptavidin/biotin monolayer assemblies. The bimetallic gold-silver nanoplate arrays were fabricated by coating silver nanoparticles uniformly on the gold nanoplate arrays. Depending on silver nanoparticle coating, the localized surface plasmon resonance (LSPR) peak of the bimetallic gold-silver nanoplate arrays blue-shifted and broadened significantly. The common probe molecule, Niel Blue A sulfate (NBA) was used for testing the SERS activity of the bimetallic gold-silver nanoplate arrays. The SERS intensity increased with the silver nanoparticle coating, due to a large number of hot spots and nanoparticle interfaces. The platforms were tested against a monolayer of streptavidin functionalized over the bimetallic gold-silver nanoplate arrays showing that good quality spectra could be acquired with a short acquisition time. The supramolecular interaction between streptavidin (strep) and biotin showed subsequent modification of Raman spectra that implied a change of the secondary structure of the host biomolecule. And the detection concentration for biotin by this method was as low as 1.0 nM. The enhanced SERS performance of such bimetallic gold-silver nanoplate arrays could spur further interest in the integration of highly sensitive biosensors for rapid, nondestructive, and quantitative bioanalysis, particularly in microfluidics.

  20. Controlled Surface Segregation Leads to Efficient Coke-Resistant Nickel/Platinum Bimetallic Catalysts for the Dry Reforming of Methane

    Energy Technology Data Exchange (ETDEWEB)

    Li, Lidong [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Zhou, Lu [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Ould-Chikh, Samy [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Anjum, Dalaver H. [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Kanoun, Mohammed B. [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Scaranto, Jessica [SABIC Corporate Research and Innovation Center, Thuwal (Saudi Arabia); Hedhili, Mohamed N. [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Khalid, Syed [Brookhaven National Lab. (BNL), Upton, NY (United States); Laveille, Paco V. [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); D' Souza, Lawrence [SABIC Corporate Research and Innovation Center, Thuwal (Saudi Arabia); Clo, Alain [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia); Basset, Jean-Marie [King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia)

    2015-02-03

    The surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. Moreover, the evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. The catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

  1. Understanding the atomic-level process of CO-adsorption-driven surface segregation of Pd in (AuPd)147 bimetallic nanoparticles.

    Science.gov (United States)

    An, Hyesung; Ha, Hyunwoo; Yoo, Mi; Kim, Hyun You

    2017-08-24

    When the elements that compose bimetallic catalysts interact asymmetrically with reaction feedstock, the surface concentration of the bimetallic catalysts and the morphology of the reaction center evolve dynamically as a function of environmental factors such as the partial pressure of the triggering molecule. Relevant experimental and theoretical findings of the dynamic structural evolution of bimetallic catalysts under the reaction conditions are emerging, thus enabling the design of more consistent, reliable, and efficient bimetallic catalysts. In an initial attempt to provide an atomic-level understanding of the adsorption-induced structural evolution of bimetallic nanoparticles (NPs) under CO oxidation conditions, we used density functional theory to study the details of CO-adsorption-driven Pd surface segregation in (AuPd)147 bimetallic NPs. The strong CO affinity of Pd provides a driving force for Pd surface segregation. We found that the vertex site of the NP becomes a gateway for the initial Pd-Au swapping and the subsequent formation of an internal vacancy. This self-generated internal vacancy easily diffuses inside the NP and activates Pd-Au swapping pathways in the (100) NP facet. Our results reveal how the surface and internal concentrations of bimetallic NPs respond immediately to changes in the reaction conditions. Our findings should aid in the rational design of highly active and versatile bimetallic catalysts by considering the environmental factors that systematically affect the structure of bimetallic catalysts under the reaction conditions.

  2. Growth of Three-Shell Onionlike Bimetallic Nanoparticles

    Science.gov (United States)

    Baletto, F.; Mottet, C.; Ferrando, R.

    2003-04-01

    We show by molecular dynamics simulations on three systems (B/A=Pd/Ag, Cu/Ag, and Ni/Ag) that three-shell metallic nanoparticles made by a core of a metal A, an intermediate shell of metal B and an external shell of metal A (A-B-A nanoparticles) can be grown by deposition of B atoms onto an A core. The growth of the intermediate B shell is triggered by the fact that the most favorable positions for isolated B impurities inside A clusters are located just one layer below the cluster surface.

  3. Synthesis and characterization of (smif)2M(n) (n = 0, M = V, Cr, Mn, Fe, Co, Ni, Ru; n = +1, M = Cr, Mn, Co, Rh, Ir; smif =1,3-di-(2-pyridyl)-2-azaallyl).

    Science.gov (United States)

    Frazier, Brenda A; Bartholomew, Erika R; Wolczanski, Peter T; DeBeer, Serena; Santiago-Berrios, Mitk'El; Abruña, Hector D; Lobkovsky, Emil B; Bart, Suzanne C; Mossin, Susanne; Meyer, Karsten; Cundari, Thomas R

    2011-12-19

    A series of Werner complexes featuring the tridentate ligand smif, that is, 1,3-di-(2-pyridyl)-2-azaallyl, have been prepared. Syntheses of (smif)(2)M (1-M; M = Cr, Fe) were accomplished via treatment of M(NSiMe(3))(2)(THF)(n) (M = Cr, n = 2; Fe, n = 1) with 2 equiv of (smif)H (1,3-di-(2-pyridyl)-2-azapropene); ortho-methylated ((o)Mesmif)(2)Fe (2-Fe) and ((o)Me(2)smif)(2)Fe (3-Fe) were similarly prepared. Metatheses of MX(2) variants with 2 equiv of Li(smif) or Na(smif) generated 1-M (M = Cr, Mn, Fe, Co, Ni, Zn, Ru). Metathesis of VCl(3)(THF)(3) with 2 Li(smif) with a reducing equiv of Na/Hg present afforded 1-V, while 2 Na(smif) and IrCl(3)(THF)(3) in the presence of NaBPh(4) gave [(smif)(2)Ir]BPh(4) (1(+)-Ir). Electrochemical experiments led to the oxidation of 1-M (M = Cr, Mn, Co) by AgOTf to produce [(smif)(2)M]OTf (1(+)-M), and treatment of Rh(2)(O(2)CCF(3))(4) with 4 equiv Na(smif) and 2 AgOTf gave 1(+)-Rh. Characterizations by NMR, EPR, and UV-vis spectroscopies, SQUID magnetometry, X-ray crystallography, and DFT calculations are presented. Intraligand (IL) transitions derived from promotion of electrons from the unique CNC(nb) (nonbonding) orbitals of the smif backbone to ligand π*-type orbitals are intense (ε ≈ 10,000-60,000 M(-1)cm(-1)), dominate the UV-visible spectra, and give crystals a metallic-looking appearance. High energy K-edge spectroscopy was used to show that the smif in 1-Cr is redox noninnocent, and its electron configuration is best described as (smif(-))(smif(2-))Cr(III); an unusual S = 1 EPR spectrum (X-band) was obtained for 1-Cr.

  4. Weighted Clustering

    DEFF Research Database (Denmark)

    Ackerman, Margareta; Ben-David, Shai; Branzei, Simina

    2012-01-01

    We investigate a natural generalization of the classical clustering problem, considering clustering tasks in which different instances may have different weights.We conduct the first extensive theoretical analysis on the influence of weighted data on standard clustering algorithms in both...... the partitional and hierarchical settings, characterizing the conditions under which algorithms react to weights. Extending a recent framework for clustering algorithm selection, we propose intuitive properties that would allow users to choose between clustering algorithms in the weighted setting and classify...

  5. Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng; Lu, Weigang; Wang, Xuan; Zhang, Qiang; Bosch, Mathieu; Liu, Tian-Fu; Lian, Xizhen; Zhou, Hong-Cai

    2015-10-23

    Cooperative cluster metalation and ligand migration were performed on a Zr-MOF, leading to the isolation of unique bimetallic MOFs based on decanuclear Zr6M4 (M=Ni, Co) clusters. The M2+ reacts with the μ3-OH and terminal H2O ligands on an 8-connected [Zr6O4(OH)8(H2O)4] cluster to form a bimetallic [Zr6M4O8(OH)8(H2O)8] cluster. Along with the metalation of Zr6 cluster, ligand migration is observed in which a Zr–carboxylate bond dissociates to form a M–carboxylate bond. Single-crystal to single-crystal transformation is realized so that snapshots for cooperative cluster metalation and ligand migration processes are captured by successive single-crystal X-ray structures. In3+ was metalated into the same Zr-MOF which showed excellent catalytic activity in the acetaldehyde cyclotrimerization reaction. This work not only provides a powerful tool to functionalize Zr-MOFs with other metals, but also structurally elucidates the formation mechanism of the resulting heterometallic MOFs.

  6. Photochemistry and Redox Chemistry of an Unsymmetrical Bimetallic Copper(I) Complex.

    Science.gov (United States)

    Back, Oliver; Leppin, Jana; Förster, Christoph; Heinze, Katja

    2016-10-03

    The bimetallic copper(I) complex Cu2L2 (cis-1) is formed with high diasteroselectivity from [Cu(NCCH3)4][BF4] and HL (4-tert-butyl phenyl(pyrrolato-2-yl-methylene)amine) in a kinetically controlled reaction. cis-1 features a rather short Cu···Cu distance of 2.4756(6) Å and is weakly emissive at room temperature in solution. Oxidatively triggered disproportionation of cis-1 yields elemental copper and the mononuclear copper(II) complex CuL2 (trans-2). One-electron reduction of trans-2 gives cuprate [2](-) with a bent bis(pyrrolato) coordinated copper(I) entity. The imine donor atoms of [2](-) can insert an additional copper(I) ion giving exclusively the bimetallic complex cis-1 closing the oxidation-elimination-reduction-insertion cycle.

  7. Template-Directed Approach Towards the Realization of Ordered Heterogeneity in Bimetallic Metal-Organic Frameworks.

    Science.gov (United States)

    Kim, Daeok; Coskun, Ali

    2017-04-24

    Controlling the arrangement of different metal ions to achieve ordered heterogeneity in metal-organic frameworks (MOFs) has been a great challenge. Herein, we introduce a template-directed approach, in which a 1D metal-organic polymer incorporating well-defined binding pockets for the secondary metal ions used as a structural template and starting material for the preparation of well-ordered bimetallic MOF-74s under heterogeneous-phase hydrothermal reaction conditions in the presence of secondary metal ions such as Ni(2+) and Mg(2+) in 3 h. The resulting bimetallic MOF-74s were found to possess a nearly 1:1 metal ratio regardless of their initial stoichiometry in the reaction mixture, thus demonstrating the possibility of controlling the arrangement of metal ions within the secondary building blocks in MOFs to tune their intrinsic properties such as gas affinity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Synthesis of a discrete-action thermo-bimetallic actuator with a tongue

    Science.gov (United States)

    Nikolaeva, A.; McMillan, AJ; Gavriushin, S.

    2016-10-01

    The selection of suitable parameters, by experimental or intuitive processes for snap-through actuation of a bimetallic actuator at a prescribed temperature is an extremely time-consuming task. This paper describes a new methodology for the optimization of a discrete action thermo-bimetallic actuator with a tongue. This methodology makes it possible to solve the optimization task with higher efficiency. The requirement is to find optimal parameters values so that the actuator will make a snap-through at a given temperature. The constrained optimization task was performed using an evolutional algorithm and surrogate modelling and this was coded in Matlab. Functional relationships between the criteria and parameters were not set explicitly, but they were calculated using finite element method, each simulation of which was performed in Abaqus.

  9. A Highly Efifcient and Selective Water-Soluble Bimetallic Catalyst for Hydrogenation of Chloronitrobenzene to Chloroaniline

    Institute of Scientific and Technical Information of China (English)

    Zhou Yafen; Yang Wenjuan; Zhou Limei; Wang Manman; Ma Xiaoyan

    2015-01-01

    Selective hydrogenation of chloronitrobenzene (CNB) to chloroaniline (CAN) catalyzed by water-soluble Ru/Pt bimetallic catalyst in an aqueous-organic biphasic system was studied. It was found that the catalytic activity increased ob-viously due to the addition of platinum. Ru/Pt bimetallic catalysts exhibited a strong synergistic effect when the molar ratio of Pt was in the range of 5%—80%. Under the mild conditions including a temperature of 25℃, a hydrogen pressure of 1.0 MPa and a Pt molar ratio of 20%, the conversion of p-chloronitrobenzene (p-CNB) reached 99.9%, with the selectivity to p-chloroaniline (p-CAN) equating to 99.4%. The Ru/Pt catalyst also showed high activity and selectivity for the hydrogena-tion of other chloro-and dichloro-nitrobenzenes with different substituted positions. In addition, the catalyst can be recycled ifve times without signiifcant loss of activity.

  10. The adsorption and decomposition of methane on Fe/Cu(110)bimetallic surface

    Institute of Scientific and Technical Information of China (English)

    鲍世宁; 范朝阳; 李海洋; 徐亚伯

    1995-01-01

    The adsorption and decomposition of methane on Fe/Cu(110) bimetallic surface have been studied by HREELS and ARUPS. The results show that the activation energy of dissociative chemisorption for methane is reduced obviously by preadsorption of iron on copper surface. The chemisorption probability of methane is so high on Fe/Cu(110) bimetallic surface that chemisorption of methane can be observed at room temperature and low pressure. When the iron coverage is lower than 1 ML, the chemisorption probability increases linearly with increasing iron coverage. After the iron coverage is beyond 1 ML(<2ML) the probability continues increasing. The iron atom with disordered structure can offer the site of dissociative chemisorption to methane too. A hydroformyl species is formed through interaction between methane and the preadsorbed oxygen atoms. The reaction enhances the dissociative chemisorption of methane on the surface.

  11. Kinetic Study on the Formation of Bimetallic Core-Shell Nanoparticles via Microemulsions

    Directory of Open Access Journals (Sweden)

    Concha Tojo

    2014-11-01

    Full Text Available Computer calculations were carried out to determine the reaction rates and the mean structure of bimetallic nanoparticles prepared via a microemulsion route. The rates of reaction of each metal were calculated for a particular microemulsion composition (fixed intermicellar exchange rate and varying reduction rate ratios between both metal and metal salt concentration inside the micelles. Model predictions show that, even in the case of a very small difference in reduction potential of both metals, the formation of an external shell in a bimetallic nanoparticle is possible if a large reactant concentration is used. The modification of metal arrangement with concentration was analyzed from a mechanistic point of view, and proved to be due to the different impact of confinement on each metal: the reaction rate of the faster metal is only controlled by the intermicellar exchange rate but the slower metal is also affected by a cage-like effect.

  12. Kinetic Study on the Formation of Bimetallic Core-Shell Nanoparticles via Microemulsions

    Science.gov (United States)

    Tojo, Concha; Vila-Romeu, Nuria

    2014-01-01

    Computer calculations were carried out to determine the reaction rates and the mean structure of bimetallic nanoparticles prepared via a microemulsion route. The rates of reaction of each metal were calculated for a particular microemulsion composition (fixed intermicellar exchange rate) and varying reduction rate ratios between both metal and metal salt concentration inside the micelles. Model predictions show that, even in the case of a very small difference in reduction potential of both metals, the formation of an external shell in a bimetallic nanoparticle is possible if a large reactant concentration is used. The modification of metal arrangement with concentration was analyzed from a mechanistic point of view, and proved to be due to the different impact of confinement on each metal: the reaction rate of the faster metal is only controlled by the intermicellar exchange rate but the slower metal is also affected by a cage-like effect. PMID:28788260

  13. Core–Shell Bimetallic Nanoparticles Robustly Fixed on the Outermost Surface of Magnetic Silica Microspheres

    Science.gov (United States)

    Park, Hye Hun; Woo, Kyoungja; Ahn, Jae-Pyoung

    2013-01-01

    The major challenges in practically utilising the immense potential benefits of nanomaterials are controlling aggregation, recycling the nanomaterials, and fabricating well-defined nanoparticulate materials using innovative methods. We present a novel innovative synthetic strategy for core–shell bimetallic nanoparticles that are well-defined, ligand-free, and robustly fixed on the outermost surface of recyclable magnetic silica microspheres. The strategy includes seeding, coalescing the seeds to cores, and then growing shells from the cores on aminopropyl-functionalised silica microspheres so that the cores and aminopropyl moieties are robustly embedded in the shell materials. The representative Au–Ag bimetallic nanoparticles fixed on the microsphere showed excellent catalytic performance that remained consistent during repeated catalytic cycles. PMID:23511209

  14. LPG sensing performance of CuO–Ag2O bimetallic oxide nanoparticles

    Directory of Open Access Journals (Sweden)

    K.R. Nemade

    2015-10-01

    Full Text Available In the present article, we synthesized CuO–Ag2O bimetallic oxide nanoparticles by using microwave assisted and solid state diffusion routes. The structural, morphological, optical and thermal study of as-synthesized materials were done through X-ray diffractometer (XRD, scanning electron microscope (SEM, Fourier transform infrared (FTIR, ultraviolet–visible (UV–vis and thermogravimetric analysis (TGA, respectively. Comparatively different sensing parameters such as sensing response at room temperature, operating temperature, response and recovery time and stability characteristics were investigated and discussed for liquefied petroleum gas (LPG. The CuO–Ag2O bimetallic oxide nanoparticles synthesized by microwave assisted route shows good gas sensing properties.

  15. Synthesis and exceptional thermal stability of Mg-based bimetallic nanoparticles during hydrogenation

    Science.gov (United States)

    Krishnan, Gopi; Negrea, Raluca F.; Ghica, Corneliu; Ten Brink, Gert H.; Kooi, Bart J.; Palasantzas, George

    2014-09-01

    Here we report the extraordinary thermal stability of Mg rich bimetallic nanoparticles (NPs), which is important for hydrogen storage technology. The enhanced NP stability is accomplished because of two critical improvements: (i) no void development within NPs (nanoscale Kirkendall effect) during their formation and (ii) suppressed Mg evaporation and NP hollowing during Mg hydrogenation at elevated temperature. The mechanism leading to the improved thermal stability of Mg-based bimetallic NPs is shown to be due to MgH2 hydride formation before evaporation can take place. These findings were tested for various compositions of Mg with Ni, Cu, and Ti, which are interesting combinations of materials for hydrogen storage systems. To achieve this we first demonstrate the synthesis mechanism of Mg-Ni and Mg-Cu NPs, which is well controlled at the single particle level, in order to accomplish multi-shell, alloy and intermetallic structures of interest for hydrogen storage tests. Aberration corrected transmission electron microscopy was carried out to unravel the detailed atomic structure and composition of the bimetallic NPs after production, processing, and hydrogenation. Finally, a simple and effective methodology is proposed for tuning the composition of the Mg-based bimetallic NPs based on the temperature-dependent nucleation behavior of NPs in the gas-phase.Here we report the extraordinary thermal stability of Mg rich bimetallic nanoparticles (NPs), which is important for hydrogen storage technology. The enhanced NP stability is accomplished because of two critical improvements: (i) no void development within NPs (nanoscale Kirkendall effect) during their formation and (ii) suppressed Mg evaporation and NP hollowing during Mg hydrogenation at elevated temperature. The mechanism leading to the improved thermal stability of Mg-based bimetallic NPs is shown to be due to MgH2 hydride formation before evaporation can take place. These findings were tested for various

  16. Synthesis, characterization, and growth simulations of Cu–Pt bimetallic nanoclusters

    Directory of Open Access Journals (Sweden)

    Subarna Khanal

    2014-08-01

    Full Text Available Highly monodispersed Cu–Pt bimetallic nanoclusters were synthesized by a facile synthesis approach. Analysis of transmission electron microscopy (TEM and spherical aberration (Cs-corrected scanning transmission electron microscopy (STEM images shows that the average diameter of the Cu–Pt nanoclusters is 3.0 ± 1.0 nm. The high angle annular dark field (HAADF-STEM images, intensity profiles, and energy dispersive X-ray spectroscopy (EDX line scans, allowed us to study the distribution of Cu and Pt with atomistic resolution, finding that Pt is embedded randomly in the Cu lattice. A novel simulation method is applied to study the growth mechanism, which shows the formation of alloy structures in good agreement with the experimental evidence. The findings give insight into the formation mechanism of the nanosized Cu–Pt bimetallic catalysts.

  17. Porous Diatomite-Immobilized Cu–Ni Bimetallic Nanocatalysts for Direct Synthesis of Dimethyl Carbonate

    Directory of Open Access Journals (Sweden)

    Yong Chen

    2012-01-01

    Full Text Available A series of diatomite-immobilized Cu–Ni bimetallic nanocatalysts was prepared under ultrasonication and evaluated for the direct synthesis of dimethyl carbonate under various conditions. Upon being fully characterized by TPR, TPD, BET, SEM, XRD, and XPS methodologies, it is found that the bimetallic composite is effectively alloyed and well immobilized inside or outside the pore of diatomite. Under the optimal conditions of 1.2 MPa and 120∘C, the prepared catalyst with loading of 15% exhibited the highest methanol conversion of 6.50% with DMC selectivity of 91.2% as well as more than 10-hour lifetime. The possible reaction mechanism was proposed and discussed in detail. To our knowledge, this is the first report to use diatomite as a catalyst support for direct DMC synthesis from methanol and CO2.

  18. Effect of annealing on martensitic transformations in "steel - TiNi alloy" explosion welded bimetallic composite

    Science.gov (United States)

    Belyaev, S. P.; Rubanik, V. V.; Resnina, N. N.; Rubanik, V. V.; Rubanik, O. E.

    2011-01-01

    The effect of explosion welding on the kinetics of martensitic transformations in a "steel - TiNi alloy" bimetallic composite and the effect of the temperature and duration of annealing on recovery of the characteristics of the martensitic transformations are studied. It is shown that annealing in the range of 450 - 600°C accompanied by retrogression of structure causes full recovery of the transformation kinetics in the alloy.

  19. 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.

  20. 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...

  1. Stability of the Shallow Axisymmetric Parabolic-Conic Bimetallic Shell by Nonlinear Theory

    OpenAIRE

    M. Jakomin; Kosel, F.

    2011-01-01

    In this contribution, we discuss the stress, deformation, and snap-through conditions of thin, axi-symmetric, shallow bimetallic shells of so-called parabolic-conic and plate-parabolic type shells loaded by thermal loading. According to the theory of the third order that takes into account the balance of forces on a deformed body, we present a model with a mathematical description of the system geometry, displacements, stress, and thermoelastic deformations. The equations are based on the lar...

  2. Catalytic Activity of Mono- and Bi-Metallic Nanoparticles Synthesized via Microemulsions

    Directory of Open Access Journals (Sweden)

    Ramona Y.G. König

    2014-07-01

    Full Text Available Water-in-oil (w/o microemulsions were used as a template for the synthesis of mono- and bi-metallic nanoparticles. For that purpose, w/o-microemulsions containing H2PtCl6, H2PtCl6 + Pb(NO32 and H2PtCl6 + Bi(NO3, respectively, were mixed with a w/o-microemulsion containing the reducing agent, NaBH4. The results revealed that it is possible to synthesize Pt, PtPb and PtBi nanoparticles of ~3–8 nm in diameter at temperatures of about 30°C. The catalytic properties of the bimetallic PtBi and PtPb nanoparticles were studied and compared with monometallic platinum nanoparticles. Firstly, the electrochemical oxidation of formic acid to carbon monoxide was investigated, and it was found that the resistance of the PtBi and PtPb nanoparticles against the catalyst-poisoning carbon monoxide was significantly higher compared to the Pt nanoparticles. Secondly, investigating the reduction of 4-nitrophenol to 4-aminophenol,we found that the bimetallic NPs are most active at 23 °C, while the order of the activity changes at higher temperatures, i.e., that the Pt nanoparticles are the most active ones at 36 and 49 °C. Furthermore, we observed a strong influence of the support, which was either a polymer or Al2O3. Thirdly, for the hydrogenation of allylbenzene to propylbenzene, the monometallic Pt NPs turned out to be the most active catalysts, followed by the PtPb and PtBi NPs. Comparing the two bimetallic nanoparticles, one sees that the PtPb NPs are significantly more active than the respective PtBi NPs.

  3. Levulinic acid hydrogenolysis on Al2O3-based Ni-Cu bimetallic catalysts

    Institute of Scientific and Technical Information of China (English)

    Iker Obregón; Eriz Corro; Urko Izquierdo; Jesus Requies; Pedro L. Arias

    2014-01-01

    Inexpensive γ-alumina-based nickel-copper bimetallic catalysts were studied for the hydrogenolysis of levulinic acid, a key platform molecule for biomass conversion to biofuels and other valued chemicals, into γ-valerolactone as a first step towards the production of 2-methyltetrahydrofurane. The activities of both monometallic and bimetallic catalysts were tested. Their textural and chemical characteristics were determined by nitrogen physisorption, elemental analysis, temperature-pro-grammed ammonia desorption, and temperature-programmed reduction. The monometallic nickel catalyst showed high activity but the highest by-product production and significant amounts of carbon deposited on the catalyst surface. The copper monometallic catalyst showed the lowest activity but the lowest carbon deposition. The incorporation of the two metals generated a bimetal-lic catalyst that displayed a similar activity to that of the Ni monometallic catalyst and significantly low by-product and carbon contents, indicating the occurrence of important synergetic effects. The influence of the preparation method was also examined by studying impregnated- and sol-gel-derived bimetallic catalysts. A strong dependency on the preparation procedure and calcina-tion temperature was observed. The highest activity per metal atom was achieved using the sol-gel-derived catalyst that was calcined at 450 °C. High reaction rates were achieved;the total levulinic acid conversion was obtained in less than 2 h of reaction time, yielding up to 96%γ-valerolactone, at operating temperature and pressure of 250 °C and 6.5 MPa hydrogen, respec-tively.

  4. Desorption of Furfural from Bimetallic Pt-Fe Oxides/Alumina Catalysts

    OpenAIRE

    Gloria Lourdes Dimas-Rivera; Javier Rivera de la Rosa; Carlos J. Lucio-Ortiz; José Antonio De los Reyes Heredia; Virgilio González González; Tomás Hernández

    2014-01-01

    In this work, the desorption of furfural, which is a competitive intermediate during the production of biofuel and valuable aromatic compounds, was studied using pure alumina, as well as alumina impregnated with iron and platinum oxides both individually and in combination, using thermogravimetric analysis (TGA). The bimetallic sample exhibited the lowest desorption percentage for furfural. High-resolution transmission electron microscopy (HRTEM) imaging revealed the intimate connection betwe...

  5. LPG sensing performance of CuO–Ag2O bimetallic oxide nanoparticles

    OpenAIRE

    K.R. Nemade; S.A. Waghuley

    2015-01-01

    In the present article, we synthesized CuO–Ag2O bimetallic oxide nanoparticles by using microwave assisted and solid state diffusion routes. The structural, morphological, optical and thermal study of as-synthesized materials were done through X-ray diffractometer (XRD), scanning electron microscope (SEM), Fourier transform infrared (FTIR), ultraviolet–visible (UV–vis) and thermogravimetric analysis (TGA), respectively. Comparatively different sensing parameters such as sensing response at ro...

  6. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Chunshan Song; Schobert, H.H.; Parfitt, D.P. [and others

    1997-11-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on exploring novel bimetallic dispersed catalysts for coal liquefaction and the effectiveness of temperature-programmed liquefaction using dispersed catalysts. The primary objective of this research was to explore novel bimetallic dispersed catalysts from organometallic molecular precursors, that could be used in low concentrations but exhibit relatively high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. We have synthesized and tested various catalyst precursors in liquefaction of subbituminous and bituminous coals and in model compound studies to examine how do the composition and structure of the catalytic precursors affect their effectiveness for coal liquefaction under different reaction conditions, and how do these factors affect their catalytic functions for hydrogenation of polyaromatic hydrocarbons, for cleavage of C-C bonds in polycyclic systems such as 4-(1-naphthylmethyl)bibenzyl, for hydrogenolysis of C-O bond such as that in dinaphthylether, for hydrodeoxygenation of phenolic compounds and other oxygen-containing compounds such as xanthene, and for hydrodesulfurization of polycyclic sulfur compounds such as dibenzothiophene. The novel bimetallic and monometallic precursors synthesized and tested in this project include various Mo- and Fe-based compounds.

  7. Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Jianlong; Li, Pengwei; Sang, Shengbo, E-mail: sbsang@tyut.edu.cn; Zhang, Wendong, E-mail: wdzhang@tyut.edu.cn; Li, Gang; Hu, Jie [Micro and Nano-system Research Centre, College of Information Engineering, Taiyuan University of Technology, 030024, Taiyuan (China); Zhou, Zhaoying, E-mail: zhouzy@mail.tsinghua.edu.cn; Yang, Xing; Dong, Hualai [MEMS Laboratory, Department of Precision Instruments, Tsinghua University, 100084, Beijing (China)

    2014-03-15

    Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and UV–vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA) models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electric field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO) flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS) activity, using 4-mercaptopyridine (4-MP) as model molecules.

  8. Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

    Science.gov (United States)

    Ji, Jianlong; Li, Pengwei; Sang, Shengbo; Zhang, Wendong; Zhou, Zhaoying; Yang, Xing; Dong, Hualai; Li, Gang; Hu, Jie

    2014-03-01

    Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and UV-vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA) models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electric field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO) flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS) activity, using 4-mercaptopyridine (4-MP) as model molecules.

  9. Characterization of Bimetallic Castings with an Austenitic Working Surface Layer and an Unalloyed Cast Steel Base

    Science.gov (United States)

    Wróbel, Tomasz

    2014-05-01

    The paper presents the technology of bimetallic castings based on the founding method of layer coating directly in the cast process of the so-called method of mold cavity preparation. The prepared castings consist of two fundamental parts, i.e., the base and the working surface layer. The base part of the bimetallic casting is typical foundry material, i.e., unalloyed cast steel, whereas the working layer is a plate of austenitic alloy steel sort X2CrNi 18-9. The quality of the joint between the base part and the working layer was evaluated on the basis of ultrasonic non-destructive testing and structure examinations containing metallographic macro- and microscopic studies with the use of a light microscope (LOM) with microhardness measurements and a scanning electron microscope (SEM) with microanalysis of the chemical composition (energy dispersive spectroscopy—EDS). On the basis of the obtained results it was confirmed that the decisive phenomena needed to create a permanent joint between the two components of the bimetallic casting are carbon and heat transport in the direction from the high-carbon and hot base material which was poured into the mold in the form of liquid metal to the low-carbon and cold material of the working layer which was placed in the mold cavity in the form of a monolithic insert.

  10. Ionic liquid assisted synthesis of Au-Pd bimetallic particles with enhanced electrocatalytic activity.

    Science.gov (United States)

    Li, Zhonghao; Li, Rui; Mu, Tiancheng; Luan, Yuxia

    2013-05-03

    Morphology- and composition-controlled synthesis of Au-Pd bimetallic particles was realized by a facile ionic liquid assisted route at room temperature. The morphologies of the synthesized particles, such as nanoflake-constructed spheres with a core-shell structure, nanoparticle-constructed spheres, and nanoparticle-constructed dendrites, could be well controlled by the present route. The ionic liquid was found to play a key role in the formation of these interesting particles. Moreover, the composition (Au:Pd) of the particles could be modulated by means of the molar ratio of the metal precursors in the feeding solutions. The Au-Pd bimetallic particles exhibit high electrocatalytic activity toward oxidation of ethanol and formic acid. Furthermore, cyclic voltammetric studies on the as-prepared Au-Pd bimetallic particles revealed good electroactivity for H2O2, which results in an effective amperometric H2O2 sensor. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Prediction of atomic structure of Pt-based bimetallic nanoalloys by using genetic algorithm

    Science.gov (United States)

    Oh, Jung Soo; Nam, Ho-Seok; Choi, Jung-Hae; Lee, Seung-Cheol

    2013-05-01

    The atom-arrangements in Pt-based bimetallic nanoalloys were predicted by the combined use of genetic algorithm (GA) and molecular dynamics (MD) simulations. The nanoparticles of these nanoalloys were assumed to be a 3.5 nm-diameter truncated octahedron with Pt and noble metals of fixed composition ratio of 1:1. For the GA, a Python code, which concurrently linked with the MD method that uses the embedded atom method inter-atomic potentials, was developed for the prediction of the atom arrangements in these bimetallic nanoalloys. Successfully, the GA calculation predicted the core-shell structures for both Pt-Ag and Pt-Au nanoalloy, but an onion-like multilayered core-shell structure for Pt-Cu nanoalloy. The structural characteristics in the bimetallic nanoalloy were mainly due to the differences in the surface energy and cohesive energy between Pt and the other alloying metal elements and their miscibility gap and so on. Briefly, the prediction performance was analyzed to show the superior searching ability of GA.

  12. Synthesis and characterization of immobilized Ni-Co bimetallic using Tapanuli clay for catalyst application

    Energy Technology Data Exchange (ETDEWEB)

    Nuryanti,; Juwono, Ariadne L., E-mail: ariadne@sci.ui.ac.id [Department of Physics, FMIPA, Universitas Indonesia, Kampus UI Depok (Indonesia); Krisnandi, Yuni K. [Department of Chemistry, FMIPA, Universitas Indonesia, Kampus UI Depok (Indonesia)

    2016-04-19

    Heterogeneous catalysts hold various advantages, namely, easy to separate from their products, reusable and regarded as environmental friendly materials. The synthesis of immobilized Ni monometallic, Co monometallic and Ni-Co bimetallic by Tapanuli clay were carried out using intercalation method. Firstly, the synthesis of Na-Bentonite was conducted to provide sufficient area to immobilize bimetal in the clay interlayer. Secondly, Ni, Co and Ni-Co were immobilized in the Tapanuli clay interlayer. Several techniques, such as X-Ray Diffraction, Fourier Transform Infra Red and Energy Dispersive X-Ray Analysis were applied to characterize and compare the properties of the synthesized materials. The results showed that the insertion of Ni, Co and Ni-Co in the clay interlayer occurred through a cation exchange reaction. The Energy Dispersive X-Ray analysis for Ni-Co bimetallic showed that the immobilized Ni and Co in the clay is in the ratio of 1:1. Catalytic test with Gas Chromatography showed that Ni-Co bimetallic generates a higher yield percentage compared to Ni and Co monometallic.

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

    Science.gov (United States)

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

    2014-12-24

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

  14. DNA-Mediated Morphological Control of Pd-Au Bimetallic Nanoparticles.

    Science.gov (United States)

    Satyavolu, Nitya Sai Reddy; Tan, Li Huey; Lu, Yi

    2016-12-21

    Recent reports have shown that different DNA sequences can mediate the control of shapes and surface properties of nanoparticles. However, all previous studies have involved only monometallic particles, most of which were gold nanoparticles. Controlling the shape of bimetallic nanoparticles is more challenging, and there is little research into the use of DNA-based ligands for their morphological control. We report the DNA-templated synthesis of Pd-Au bimetallic nanoparticles starting from palladium nanocube seeds. The presence of different homo-oligomer DNA sequences containing 10 deoxy-ribonucleotides of thymine, adenine, cytosine, or guanine results in the growth of four distinct morphologies. Through detailed kinetic studies by absorption spectroscopy, scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM), we have determined the role of DNA in controlling Pd-Au nanoparticle growth morphologies. One major function of DNA is affecting various properties of the incoming metal atoms, including their diffusion and deposition on the Pd nanocube seed. Interestingly, nanoparticle growth in the presence of A10 follows an aggregative growth mechanism that is unique when compared to the other base oligomers. These findings demonstrate that DNA can allow for programmable control of bimetallic nanoparticle morphologies, resulting in more complex hybrid materials with different plasmonic properties. The capability to finely tune multimetallic nanoparticle morphology stems from the versatile structure that is unique to DNA in comparison to conventionally used capping agents in colloidal nanomaterial synthesis.

  15. Tuning the composition of AuPt bimetallic nanoparticles for antibacterial application.

    Science.gov (United States)

    Zhao, Yuyun; Ye, Chunjie; Liu, Wenwen; Chen, Rong; Jiang, Xingyu

    2014-07-28

    We show that bimetallic nanoparticles (NPs) of AuPt without any surface modification are potent antibiotic reagents, while pure Au NPs or pure Pt NPs display no antibiotic activities. The most potent antibacterial AuPt NPs happen to be the most effective catalysts for chemical transformations. The mechanism of antibiotic action includes the dissipation of membrane potential and the elevation of adenosine triphosphate (ATP) levels. These bimetallic NPs are unique in that they do not produce reactive oxygen species as most antibiotics do. Being non-toxic to human cells, these bimetallic noble NPs might open an entry to a new class of antibiotics. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

  16. Laser synthesis of ligand-free bimetallic nanoparticles for plasmonic applications.

    Science.gov (United States)

    Intartaglia, R; Das, G; Bagga, K; Gopalakrishnan, A; Genovese, A; Povia, M; Di Fabrizio, E; Cingolani, R; Diaspro, A; Brandi, F

    2013-03-07

    A picosecond laser ablation approach has been developed for the synthesis of ligand-free AuAg bimetallic NPs where the relative amount of Ag is controlled in situ through a laser shielding effect. Various measurements, such as optical spectroscopy, transmission electron microscopy combined with energy dispersive X-ray spectroscopy and inductively coupled plasma optical emission spectrometry, revealed the generation of homogenous 15 nm average size bimetallic NPs with different compositions and tunable localized surface plasmon resonance. Furthermore, ligand-free metallic nanoparticles with respect to chemically synthesized nanoparticles display outstanding properties, i.e. featureless Raman background spectrum, which is a basic requirement in many plasmonic applications such as Surface Enhanced Raman Spectroscopy. Various molecules were chemisorbed on the nanoparticle and SERS investigations were carried out, by varying the laser wavelength. The SERS enhancement factor for AuAg bimetallic NPs shows an enhancement factor of about 5.7 × 10(5) with respect to the flat AuAg surface.

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

    Science.gov (United States)

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

    2014-03-10

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

  18. Effects of bimetallic nanoparticles on seed germination frequency and biochemical characterisation of Eruca sativa.

    Science.gov (United States)

    Zaka, Mehreen; Abbasi, Bilal Haider

    2017-04-01

    In the modern era of science and technology, nanotechnology is becoming popular science field because materials at nanoscale contain improved physical, chemical and biological properties. This study aimed to explore the capacity of bimetallic nanoparticle alloys of silver (Ag), copper (Cu), gold (Au) in different ratios to evaluate the effects on medicinally important plant Eruca sativa. Biochemical parameters of Eruca sativa were studied by applying bimetallic alloy nanoparticles. Seeds of Eruca sativa were germinated on Murashige and Skoog medium with various combinations of nanoparticles suspension employed in concentration of (30 µg/ml). Bimetallic alloys were considered as a stress inducing factor in plants while studying the phytotoxicity. Many secondary metabolites were released because defensive mechanism of plants was active in response to stress. Such secondary metabolites produced in medicinal plants have a great capability in treating the human diseases. In the authors' study, nanoparticles of small size and of high toxicity effect produced more secondary metabolites like total protein content, total flavonoids and total phenolic content.

  19. Air stable magnetic bimetallic Fe-Ag nanoparticles for advanced antimicrobial treatment and phosphorus removal.

    Science.gov (United States)

    Marková, Zdenka; Šišková, Karolína Machalová; Filip, Jan; Čuda, Jan; Kolář, Milan; Šafářová, Klára; Medřík, Ivo; Zbořil, Radek

    2013-05-21

    We report on new magnetic bimetallic Fe-Ag nanoparticles (NPs) which exhibit significant antibacterial and antifungal activities against a variety of microorganisms including disease causing pathogens, as well as prolonged action and high efficiency of phosphorus removal. The preparation of these multifunctional hybrids, based on direct reduction of silver ions by commercially available zerovalent iron nanoparticles (nZVI) is fast, simple, feasible in a large scale with a controllable silver NP content and size. The microscopic observations (transmission electron microscopy, scanning electron microscopy/electron diffraction spectroscopy) and phase analyses (X-ray diffraction, Mössbauer spectroscopy) reveal the formation of Fe₃O₄/γ-FeOOH double shell on a "redox" active nZVI surface. This shell is probably responsible for high stability of magnetic bimetallic Fe-Ag NPs during storage in air. Silver NPs, ranging between 10 and 30 nm depending on the initial concentration of AgNO₃, are firmly bound to Fe NPs, which prevents their release even during a long-term sonication. Taking into account the possibility of easy magnetic separation of the novel bimetallic Fe-Ag NPs, they represent a highly promising material for advanced antimicrobial and reductive water treatment technologies.

  20. Fractal Dimension Calculation of a Manganese-Chromium Bimetallic Nanocomposite Using Image Processing

    Directory of Open Access Journals (Sweden)

    Amir Lashgari

    2015-01-01

    Full Text Available Bimetallic materials, which have the ability to convert heat change into mechanical movement, normally consist of two bonded strips of dissimilar metals that expand at different rates. We describe how we made a manganese-chromium (Mn-Cr bimetallic nanocomposite using the centrifuge method and a low-to-high approach. We conducted scanning electron microscope (SEM imaging, energy-dispersive X-ray spectroscopy (EDX analysis, and X-ray diffraction spectra of the nanocomposite to prove its identity. We examined how centrifuge speed, process time, and the use of an “intruder agent” affected the properties of the material. The fractal dimension is a significant factor that can be used to approximate the surface roughness, the texture segmentation, and an image of the studied compounds. We calculated the technique of fractal dimensions using image-processing values on a computer and histogram plot with the SEM image of the Mn-Cr bimetallic nanocomposite using MATLAB software. We applied the Statistical Package for the Social Sciences software for statistics data extracted from the SEM image of the nanocomposite and obtained the following results: mean = 1.778, median = 1.770, max = 1.98, min = 1.60, skewness = 0.177, range = 0.38, and harmonic mean = 1.771 for fractal dimension of the SEM image.

  1. Cation exchange resin immobilized bimetallic nickel-iron nanoparticles to facilitate their application in pollutants degradation.

    Science.gov (United States)

    Ni, Shou-Qing; Yang, Ning

    2014-04-15

    Nanoscale zerovalent iron (nZVI) usually suffers from reduction of reactivity by aggregation, difficulty of assembling, environmental release and health concerns. Furthermore, data are lacking on the effect of cheap nickel on debromination of decabromodiphenyl ether (DBDE) by immobilized nZVI in aqueous system. In this study, strong acid polystyrene cation-exchange resins with particle diameter from 0.4 to 0.6 mm were utilized as matrices to immobilize bimetallic nickel-iron nanoparticles in order to minimize aggregation and environmental leakage risks of nZVI and to enhance their reactivity. Elemental distribution mapping showed that iron particles distributed uniformly on the surface of the resin and nickel particles were dispersed homogeneously into Fe phase. The reaction rate of resin-bound nZVI is about 55% higher than that of dispersed nZVI. The immobilized bimetallic nanoparticles with 9.69% Ni had the highest debromination percent (96%) and reaction rate (0.493 1/h). The existence of Ni significantly improved the debromination rate, due to the surface coverage of catalytic metal on the reductive metal and the formation of a galvanic cell. The environmental dominant congeners, such as BDE 154, 153, 100, 99 and 47, were produced during the process. Outstanding reactive performance, along with magnetic separation assured that resin-bound bimetallic nickel-iron nanoparticles are promising material that can be utilized to remediate a wide variety of pollutants contaminated sites including polybrominated diphenyl ethers. Copyright © 2014 Elsevier Inc. All rights reserved.

  2. Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

    Directory of Open Access Journals (Sweden)

    Jianlong Ji

    2014-03-01

    Full Text Available Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM, energy dispersive X-ray spectrometer (EDS, transmission electron microscopy (TEM and UV–vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electric field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS activity, using 4-mercaptopyridine (4-MP as model molecules.

  3. The effect of intermolecular hydrogen bonding on the fluorescence of a bimetallic platinum complex.

    Science.gov (United States)

    Zhao, Guang-Jiu; Northrop, Brian H; Han, Ke-Li; Stang, Peter J

    2010-09-02

    The bimetallic platinum complexes are known as unique building blocks and arewidely utilized in the coordination-driven self-assembly of functionalized supramolecular metallacycles. Hence, photophysical study of the bimetallic platinum complexes will be very helpful for the understanding on the optical properties and further applications of coordination-driven self-assembled supramolecular metallacycles. Herein, we report steady-state and time-resolved spectroscopic experiments as well as quantum chemistry calculations to investigate the significant intermolecular hydrogen bonding effects on the intramolecular charge transfer (ICT) fluorescence of a bimetallic platinum compound 4,4'-bis(trans-Pt(PEt(3))(2)OTf)benzophenone 3 in solution. We demonstrated that the fluorescent state of compound 3 can be assigned as a metal-to-ligand charge transfer (MLCT) state. Moreover, it was observed that the formation of intermolecular hydrogen bonds can effectively lengthen the fluorescence lifetime of 3 in alcoholic solvents compared with that in hexane solvent. At the same time, the electronically excited states of 3 in solution are definitely changed by intermolecular hydrogen bonding interactions. As a consequence, we propose a new fluorescence modulation mechanism by hydrogen bonding to explain different fluorescence emissions of 3 in hydrogen-bonding solvents and nonhydrogen-bonding solvents.

  4. Ferrocenyl-cymantrenyl hetero-bimetallic chalcones: Synthesis, structure and biological properties

    Science.gov (United States)

    Mishra, Sasmita; Tirkey, Vijaylakshmi; Ghosh, Avishek; Dash, Hirak R.; Das, Surajit; Shukla, Madhulata; Saha, Satyen; Mobin, Sheikh M.; Chatterjee, Saurav

    2015-04-01

    Two new ferrocenyl-cymantrenyl bimetallic chalcones, [(CO)3Mn(η5-C5H4)C(O)CHdbnd CH(η5-C5H4)Fe(η5-C5H5)] (1) and [{(CO)3Mn(η5-C5H4)C(O)CHdbnd CH(η5-C5H4)}2Fe] (2) have been synthesized. Their reactivity study with triphenylphosphine and bis-(diphenylphosphino)ferrocene led to the isolation of phosphine substituted bimetallic chalcones (3-6). Single crystal X-ray structural characterization for 1 and its phosphine analogue (3) reveals their different conformational identity with anti-conformation for 1, while syn-conformation for 3. Investigation of antimalarial and antibacterial activities was carried out for compounds 1 and 2 against two strains of Plasmodium falciparum (3D7, K1) and four bacterial strains. TD-DFT calculation was performed for compound 1 and electrochemical properties were studied for bimetallic chalcone compounds by cyclic voltammetric technique.

  5. Synthesis and characterization of highly conductive Sn-Ag bimetallic nanoparticles for printed electronics

    Energy Technology Data Exchange (ETDEWEB)

    Jo, Yun Hwan; Jung, Inyu; Kim, Na Rae; Lee, Hyuck Mo, E-mail: hmlee@kaist.ac.kr [KAIST, Department of Materials Science and Engineering (Korea, Republic of)

    2012-03-15

    To synthesize low-cost, highly conductive metal nanoparticles for inkjet printing materials, we synthesized Sn-Ag bimetallic nanoparticles using a polyol process with poly(vinyl pyrrolidone). Because a surface oxidation layer forms on Sn nanoparticles, various compositions of Sn-xAg [x = 0, 20, 40, 60, 80, 100 (wt%)] nanoparticles were synthesized and characterized for the purpose of removing the {beta}-Sn phase. The results of XPS, TEM, and XRD analyses confirm that the formation of a bimetallic phase, such as Ag{sub 4}Sn or Ag{sub 3}Sn, hinders the {beta}-Sn phase and, consequently, leads to the removal of the surface oxidation layer. To measure the sheet resistance of various compositions of Sn-Ag nanoparticles, we made the ink that contains Sn-Ag by dispersing 10 wt% of Sn-Ag nanoparticles in methanol. The sheet resistance is decreased by the conductive Sn-Ag phases, such as the fcc, Ag{sub 4}Sn, and Ag{sub 3}Sn phases, but sharply increased by the low-conductive Sn nanoparticles and the surface oxidation layer on the Sn nanoparticles. The sheet resistance results confirm that 80Ag20Sn and 60Ag40Sn bimetallic nanoparticles are suitable candidates for inkjet printing materials.

  6. In Situ Synthesis of Bimetallic Hybrid Nanocatalysts on a Paper-Structured Matrix for Catalytic Applications

    Directory of Open Access Journals (Sweden)

    Hirotaka Koga

    2011-11-01

    Full Text Available Bimetallic nanoparticles have attracted significant attention as their electrochemical and catalytic properties being superior to those of the individual component nanoparticles. In this study, gold-silver hybrid nanoparticles (AuAgNPs with an Aucore-Agshell nanostructure were successfully synthesized on zinc oxide (ZnO whiskers. The as-prepared nanocatalyst, denoted AuAgNPs@ZnO whisker, exhibits an excellent catalytic efficiency in the aqueous reduction of 4-nitrophenol to 4-aminophenol; the turnover frequency was up to 40 times higher than that of each component nanoparticle. Their unique features were attributed to the electronic ligand effect at the bimetallic interface. In addition, the AuAgNPs were synthesized on a ZnO whisker-containing paper with a fiber-network microstructure, which was prepared via a papermaking technique. The paper-structured AuAgNPs composite possessed both a paper-like practical utility and a good catalytic performance. Furthermore, the on-paper synthesis process for these bimetallic nanocatalysts is facile. These easy-to-handle nanocatalyst hybrid composites are expected to find a wide range of applications in various chemical and catalytic processes.

  7. Vegard's law-like behavior for Mn(m)Tc(n) alloy clusters: a first-principles prediction.

    Science.gov (United States)

    Datta, S; Saha-Dasgupta, T

    2014-05-07

    With a view to gaining an understanding of the alloying tendency of bimetallic nanoalloy clusters of isoelectronic constituents, we studied the structural and mixing behavior of MnmTcn alloy clusters with m + n = 13 for all possible compositions, using first-principles electronic structure calculations. Our study reports a favorable mixing tendency for the alloy clusters. The average bond lengths of the minimum energy structures show an overall linear variation with concentration, indicating a Vegard's law-like variation for the nanoalloy clusters, though the optimized structures undergo a structural transition from a closed and compact structure for the Mn-rich alloy clusters to an open layered-like structure for the Tc-rich alloy clusters. We work out a continuous and smooth interplay between hybridization and magnetization properties of the alloy clusters, which plays a vital role in the Vegard's law-like variation in their average bond lengths.

  8. Magnetic order and interaction in garnet lattice antiferromagnets AgCa{sub 2}M{sub 2}V{sub 3}O{sub 12}(M=Mn, Co, Ni) and NaPb{sub 2}Mn{sub 2}V{sub 3}O{sub 12}

    Energy Technology Data Exchange (ETDEWEB)

    Terada, N; Suzuki, H S; Kitazawa, H [National Institute for Materials Science (NIMS), Tsukuba, Ibaraki, 305-0047 (Japan); Kaneko, K; Metoki, N [Japan Atomic Energy Agency, Tokai, Ibaraki, 319-1195 (Japan); Awaka, J [National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565 (Japan); Nagata, S, E-mail: terada.noriki@nims.go.j [Muroran Institute of Technology, 27-1 Mizumoto-cho, Muroran, Hokkaido, 050-8585 (Japan)

    2010-01-01

    We have investigated the magnetic orderings and the magnetic interactions in garnet antiferromagnets AgCa{sub 2}M{sub 2}V{sub 3}O{sub 12}(M=Mn, Co, Ni) and NaPb{sub 2}Mn{sub 2}V{sub 3}O{sub 12}, using the powder neutron diffraction and magnetization measurements. In the neutron diffraction measurements, we revealed that the magnetic structures in all samples measured are simple two sublattice antiferromagnetic structures with collinear magnetic moments. We also determined the exchange interactions from the critical magnetic fields H{sup sat} observed in the high field magnetization processes up to 30 T.

  9. Magnetism in segregated bimetallic CoRh nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Berlanga-Ramirez, E.O. [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, 78000 San Luis Potosi, SLP (Mexico)]. E-mail: berlanga@dec1.ifisica.uaslp.mx; Aguilera-Granja, F. [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, 78000 San Luis Potosi, SLP (Mexico); Montejano-Carrizales, J.M. [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, 78000 San Luis Potosi, SLP (Mexico); Diaz-Ortiz, A. [Centro Nacional de Supercomputo, IPICyT, Apartado Postal 3-74 Tangamanga, 78231 San Luis Potosi, SLP (Mexico); Michaelian, K. [Instituto de Fisica, Universidad Nacional Autonoma de Mexico. 20-364, 01000 DF (Mexico); Vega, A. [Departamento de Fisica Teorica, Atomica y Optica, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2004-12-31

    The magnetic properties of free-standing ConRhm clusters (N=n+m{approx}110 and n{approx}m) of three different symmetries: cubo-octahedral, icosahedral and HCP, were investigated in the segregated case. The initial geometrical structures constructed at Rh bulk distances were relaxed with a many-body Gupta potential to obtain the cluster geometries and energies. We find that the lowest energy is associated with the HCP structure. The relaxed interatomic distance for all the structures is slightly lower than the Rh bulk distance. The spin-polarized electronic structure and related magnetic properties of these optimized geometries were calculated by solving self-consistently a spd tight-binding Hamiltonian. The magnetic moment of the Rh atoms shows strong dependence on the position and environment, whereas the Co atoms show a smoother dependence. Results are compared with the experimental data and with other theoretical calculations available in the literature.

  10. Bimetallic Nanocatalysts in Mesoporous Silica for Hydrogen Production from Coal-Derived Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Kuila, Debasish [North Carolina Agricultural & Technical State Univ., Greensboro, NC (United States); Ilias, Shamsuddin [North Carolina Agricultural & Technical State Univ., Greensboro, NC (United States)

    2013-02-13

    In steam reforming reactions (SRRs) of alkanes and alcohols to produce H2, noble metals such as platinum (Pt) and palladium (Pd) are extensively used as catalyst. These metals are expensive; so, to reduce noble-metal loading, bi-metallic nanocatalysts containing non-noble metals in MCM-41 (Mobil Composition of Material No. 41, a mesoporous material) as a support material with high-surface area were synthesized using one-pot hydrothermal procedure with a surfactant such as cetyltrimethylammonium bromide (CTAB) as a template. Bi-metallic nanocatalysts of Pd-Ni and Pd-Co with varying metal loadings in MCM-41 were characterized by x-ray diffraction (XRD), N2 adsorption, and Transmission electron microscopy (TEM) techniques. The BET surface area of MCM-41 (~1000 m2/g) containing metal nanoparticles decreases with the increase in metal loading. The FTIR studies confirm strong interaction between Si-O-M (M = Pd, Ni, Co) units and successful inclusion of metal into the mesoporous silica matrix. The catalyst activities were examined in steam reforming of methanol (SRM) reactions to produce hydrogen. Reference tests using catalysts containing individual metals (Pd, Ni and Co) were also performed to investigate the effect of the bimetallic system on the catalytic behavior in the SRM reactions. The bimetallic system remarkably improves the hydrogen selectivity, methanol conversion and stability of the catalyst. The results are consistent with a synergistic behavior for the Pd-Ni-bimetallic system. The performance, durability and thermal stability of the Pd-Ni/MCM-41 and Pd-Co/MCM-41 suggest that these materials may be promising catalysts for hydrogen production from biofuels. A part of this work for synthesis and characterization of Pd-Ni-MCM-41 and its activity for SRM reactions has been published (“Development of Mesoporous Silica Encapsulated Pd-Ni Nanocatalyst for Hydrogen Production” in “Production and Purification of Ultraclean

  11. Geometries, stabilities, and electronic properties of Be-doped gold clusters: a density functional theory study

    Institute of Scientific and Technical Information of China (English)

    Chen Dong-Dong; Kuang Xiao-Yu; Zhao Ya-Ru; Shao Peng; Li Yan-Fang

    2011-01-01

    We have systematically investigated the geometrical structures, relative stabilities and electronic properties of small bimetallic AunBe (n = 1, 2, ..., 8) clusters using a density functional method at BP86 level. The optimized geometries reveal that the impurity beryllium atom dramatically affects the structures of the Aun clusters. The averaged binding energies, fragmentation energies, second-order difference of energies, the highest occupied-lowest unoccupied molecular orbital energy gaps and chemical hardness are investigated. All of them exhibit a pronounced odd-even alternation,manifesting that the clusters with even number of gold atoms possess relatively higher stabilities. Especially, the linear Au2Be cluster is magic cluster with the most stable chemical stability. According to the natural population analysis, it is found that charge-transferring direction between Au atom and Be atom changes at the size of n = 4.

  12. Electrocatalytic oxidation of ethylene glycol at palladium-bimetallic nanocatalysts (PdSn and PdNi) supported on sulfonate-functionalised multi-walled carbon nanotubes

    CSIR Research Space (South Africa)

    Ramulifho, T

    2013-04-01

    Full Text Available Electrocatalytic oxidation of ethylene glycol (EG) in alkaline medium using nano-scaled palladium-based bimetallic catalysts (PdM, where M = Ni and Sn) supported on sulfonated multi-walled carbon nanotubes (SF-MWCNTs) is compared. The bimetallic...

  13. Plasmonic Properties of Bimetallic Nanostructures and Their Applications in Hydrogen Sensing and Chemical Reactions

    Science.gov (United States)

    Jiang, Ruibin

    Noble metal nanocrystals have attracted great interest from a wide range of research fields because of their intriguing properties endowed by their localized surface plasmon resonances, which are the collective oscillations of free electrons. Under resonant excitation, metal nanostructures exhibit very large scattering and absorption cross sections and large near-field enhancement. These extraordinary properties can be used in different applications, such as plasmonic sensing and imaging, plasmon-controlled optics, photothermal therapy, photocatalysis, solar cells, and so on. Gold and Silver nanocrystals have plasmon resonances in the visible and near-infrared regions. However, gold and silver are not suitable for some applications. For example, they are generally inactive for catalyzing chemical reactions. The integration of plasmonic metals with other metals can offer superior or new physical/chemical properties. In this thesis, I prepared Au/Ag and Au/Pd bimetallic nanostructures and studied their plasmonic properties and applications in hydrogen sensing and photocatalysis. Seeds have a crucial importance in the synthesis of bimetallic nanostructures. I therefore first studied the roles of the crystalline structure and shape of seeds on the overgrowth of bimetallic nanostructures. The overgrowth of silver and palladium on single crystalline Au nanorods, multicrystalline Au nanorods, and nanobipyramids were studied under the same conditions for each metal. The growths of silver and palladium on single crystalline Au nanorods gave cuboidal nanostructures, while rod-shaped nanostructures were obtained from the growths of silver and palladium on multicrystalline Au nanorods and nanobipyramids. Moreover, the growths of silver and palladium on multicrystalline Au nanobipyramids started at the stepped side facets, while the growths started at the twin boundaries on multicrystalline Au nanorods. These results unambiguously indicate that the crystalline structure of

  14. Meaningful Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Sanfilippo, Antonio P.; Calapristi, Augustin J.; Crow, Vernon L.; Hetzler, Elizabeth G.; Turner, Alan E.

    2004-05-26

    We present an approach to the disambiguation of cluster labels that capitalizes on the notion of semantic similarity to assign WordNet senses to cluster labels. The approach provides interesting insights on how document clustering can provide the basis for developing a novel approach to word sense disambiguation.

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

    Energy Technology Data Exchange (ETDEWEB)

    Liu Wei; Repo, Eveliina; Sillanpaeae, Mika [Laboratory of Applied Environmental Chemistry, University of Eastern Finland, Patteristonkatu 1, FI-50100 Mikkeli (Finland); Heikkilae, Mikko; Leskelae, Markku, E-mail: weiliuzk@yahoo.cn, E-mail: mika.sillanpaa@uef.fi [Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, PO Box 55 (A.I. Virtasen aukio 1), FI-00014, Helsinki (Finland)

    2010-10-01

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

  16. Gas-Phase Synthesis of Bimetallic Oxide Nanoparticles with Designed Elemental Compositions for Controlling the Explosive Reactivity of Nanoenergetic Materials

    Directory of Open Access Journals (Sweden)

    Ji Young Ahn

    2011-01-01

    Full Text Available We demonstrate a simple and viable method for controlling the energy release rate and pressurization rate of nanoenergetic materials by controlling the relative elemental compositions of oxidizers. First, bimetallic oxide nanoparticles (NPs with a homogeneous distribution of two different oxidizer components (CuO and Fe2O3 were generated by a conventional spray pyrolysis method. Next, the Al NPs employed as a fuel were mixed with CuO-Fe2O3 bimetallic oxide NPs by an ultrasonication process in ethanol solution. Finally, after the removal of ethanol by a drying process, the NPs were converted into energetic materials (EMs. The effects of the mass fraction of CuO in the CuO-Fe2O3 bimetallic oxide NPs on the explosive reactivity of the resulting EMs were examined by using a differential scanning calorimeter and pressure cell tester (PCT systems. The results clearly indicate that the energy release rate and pressurization rate of EMs increased linearly as the mass fraction of CuO in the CuO-Fe2O3 bimetallic oxide NPs increased. This suggests that the precise control of the stoichiometric proportions of the strong oxidizer (CuO and mild oxidizer (Fe2O3 components in the bimetallic oxide NPs is a key factor in tuning the explosive reactivity of EMs.

  17. Synergistic effect in the oxidation of benzyl alcohol using citrate-stabilized gold bimetallic nanoparticles supported on alumina

    Science.gov (United States)

    Gómez-Villarraga, Fernando; Radnik, Jörg; Martin, Andreas; Köckritz, Angela

    2016-06-01

    Bimetallic nanoparticles (NPs) containing gold and various second metals ( M = Pd, Pt, Cu, and Ag) supported on alumina (AuM/Alumina) were prepared using sodium citrate as stabilizer. In addition, supported monometallic Au/Alumina and Pd/Alumina were synthesized and tested to reveal synergistic effects in the catalytic evaluation of the bimetallic catalysts. The monometallic and bimetallic NPs revealed average sizes below 10 nm. The oxidation of benzyl alcohol with molecular oxygen as oxidant at mild conditions in liquid phase in the absence and presence (toluene or NaOH aqueous solution, 0.2 M) of a solvent was selected as test reaction to evaluate the catalytic properties of the above-mentioned solids. AuPd/Alumina exhibited the best catalytic activity among all bimetallic catalysts using toluene as solvent and under solvent-free conditions, respectively. In comparison to the monometallic catalysts, a synergistic effect with AuPd/Alumina was only evident in the solvent-free reaction. The AuPd/Alumina catalyst was able to oxidize benzyl alcohol selectively depending on the reaction medium into benzaldehyde (toluene or solvent-free) or benzoic acid (NaOH aqueous solution, 0.2 M). However, the catalyst deactivated due to particle growth of the bimetallic AuPd NPs by Ostwald ripening and leaching was not observed in the oxidation using toluene as solvent. The size of the catalytically active NPs, the metal composition of the particles, and the reaction conditions greatly influenced the catalytic oxidation results.

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

    Science.gov (United States)

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

    2010-10-01

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

  19. A new ligand system based on a bipyridine-functionalized calix[4]arene backbone leading to mono- and bimetallic complexes.

    Science.gov (United States)

    Dorta, Reto; Shimon, Linda J W; Rozenberg, Haim; Ben-David, Yehoshoa; Milstein, David

    2003-05-19

    The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4'-dimethyl-2,2'-bipyridine in two steps and subsequently reacting it with p-tert-butylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)(2)]BF(4) or [Rh(NBD)(CH(3)CN)(2)]BF(4) (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF(4)](2) (4). Treatment of the ligand with PdCl(2)(CH(3)CN)(2) leads to the isolation of the bimetallic complex BBPC[PdCl(2)](2) (5). When the nickel precursor NiBr(2)(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr(2)](2) (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334 A (for 4) and 3.224 A (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.

  20. Adsorption of a single gold or silver atom on vanadium oxide clusters.

    Science.gov (United States)

    Ding, Xun-Lei; Wang, Dan; Li, Rui-Jie; Liao, Heng-Lu; Zhang, Yan; Zhang, Hua-Yong

    2016-04-14

    The bonding properties between a single atom and its support have a close relationship with the stability and reactivity of single-atom catalysts. As a model system, the structural and electronic properties of bimetallic oxide clusters MV3Oy(q) (M = Au or Ag, q = 0, ±1, and y = 6-8) are systematically studied using density functional theory. The single noble metal atom Au or Ag tends to be adsorbed on the periphery of the V oxide clusters. Au prefers V sites for oxygen-poor clusters and O sites for oxygen-rich clusters, while Ag prefers O sites for most cases. According to natural population analysis, Au may possess positive or negative charges in the bimetallic oxide clusters, while Ag usually possesses positive charges. The bonding between Au and V has relatively high covalent character according to the bond order analysis. This work may provide some clues for understanding the bonding properties of single noble metal atoms on the support in practical single-atom catalysts, and serve as a starting point for further theoretical studies on the reaction mechanisms of related catalytic systems.

  1. Insertion of a single-molecule magnet inside a ferromagnetic lattice based on a 3D bimetallic oxalate network: towards molecular analogues of permanent magnets.

    Science.gov (United States)

    Clemente-León, Miguel; Coronado, Eugenio; Gómez-García, Carlos J; López-Jordà, Maurici; Camón, Agustín; Repollés, Ana; Luis, Fernando

    2014-02-03

    The insertion of the single-molecule magnet (SMM) [Mn(III)(salen)(H2O)]2(2+) (salen(2-) = N,N'-ethylenebis-(salicylideneiminate)) into a ferromagnetic bimetallic oxalate network affords the hybrid compound [Mn(III)(salen)(H2O)]2[Mn(II)Cr(III)(ox)3]2⋅(CH3OH)⋅(CH3CN)2 (1). This cationic Mn2 cluster templates the growth of crystals formed by an unusual achiral 3D oxalate network. The magnetic properties of this hybrid magnet are compared with those of the analogous compounds [Mn(III)(salen)(H2O)]2[Zn(II)Cr(III)(ox)3]2⋅(CH3OH)⋅(CH3CN)2 (2) and [In(III)(sal2-trien)][Mn(II)Cr(III)(ox)3]⋅(H2O)0.25⋅(CH3OH)0.25⋅(CH3CN)0.25 (3), which are used as reference compounds. In 2 it has been shown that the magnetic isolation of the Mn2 clusters provided by their insertion into a paramagnetic oxalate network of Cr(III) affords a SMM behavior, albeit with blocking temperatures well below 500 mK even for frequencies as high as 160 kHz. In 3 the onset of ferromagnetism in the bimetallic Mn(II) Cr(III) network is observed at Tc = 5 K. Finally, in the hybrid compound 1 the interaction between the two magnetic networks leads to the antiparallel arrangement of their respective magnetizations, that is, to a ferrimagnetic phase. This coupling induces also important changes on the magnetic properties of 1 with respect to those of the reference compounds 2 and 3. In particular, compound 1 shows a large magnetization hysteresis below 1 K, which is in sharp contrast with the near-reversible magnetizations that the SMMs and the oxalate ferromagnetic lattice show under the same conditions. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Cluster Lenses

    CERN Document Server

    Kneib, Jean-Paul; 10.1007/s00159-011-0047-3

    2012-01-01

    Clusters of galaxies are the most recently assembled, massive, bound structures in the Universe. As predicted by General Relativity, given their masses, clusters strongly deform space-time in their vicinity. Clusters act as some of the most powerful gravitational lenses in the Universe. Light rays traversing through clusters from distant sources are hence deflected, and the resulting images of these distant objects therefore appear distorted and magnified. Lensing by clusters occurs in two regimes, each with unique observational signatures. The strong lensing regime is characterized by effects readily seen by eye, namely, the production of giant arcs, multiple-images, and arclets. The weak lensing regime is characterized by small deformations in the shapes of background galaxies only detectable statistically. Cluster lenses have been exploited successfully to address several important current questions in cosmology: (i) the study of the lens(es) - understanding cluster mass distributions and issues pertaining...

  3. La0.9Sr0.1Ga0.8M0.2O3– (M = Mn, Co, Ni, Cu or Zn): Transition metal-substituted derivatives of lanthanum–strontium–gallium–magnesium (LSGM) perovskite oxide ion conductor

    Indian Academy of Sciences (India)

    Litty Sebastian; A K Shukla; J Gopalakrishnan

    2000-06-01

    Perovskite oxides of the general formula, La0.9Sr0.1Ga0.8M0.2O3– for M = Mn, Co, Ni, Cu and Zn, have been prepared and investigated. All the oxides exhibit high electrical conductivities ( ∼ 10–2 S/cm at 800°C) comparable to that of the best perovskite oxide ion conductor, La0.9Sr0.1Ga0.8Mg0.2O2.85 (LSGM) ( ∼ 8 × 10–2 S/cm at 800°C). While M = Mn, Co, Ni, Cu members appear to be mixed conductors with a variable electronic contribution to the conductivity, especially at high oxygen partial pressures (O2 \\geq 1 atm), arising from mixed-valency of the transition metals, the M = Zn(II) phase is a pure oxide ion conductor exhibiting a conductivity ( ∼ 1.5 × 10–2 S/cm at 800°C) that is slightly lower than that of LSGM. The lower conductivity of the M = Zn(II) derivative could be due to the preference of Zn(II) for a tetrahedral oxygen coordination.

  4. Synthesis of Ag-Au bimetallic film at liquid-liquid interface and its application in vapor sensing

    Energy Technology Data Exchange (ETDEWEB)

    Pasricha, Renu, E-mail: pasrichar@mail.nplindia.ernet.i [Material Characterization Division, National Physical Laboratory, New Delhi-110012 (India); Gupta, Shweta [Material Characterization Division, National Physical Laboratory, New Delhi-110012 (India); Sastry, M. [Tata Chemical Innovation Center, Anmol Pride, Baner Road, Pune-45 (India); Singh, Nahar; Gupta, Prabhat [Material Characterization Division, National Physical Laboratory, New Delhi-110012 (India)

    2010-11-30

    We demonstrate a novel process for preparing densely packed film of silver nanoparticles at the liquid-liquid interface followed by a transmetallation reaction with gold ion to yield a film of bimetallic nanoparticles. Films of assembled silver as well as Ag-Au bimetallic were characterized by UV-vis-spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) analysis. I-V measurement shows linear behavior for both the films with ca. five orders of magnitude drop in resistance for the Ag-Au bimetallic film. Temperature dependent I-V measurement revealed a semiconductor to metal transition after transmetallation reaction. The films where checked for their potential application in chemical vapor sensing to ammonia vapors.

  5. Facile Fabrication of Composition-Tuned Ru-Ni Bimetallics in Ordered Mesoporous Carbon for Levulinic Acid Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ying; Gao, Guang; Zhang, Xin; Li, Fuwei [ChinaU - Petroleum; (Chinese Aca. Sci.)

    2016-02-04

    Bimetallic catalysts are of great importance due to their unique catalytic properties. However, their conventional synthesis requires tedious multistep procedures and prolonged synthetic time, and the resulting bimetallics usually disperse unevenly and show poor stability. It is challenging to develop a facile and step-economic synthetic methodology for highly efficient bimetallic catalysts. In this study, we report an elegant metal complex-involved multicomponent assembly route to highly efficient Ru–Ni bimetallics in ordered mesoporous carbons (OMC). The fabrication of composition-tuned Ru–Ni bimetallics in OMC (RuxNi1–x–OMC, x = 0.5–0.9) was facilely realized via in situ construction of CTAB-directed cubic Ia3d chitosan-ruthenium–nickel–silica mesophase before pyrolysis and silica removal. The resulting RuxNi1–x–OMC materials are in-depth characterized with X-ray diffraction, N2 adsorption–desorption, transmission electron microscopy, infrared spectrum, and X-ray absorption fine structure. This facile fabrication method renders homogeneously dispersed Ru–Ni bimetallics embedded in the mesoporous carbonaceous framework and creates a highly active and stable Ru0.9Ni0.1–OMC catalyst for the hydrogenation of levulinic acid (LA) to prepare γ-valerolactone (GVL), a biomass-derived platform molecule with wide application in the preparation of renewable chemicals and liquid transportation fuels. A high TOF (>2000 h–1) was obtained, and the Ru0.9Ni0.1–OMC catalyst could be used at least 15 times without obvious loss of its catalytic performance.

  6. Bimetallic and Trimetallic Nanoparticles for Fuel Cell Electrocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    Perla B. Balbuena; Jorge M. Seminario

    2005-10-31

    Theoretical, high level ab initio investigations on representative clusters as well as on extended systems are conducted to determine the electronic, geometric, and thermodynamic factors that determine catalytic and electrocatalytic behavior, focusing in the reduction of oxygen in acid medium. The study of adsorption and reaction processes generates the information needed for force field development to be used in the analysis of nanocatalyst particles, their support, and their environment through large-scale molecular dynamics simulations, which include collective effects at the nanosecond time scale. Ab initio molecular dynamics simulations are used to explore reaction mechanisms, and this technique along with transition state theory calculations allows us to obtain the information needed about activation energies and estimates of the rate constants. Dynamic Monte Carlo simulations combine the results of the first three sets of studies yielding kinetics information within a time scale in the range of seconds and length scales of the order of hundreds of nanometers, including nanocatalyst/support/environment.

  7. Data Clustering

    Science.gov (United States)

    Wagstaff, Kiri L.

    2012-03-01

    On obtaining a new data set, the researcher is immediately faced with the challenge of obtaining a high-level understanding from the observations. What does a typical item look like? What are the dominant trends? How many distinct groups are included in the data set, and how is each one characterized? Which observable values are common, and which rarely occur? Which items stand out as anomalies or outliers from the rest of the data? This challenge is exacerbated by the steady growth in data set size [11] as new instruments push into new frontiers of parameter space, via improvements in temporal, spatial, and spectral resolution, or by the desire to "fuse" observations from different modalities and instruments into a larger-picture understanding of the same underlying phenomenon. Data clustering algorithms provide a variety of solutions for this task. They can generate summaries, locate outliers, compress data, identify dense or sparse regions of feature space, and build data models. It is useful to note up front that "clusters" in this context refer to groups of items within some descriptive feature space, not (necessarily) to "galaxy clusters" which are dense regions in physical space. The goal of this chapter is to survey a variety of data clustering methods, with an eye toward their applicability to astronomical data analysis. In addition to improving the individual researcher’s understanding of a given data set, clustering has led directly to scientific advances, such as the discovery of new subclasses of stars [14] and gamma-ray bursts (GRBs) [38]. All clustering algorithms seek to identify groups within a data set that reflect some observed, quantifiable structure. Clustering is traditionally an unsupervised approach to data analysis, in the sense that it operates without any direct guidance about which items should be assigned to which clusters. There has been a recent trend in the clustering literature toward supporting semisupervised or constrained

  8. Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

    KAUST Repository

    Widger, Peter C. B.

    2011-07-26

    Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

  9. Cluster Chemistry

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    @@ Cansisting of eight scientists from the State Key Laboratory of Physical Chemistry of Solid Surfaces and Xiamen University, this creative research group is devoted to the research of cluster chemistry and creation of nanomaterials.After three-year hard work, the group scored a series of encouraging progresses in synthesis of clusters with special structures, including novel fullerenes, fullerene-like metal cluster compounds as well as other related nanomaterials, and their properties study.

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

    Science.gov (United States)

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

    2014-09-10

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

  11. RESOURCE-SAVING TECHNOLOGY FOR HIGH-SPEED HOT EXTRUSION OF BIMETALLIC ROD PARTS

    Directory of Open Access Journals (Sweden)

    I. V. Kachanov

    2016-01-01

    Full Text Available Processes of high-speed shaping changes and especially high-speed hot extrusion create efficient conditions for treatment of weakly plastic and poorly deformable materials which are widely used in tool making facilities. Due to the fact that high-speed stamping provides accurate billets with increased mechanical properties, it can be used as a technological process for manufacturing rod parts of die tooling operating under conditions of increased loads and wear. The purpose of the given paper is to carry out experimental investigations on the possibility to obtain a bimetallic rod tool where structural steel is considered as a basis of the tool and a working cavity is made of high-alloyed tool steel with its saving up to 90 %. A scheme of loading and geometry of conjugated surfaces of the composite billet have been developed in the paper. Technology for obtaining bimetallic rod parts of die tooling with deformation at speed of vд = 70–80 m/s and composite billet temperature of Т = (1150±20 ºС has been experimentally tested with formation of a compound due to plastic flow of two billet parts on contact surface with removal of surface oxide films. Microstructures of the bimetallic compounds obtained with the help of high-speed hot extrusion method for compositions of structural and high-alloy steels have been investigated and their high quality has been proved during the investigations. Dependences of micro-hardness distribution have been established outbound two steel contact plane in the zone of connection that are characterized by a minimum micro-hardness value in the connection joint. Availability of more plastic zone in the contact plane contributes to reduction of residual stresses due to their relaxation in this zone and higher joint strength.

  12. One-step green synthesis of bimetallic Fe/Pd nanoparticles used to degrade Orange II

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Fang; Yang, Die; Chen, Zuliang, E-mail: zuliang.chen@newcastle.edu.au; Megharaj, Mallavarapu; Naidu, Ravendra

    2016-02-13

    Highlights: • Green synthesis of bimetallic Fe/Pd NPs was firstly reported using the one-step method. • 98.0% of Orange II was removed by Fe/Pd NPs, but only 16.0% by Fe NPs. • Fe/Pd NPs with a diameter ranging from 10 to 100 nm were observed. • Removing Orange II using Fe/Pd NPs involved both adsorption and catalytic degradation. - Abstract: To reduce cost and enhance reactivity, bimetallic Fe/Pd nanoparticles (NPs) were firstly synthesized using grape leaf aqueous extract to remove Orange II. Green synthesized bimetallic Fe/Pd NPs (98.0%) demonstrated a far higher ability to remove Orange II in 12 h compared to Fe NPs (16.0%). Meanwhile, all precursors, e.g., grape leaf extract, Fe{sup 2+} and Pd{sup 2+}, had no obvious effect on removing Orange II since less than 2.0% was removed. Kinetics study revealed that the removal rate fitted well to the pseudo-first-order reduction and pseudo-second-order adsorption model, meaning that removing Orange II via Fe/Pd NPs involved both adsorption and catalytic reduction. The remarkable stability of Fe/Pd NPs showed the potential application for removing azo dyes. Furthermore, Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed the changes in Fe/Pd NPs before and after reaction with Orange II. High Performance Liquid Chromatography–Mass Spectrum (HPLC–MS) identified the degraded products in the removal of Orange II, and finally a removal mechanism was proposed. This one-step strategy using grape leaf aqueous extract to synthesize Fe/Pd NPs is simple, cost-effective and environmentally benign, making possible the large-scale production of Fe/Pd NPs for field remediation.

  13. Comparative toxicity study of Ag, Au, and Ag-Au bimetallic nanoparticles on Daphnia magna.

    Science.gov (United States)

    Li, Ting; Albee, Brian; Alemayehu, Matti; Diaz, Rocio; Ingham, Leigha; Kamal, Shawn; Rodriguez, Maritza; Bishnoi, Sandra Whaley

    2010-09-01

    A comparative assessment of the 48-h acute toxicity of aqueous nanoparticles synthesized using the same methodology, including Au, Ag, and Ag-Au bimetallic nanoparticles, was conducted to determine their ecological effect in freshwater environments through the use of Daphnia magna, using their mortality as a toxicological endpoint. D. magna are one of the standard organisms used for ecotoxicity studies due to their sensitivity to chemical toxicants. Particle suspensions used in toxicity testing were well-characterized through a combination of absorbance measurements, atomic force or electron microscopy, flame atomic absorption spectrometry, and dynamic light scattering to determine composition, aggregation state, and particle size. The toxicity of all nanoparticles tested was found to be dose and composition dependent. The concentration of Au nanoparticles that killed 50% of the test organisms (LC(50)) ranged from 65-75 mg/L. In addition, three different sized Ag nanoparticles (diameters = 36, 52, and 66 nm) were studied to analyze the toxicological effects of particle size on D. magna; however, it was found that toxicity was not a function of size and ranged from 3-4 μg/L for all three sets of Ag nanoparticles tested. This was possibly due to the large degree of aggregation when these nanoparticles were suspended in standard synthetic freshwater. Moreover, the LC(50) values for Ag-Au bimetallic nanoparticles were found to be between that of Ag and Au but much closer to that of Ag. The bimetallic particles containing 80% Ag and 20% Au were found to have a significantly lower toxicity to Daphnia (LC(50) of 15 μg/L) compared to Ag nanoparticles, while the toxicity of the nanoparticles containing 20% Ag and 80% Au was greater than expected at 12 μg/L. The comparison results confirm that Ag nanoparticles were much more toxic than Au nanoparticles, and that the introduction of gold into silver nanoparticles may lower their environmental impact by lowering the amount

  14. Surface plasmon polariton assisted optical switching in noble bimetallic nanoparticle system

    Energy Technology Data Exchange (ETDEWEB)

    Dhara, Sandip, E-mail: dhara@igcar.gov.in, E-mail: chenkh@pub.iams.sinica.edu.tw [Surface and Nanoscience Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan (China); Lu, C.-Y.; Tu, W.-S. [Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan (China); Magudapathy, P. [Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Huang, Y.-F.; Chen, K.-H., E-mail: dhara@igcar.gov.in, E-mail: chenkh@pub.iams.sinica.edu.tw [Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan (China); Center for Condensed Matter Science, National Taiwan University, Taipei 106, Taiwan (China)

    2015-01-12

    Photoresponse of bimetallic Au-Ag nanoparticle embedded soda glass (Au-Ag@SG) substrate is reported for surface plasmon assisted optical switching using 808 nm excitation. Au-Ag@SG system is made by an ion beam technique where Ag{sup +} is introduced first in the soda glass matrix by ion exchange technique. Subsequently, 400 keV Au{sup +} is implanted in the sample for different fluences, which is followed by an ion beam annealing process using 1 MeV Si{sup +} at a fixed fluence of 2 × 10{sup 16} ions·cm{sup −2}. Characteristic surface plasmon resonance (SPR) peaks around 400 and 550 nm provided evidence for the presence of Au and Ag nanoparticles. An optical switching in the Au-Ag@SG system with 808 nm, which is away from the characteristic SPR peaks of Ag and Au nanoparticles, suggests the possible role of two photon absorption (TPA) owing to the presence of interacting electric dipole in these systems. The role of surface plasmon polariton is emphasized for the propagation of electronic carrier belonging to the conduction electron of Au-Ag system in understanding the observed photoresponse. Unique excitation dependent photoresponse measurements confirm the possible role of TPA process. A competitive interband and intraband transitions in the bimetallic system of Au and Ag, which may be primarily responsible for the observation, are validated qualitatively using finite difference time domain calculations where inter-particle separation of Au and Ag plays an important role. Thus, a smart way of optical switching can be envisaged in noble bimetallic nanocluster system where long wavelength with higher skin depth can be used for communication purpose.

  15. Bimetallic PtxCoy nanoparticles with curved faces for highly efficient hydrogenation of cinnamaldehyde

    Science.gov (United States)

    Gu, Yan; Zhao, Yonghui; Wu, Panpan; Yang, Bo; Yang, Nating; Zhu, Yan

    2016-05-01

    The control of the curved structure of bimetallic nanocrystals is a challenge, due to the rate differential for atom deposition and surface diffusion of alien atomic species on specific crystallographic planes of seeds. Herein, we report how to tune the degree of concavity of bimetallic PtxCoy concave nanoparticles using carboxylic acids as surfactants with an oleylamine system, leading to the specific crystallographic planes being exposed. The terminal carboxylic acids with a bridge ring or a benzene ring serving as structure regulators could direct the formation of curved faces with exposed high-index facets, and long-chain saturated fatty acids favored the production of curved faces with exposed low-index facets, while long-chain olefin acids alone benefited the formation of a flat surface with exposed low-index planes. Furthermore, these PtxCoy particles with curved faces displayed superior catalytic behaviour to cinnamaldehyde hydrogenation when compared with PtxCoy with flat faces. PtxCoy nanoparticles with curved faces exhibited over 6-fold increase in catalytic activity compared to PtxNiy nanoparticles with curved faces, and near 40-fold activity increase was observed in comparison with PtxFey nanoparticles with curved faces.The control of the curved structure of bimetallic nanocrystals is a challenge, due to the rate differential for atom deposition and surface diffusion of alien atomic species on specific crystallographic planes of seeds. Herein, we report how to tune the degree of concavity of bimetallic PtxCoy concave nanoparticles using carboxylic acids as surfactants with an oleylamine system, leading to the specific crystallographic planes being exposed. The terminal carboxylic acids with a bridge ring or a benzene ring serving as structure regulators could direct the formation of curved faces with exposed high-index facets, and long-chain saturated fatty acids favored the production of curved faces with exposed low-index facets, while long

  16. Enhanced antibacterial activity of bimetallic gold-silver core-shell nanoparticles at low silver concentration

    Science.gov (United States)

    Banerjee, Madhuchanda; Sharma, Shilpa; Chattopadhyay, Arun; Ghosh, Siddhartha Sankar

    2011-12-01

    Herein we report the development of bimetallic Au@Ag core-shell nanoparticles (NPs) where gold nanoparticles (Au NPs) served as the seeds for continuous deposition of silver atoms on its surface. The core-shell structure and morphology were examined by UV-Vis spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis and X-ray diffraction (XRD). The core-shell NPs showed antibacterial activity against both Gram negative (Escherichia coli and Pseudomonas aeruginosa) and Gram positive (Enterococcus faecalis and Pediococcus acidilactici) bacteria at low concentration of silver present in the shell, with more efficacy against Gram negative bacteria. TEM and flow cytometric studies showed that the core-shell NPs attached to the bacterial surface and caused membrane damage leading to cell death. The enhanced antibacterial properties of Au@Ag core-shell NPs was possibly due to the more active silver atoms in the shell surrounding gold core due to high surface free energy of the surface Ag atoms owing to shell thinness in the bimetallic NP structure.Herein we report the development of bimetallic Au@Ag core-shell nanoparticles (NPs) where gold nanoparticles (Au NPs) served as the seeds for continuous deposition of silver atoms on its surface. The core-shell structure and morphology were examined by UV-Vis spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis and X-ray diffraction (XRD). The core-shell NPs showed antibacterial activity against both Gram negative (Escherichia coli and Pseudomonas aeruginosa) and Gram positive (Enterococcus faecalis and Pediococcus acidilactici) bacteria at low concentration of silver present in the shell, with more efficacy against Gram negative bacteria. TEM and flow cytometric studies showed that the core-shell NPs attached to the bacterial surface and caused membrane damage leading to cell death. The enhanced antibacterial properties of Au@Ag core-shell NPs was

  17. Rapid dechlorination of chlorinated organic compounds by nickel/iron bimetallic system in water

    Institute of Scientific and Technical Information of China (English)

    TONG Shao-ping; WEI Hong; MA Chun-an; LIU Wei-ping

    2005-01-01

    Detoxification of chlorinated organic compounds via reaction with nickel/iron powder was implemented in aqueous solution. Compared to iron, nickel/iron bimetallic powder had higher hydrodechlorination activities for both atrazine (ATR) and p-chlorophenol (pCP); nickel/iron (2.96%, w/w) was shown to have the largest specific surface area and the optimum proportion for the dechlorination of both ATR and pCP. Electrochemical measurements showed that the adsorbed hydrogen atom on the nickel must have been the dominant reductive agent for the dechlorination of both ATR andpCP in this system.

  18. Synthesis of bimetallic gold/silver nanoparticles via in situ seeding

    Science.gov (United States)

    Gorbachevskiy, M. V.; Kopitsyn, D. S.; Tiunov, I. A.; Kotelev, M. S.; Vinokurov, V. A.; Novikov, A. A.

    2017-01-01

    A way of synthesizing bimetallic gold/silver nanoparticles with in situ seeding initiated by the addition of sodium borohydride is proposed. The obtained nanoparticles are studied by means of transmission electron microscopy (TEM). Changes in the optical density spectra of the nanoparticles during their coagulation are investigated. The technique allows the rapid acquisition of nontoxic SERS-active nanoparticles with maximum SERS enhancement factor about 105 in the near infrared range for Raman shifts typical for biological objects such as bacterial cells and spores.

  19. Free-Standing Bimetallic Nanorings and Nanoring Arrays Made by On-Wire Lithography

    Energy Technology Data Exchange (ETDEWEB)

    Liusman, C.; Li, S. Z.; Chen, X. D.; Wei, W.; Zhang, H.; Schatz, George C.; Boey, F.; Mirkin, Chad

    2010-12-28

    This paper describes a new strategy for synthesizing free-standing bimetallic nanorings and nanoring arrays based upon on-wire lithography and a galvanic replacement reaction. The strategy allows one to tune the diameter, length, and therefore aspect ratio of the nanorings. In addition, it can be used to produce arrays of nanorings in high yield with control over number and spacing. Spectroscopic studies and discrete dipole approximation calculations show that nanoring dimers exhibit greater surface enhanced Raman scattering than the analogous nanodisk dimers.

  20. Electrical performances of pyroelectric bimetallic strip heat engines describing a Stirling cycle

    Science.gov (United States)

    Arnaud, A.; Boughaleb, J.; Monfray, S.; Boeuf, F.; Cugat, O.; Skotnicki, T.

    2015-12-01

    This paper deals with the analytical modeling of pyroelectric bimetallic strip heat engines. These devices are designed to exploit the snap-through of a thermo-mechanically bistable membrane to transform a part of the heat flowing through the membrane into mechanical energy and to convert it into electric energy by means of a piezoelectric layer deposited on the surface of the bistable membrane. In this paper, we describe the properties of these heat engines in the case when they complete a Stirling cycle, and we evaluate the performances (available energy, Carnot efficiency...) of these harvesters at the macro- and micro-scale.

  1. STUDY ON POLYMER- Ru- Co BIMETALLIC COMPLEXES CATALYSTS Ⅱ. X-RAY PHOTOELECTRON SPECTROSCOPIC ANALYSIS

    Institute of Scientific and Technical Information of China (English)

    ZONG Huijuan; TANG Qi; CHEN Zonghan; JIANG Yingyan

    1991-01-01

    Polymer-Ru-Co bimetallic complexes have been examined by X-ray photoelectron spectroscopy.The catalyst is highly active only when the mole ratio of Co/Ru is 4:3. The activity of catalysts does not depend on the total Co/Ru ratio, but on the surface stoichiometry of Co and Ru. When the relative intensities of Co2p and Ru3d of XP S peaks are close to each other and both are high, the catalyst exhibits its maximum activity.The mechanism of catalytic hydroformylation has been discussed.

  2. Melting behaviour of gold-platinum nanoalloy clusters by molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Ong, Yee Pin; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    The melting behavior of bimetallic gold-platinum nanoclusters is studied by applying Brownian-type isothermal molecular dynamics (MD) simulation, a program modified from the cubic coupling scheme (CCS). The process begins with the ground-state structures obtained from global minimum search algorithm and proceeds with the investigation of the effect of temperature on the thermal properties of gold-platinum nanoalloy clusters. N-body Gupta potential has been employed in order to account for the interactions between gold and platinum atoms. The ground states of the nanoalloy clusters, which are core-shell segregated, are heated until they become thermally segregated. The detailed melting mechanism of the nanoalloy clusters is studied via this approach to provide insight into the thermal stability of the nanoalloy clusters.

  3. Clustered regression with unknown clusters

    CERN Document Server

    Barman, Kishor

    2011-01-01

    We consider a collection of prediction experiments, which are clustered in the sense that groups of experiments ex- hibit similar relationship between the predictor and response variables. The experiment clusters as well as the regres- sion relationships are unknown. The regression relation- ships define the experiment clusters, and in general, the predictor and response variables may not exhibit any clus- tering. We call this prediction problem clustered regres- sion with unknown clusters (CRUC) and in this paper we focus on linear regression. We study and compare several methods for CRUC, demonstrate their applicability to the Yahoo Learning-to-rank Challenge (YLRC) dataset, and in- vestigate an associated mathematical model. CRUC is at the crossroads of many prior works and we study several prediction algorithms with diverse origins: an adaptation of the expectation-maximization algorithm, an approach in- spired by K-means clustering, the singular value threshold- ing approach to matrix rank minimization u...

  4. Subspace clustering through attribute clustering

    Institute of Scientific and Technical Information of China (English)

    Kun NIU; Shubo ZHANG; Junliang CHEN

    2008-01-01

    Many recently proposed subspace clustering methods suffer from two severe problems. First, the algorithms typically scale exponentially with the data dimensionality or the subspace dimensionality of clusters. Second, the clustering results are often sensitive to input parameters. In this paper, a fast algorithm of subspace clustering using attribute clustering is proposed to over-come these limitations. This algorithm first filters out redundant attributes by computing the Gini coefficient. To evaluate the correlation of every two non-redundant attributes, the relation matrix of non-redundant attributes is constructed based on the relation function of two dimensional united Gini coefficients. After applying an overlapping clustering algorithm on the relation matrix, the candidate of all interesting subspaces is achieved. Finally, all subspace clusters can be derived by clustering on interesting subspaces. Experiments on both synthesis and real datasets show that the new algorithm not only achieves a significant gain of runtime and quality to find subspace clusters, but also is insensitive to input parameters.

  5. A general approach for the synthesis of bimetallic M–Sn (M = Ru, Rh and Ir) catalysts for efficient hydrogenolysis of ester

    KAUST Repository

    Samal, Akshaya K.

    2016-11-24

    A versatile synthetic method was applied for the preparation of Sn containing bimetallic catalysts. The synthesis was performed by simply mixing the super hydride [LiB(C2H5)(3)H], with a metal (Ru, Rh or Ir) salt and an organotin complex in tetrahydrofuran solvent without using any surfactant. This leads to the formation of monodispersed M-Sn (M = Ru, Rh or Ir) bimetallic nanoparticles (NPs). These bimetallic catalysts show high performances in the hydrogenolysis of ester to the corresponding alcohol.

  6. Final Technical Report: First Principles Investigations for the Ensemble Effects of PdAu and PtAu Bimetallic Nanocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ruqian Wu

    2012-05-18

    Bimetallic surfaces with tunable chemical properties have attracted broad attention in recent years due to their ample potential for heterogeneous catalysis applications. The local chemical properties of constituents are strongly altered from their parent metals by 'ligand effect', a term encompassing the influences of charge transfer, orbital rehybridization and lattice strain. In comparison to the aforementioned, the 'ensemble effect' associated with particular arrangements of the active constituents have received much less attention, despite their notable importance towards the determination of reactivity and selectivity of bimetallic catalysts. We performed theoretical studies for understanding the ensemble effects on bimetallic catalysis: (i) simulations for the formation of different ensembles on PdAu and PtAu nanoclusters; (ii) studies of the size, shape, and substrate dependence of their electronic properties; and (iii) simulations for model reactions such as CO oxidation, methanol, ethylene and water dehydrogenation on PdAu and PtAu nanoclusters. In close collaboration with leading experimental groups, our theoretical research elucidated the fundamentals of Au based bimetallic nanocatalysts.

  7. Tailoring the carbon nanostructures grown on the surface of Ni-Al bimetallic nanoparticles in the gas phase.

    Science.gov (United States)

    Kim, Whi Dong; Ahn, Ji Young; Lee, Dong Geun; Lee, Hyung Woo; Hong, Suck Won; Park, Hyun Seol; Kim, Soo H

    2011-10-15

    A gas-phase, one-step method for producing various aerosol carbon nanostructures is described. The carbon nanostructures can be selectively tailored with either straight, coiled, or sea urchin-like structures by controlling the size of Ni-Al bimetallic nanoparticles and the reaction temperature. The carbon nanostructures were grown using both conventional spray pyrolysis and thermal chemical vapor deposition. Bimetallic nanoparticles with catalytic Ni (guest) and non-catalytic Al (host) matrix were reacted with acetylene and hydrogen gases. At the processing temperature range of 650-800 °C, high concentration straight carbon nanotubes (S-CNTs) with a small amount of coiled carbon nanotubes (C-CNTs) can be grown on the surface of seeded bimetallic nanoparticle size 100 nm, resulting from the significant size reduction of the available Ni sites due to thermal expansion of molten Al matrix sites without consumption of Al matrix. However, at the processing temperature range of 500-650 °C, C-CNTs can be grown on the bimetallic nanoparticle size 100 nm due to the isolation of Ni sites in the Al matrix. Copyright © 2011 Elsevier Inc. All rights reserved.

  8. Influence of the Au/Ag ratio on the catalytic activity of dendrimer-encapsulated bimetallic nanoparticles in microreactors

    NARCIS (Netherlands)

    Ricciardi, R.; Huskens, J.; Verboom, W.

    2015-01-01

    Dendrimer-encapsulated Au/Ag alloy nanoparticles (Au/Ag DENs) were covalently attached to a monolayer-functionalized inner surface of glass microreactors. The influence of the bimetallic alloy structure and of the different metal ratios was investigated for the reduction of 4-nitrophenol using NaBH4

  9. Preparation of Au-Pd bimetallic nanoparticles in porous germania nanospheres: A study of their morphology and catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Regan, Maureen R. [Department of Chemistry, Fordham University, 441, East Fordham Road, Bronx, NY 10458 (United States); Banerjee, Ipsita A. [Department of Chemistry, Fordham University, 441, East Fordham Road, Bronx, NY 10458 (United States)]. E-mail: banerjee@fordham.edu

    2006-03-15

    Size controlled Au-Pd bimetallic nanoparticles with an average size of 7-10 nm were grown in porous germania nanospheres. The properties of the resulting nanocomposites were characterized by electron microscopy, energy dispersive spectroscopy, and ultraviolet-visible spectroscopy. The catalytic activity of the nanocomposites was also examined by studying the degradation of p-nitroaniline.

  10. Developing a Thermal- and Coking-Resistant Cobalt-Tungsten Bimetallic Anode Catalyst for Solid Oxide Fuel Cells

    NARCIS (Netherlands)

    Yan, N.; Pandey, J.; Zeng, Y.; Amirkhiz, B.S.; Hua, B.; Geels, N.J.; Luo, J.L.; Rothenberg, G.

    2016-01-01

    We report the development of a novel Co–W bimetallic anode catalyst for solid oxide fuel cells (SOFCs) via a facile infiltration-annealing process. Using various microscopic and spectroscopic measurements, we find that the formed intermetallic nanoparticles are highly thermally stable up to 900 °C

  11. Influence of the Au/Ag ratio on the catalytic activity of dendrimer-encapsulated bimetallic nanoparticles in microreactors

    NARCIS (Netherlands)

    Ricciardi, R.; Huskens, Jurriaan; Verboom, Willem

    2015-01-01

    Dendrimer-encapsulated Au/Ag alloy nanoparticles (Au/Ag DENs) were covalently attached to a monolayer-functionalized inner surface of glass microreactors. The influence of the bimetallic alloy structure and of the different metal ratios was investigated for the reduction of 4-nitrophenol using

  12. Removal of trichloroethylene DNAPL trapped in porous media using nanoscale zerovalent iron and bimetallic nanoparticles: direct observation and quantification.

    Science.gov (United States)

    Wang, Qiliang; Jeong, Seung-Woo; Choi, Heechul

    2012-04-30

    Direct trichloroethylene (TCE) dense non-aqueous phase liquid (DNAPL) removal inside pore areas using nanoscale zerovalent iron (NZVI) and bimetallic nanoparticles were first investigated in a water-saturated porous glass micromodel. Effects of nitrate, aqueous ethanol co-solvent, humic substance, and elapsed time on TCE DNAPL removal using NZVI were studied by direct visualization. The removal efficiency was then quantified by directly measuring the remaining TCE DNAPL blobs area using an image analyzer. As ethanol content of co-solvent increased, TCE DNAPL removal by NZVI was also increased implying sequential TCE DNAPL removal mechanisms: as dissolved TCE was degraded by NZVI, TCE dissolution from TCE blobs would be then facilitated and the TCE blob areas would be eventually reduced. The presence of nitrate and humic substance hindered the NZVI reactivity for the TCE DNAPL removal. In contrast, the TCE DNAPL removal efficiency was enhanced using bimetallic nanoparticles in a short-term reaction by generating atomic hydrogen for catalytic hydro-dechlorination. However, all TCE DNAPL removal efficiencies reached the same level after long-term reaction using both NZVI and bimetallic nanoparticles. Direct TCE DNAPL observation clearly implied that TCE blobs existed for long time even though all TCE blobs were fully exposed to NZVI and bimetallic nanoparticles. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. Effect of mono- and bimetallic nanoparticles Fe, Ni, & Fe/Ni based on carbon nanocomposites on electrocatalytic properties of anodes

    Science.gov (United States)

    Ranabhat, K.; Pylinina, A. I.; Skripkin, K. S.; Sofronova, E. A.; Revina, A. A.; Kasatkin, V. E.; Patrikeev, L. N.; Lapshinsky, V. A.

    2016-10-01

    The optical properties of metallic Fe nanoparticles (NPs), Ni NPs and bimetallic Fe/Ni NPs produced under radiolysis in anaerobic condition based on a chemical reduction in the presence of oxygen and quercetin in reversed micellar solutions, and electrokinetic properties of nanoparticles carbon-based nanocomposites were studied. The possibility of the preparation of coating using different nanocomposites with anomalous electrocatalytic is addressed.

  14. Core-shell Rh-Pt nanocubes: A model for studying compressive strain effects in bimetallic nanocatalysts

    Science.gov (United States)

    Harak, Ethan William

    Shape-controlled bimetallic nanocatalysts often have increased activities and stabilities over their monometallic counterparts due to surface strain effects and electron transfer between the two metals. Here, we demonstrate that the degree of surface strain can be manipulated in shape-controlled nanocrystals through a bimetallic core shell architecture. This ability is achieved in a model core shell Rh Pt nanocube system through control of shell thickness. An increase in the Pt shell thickness leads to more compressive strain, which can increase the Pt 4f7/2 binding energy by as much as 0.13 eV. This change in electronic structure is correlated with a weakening of surface-adsorbate interactions, which we exploit to reduce catalyst poisoning by CO during formic acid electrooxidation. In fact, by precisely controlling the Pt shell thickness, the maximum current density achieved with Rh Pt nanocubes was 3.5 times greater than that achieved with similarly sized Pt nanocubes, with decreased CO generation as well. This system serves as a model for how bimetallic architectures can be used to manipulate the electronic structure of nanoparticle surfaces for efficient catalysis. The strategy employed here should enable the performance of bimetallic nanomaterials comprised of more cost-effective metals to be enhanced as well.

  15. Highly selective bimetallic Pt-Cu/Mg(Al)O catalysts for the aqueous-phase reforming of glycerol

    NARCIS (Netherlands)

    Boga, D.A.; Oord, R.; Beale, A.M.; Chung, Y.M.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

    2013-01-01

    Monometallic Pt and bimetallic Pt-Cu catalysts supported on Mg(Al)O mixed oxides, obtained by calcination of the corresponding layered double hydroxides (LDHs), were prepared and tested in the aqueous-phase reforming (APR) of glycerol. The effect of the Mg/Al ratio and calcination temperature of the

  16. Selective hydrogenation of citral over Au-based bimetallic catalysts in supercritical carbon dioxide

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Selective hydrogenation of citral was investigated over Au-based bimetallic catalysts in the environmentally benign supercritical carbon dioxide (scCO2) medium.The catalytic performances were different in citral hydrogenation when Pd or Ru was mixed (physically and chemically) with Au.Compared with the corresponding monometallic catalyst,the total conversion and the selectivity to citronellal (CAL) were significantly enhanced over TiO2 supported Pd and Au bimetallic catalysts (physically and chemically mixed);however,the conversion and selectivity did not change when Ru was physically mixed with Au catalyst compared to the monometallic Ru/TiO2,and the chemically mixed Ru-Au/TiO2 catalyst did not show any activity.The effect of CO2 pressure on the conversion of citral and product selectivity was significantly different over the Au/TiO2,Pd-Au/TiO2,and Pd/TiO2 catalysts.It was assumed to be ascribed to the difference in the interactions between Au,Pd nanoparticles and CO2 under different CO2 pressures.

  17. Enhancement of Hydrogen Storage Behavior of Complex Hydrides via Bimetallic Nanocatalysts Doping

    Directory of Open Access Journals (Sweden)

    Prakash C. Sharma

    2012-10-01

    Full Text Available Pristine complex quaternary hydride (LiBH4/2LiNH2 and its destabilized counterpart (LiBH4/2LiNH2/nanoMgH2 have recently shown promising reversible hydrogen storage capacity under moderate operating conditions. The destabilization of complex hydride via nanocrystalline MgH2 apparently lowers the thermodynamic heat values and thus enhances the reversible hydrogen storage behavior at moderate temperatures. However, the kinetics of these materials is rather low and needs to be improved for on-board vehicular applications. Nanocatalyst additives such as nano Ni, nano Fe, nano Co, nano Mn and nano Cu at low concentrations on the complex hydride host structures have demonstrated a reduction in the decomposition temperature and overall increase in the hydrogen desorption reaction rates. Bi-metallic nanocatalysts such as the combination of nano Fe and nano Ni have shown further pronounced kinetics enhancement in comparison to their individual counterparts. Additionally, the vital advantage of using bi-metallic nanocatalysts is to enable the synergistic effects and characteristics of the two transitional nanometal species on the host hydride matrix for the optimized hydrogen storage behavior.

  18. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: A mechanistic study

    KAUST Repository

    Ahmed, Syud M.

    2013-12-18

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands. © 2013 American Chemical Society.

  19. Partial oxidation of methane over bimetallic copper- and nickel-actinide oxides (Th, U)

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Ana C.; Goncalves, A.P.; Gasche, T. Almeida [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal); Ferraria, A.M.; Rego, A.M. Botelho do [Universidade Tecnica de Lisboa, IST, Centro de Quimica-Fisica Molecular and IN, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Correia, M.R.; Bola, A. Margarida [I3N-Universidade de Aveiro, Department Fisica, Aveiro (Portugal); Branco, J.B., E-mail: jbranco@itn.p [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal)

    2010-05-14

    The study of partial oxidation of methane (POM) over bimetallic nickel- or copper-actinide oxides was undertaken. Binary intermetallic compounds of the type AnNi{sub 2} (An = Th, U) and ThCu{sub 2} were used as precursors and the products (2NiO.UO{sub 3}, 2NiO.ThO{sub 2} and 2CuO.ThO{sub 2}) characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and temperature-programmed reduction. The catalysts were active and selective for the conversion of methane to H{sub 2} and CO and stable for a period of time of {approx}18 h on stream. The nickel catalysts were more active and selective than the copper catalyst and, under the same conditions, show a catalytic behaviour comparable to that of a platinum commercial catalyst, 5 wt% Pt/Al{sub 2}O{sub 3}. The catalytic activity increases when uranium replaces thorium and the selectivity of this type of materials is clearly different from that of single metal oxides and/or mechanical mixtures. The good catalytic behaviour of the bimetallic copper- and nickel-actinide oxides was attributed to an unusual interaction between copper or nickel oxide and the actinide oxide phase as showed by H{sub 2}-TPR, XPS and Raman analysis of the catalysts before and after reaction.

  20. A bimetallic nanocomposite electrode for direct and rapid biosensing of p53 DNA plasmid

    Indian Academy of Sciences (India)

    Ezat Hamidi-Asl; Jahan-Bakhsh Raoof; Nahid Naghizadeh; Simin Sharifi; Mohammad Saeid Hejazi

    2015-09-01

    A new label-free electrochemical DNA biosensor is presented based on carbon paste electrode (CPE) modified with gold (Au) and platinum (Pt) nanoparticles to prepare the bimetallic nanocomposite electrode. The proposed sensor was made by immobilization of 15-mer single stranded oligonucleotide probe related to p53 gene for detection of DNA plasmid samples. The hybridization detection relied on the alternation in the guanine oxidation signal following hybridization of the probe with complementary genomic DNA.The technique of differential pulse voltammetry (DPV) was used for monitoring guanine oxidation. To optimize the performance of the modified CPE, different electrodes were prepared in various percentages of Au and Pt nanoparticles. The modified electrode containing 15% Au/Pt bimetallic nanoparticles (15% Au/Pt-MCPE) was selected as the best working electrode. The selectivity of the sensor was investigated using plasmid samples containing non-complementary oligonucleotides. The detection limit of the biosensor was studied and calculated to be 53.10 pg L−1.

  1. Bimetallic oxamato complexes synthesized into mesoporous matrix as precursor to tunable nanosized oxide

    Energy Technology Data Exchange (ETDEWEB)

    Kalinke, Lucas H.G. [Instituto de Química, Universidade Federal de Goiás—UFG, Goiânia, GO 74001-970 (Brazil); Instituto Federal de Goiás—IFG, Anápolis, GO (Brazil); Stumpf, Humberto O. [Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Minas Gerais—UFMG, Belo Horizonte, MG (Brazil); Mazali, Italo O. [Instituto de Química, Universidade Estadual de Campinas—UNICAMP, Campinas, SP (Brazil); Cangussu, Danielle, E-mail: danielle_cangussu@ufg.br [Instituto de Química, Universidade Federal de Goiás—UFG, Goiânia, GO 74001-970 (Brazil)

    2015-10-15

    Highlights: • The bimetallic oxamato complexes as single-source precursor. • We prepared into a porous silica glass tunable nanosized oxide powders. • X-ray diffraction shows the formation of CeO{sub 2}/CuO and spinel cobaltite. • The different number of IDC allows control of the nanoparticle size. - Abstract: The bimetallic complexes were employed to prepare into a porous silica glass tunable nanosized oxide powders through the single source precursor (SSP) method. These materials were prepared by first anchoring of [Cu(opba)]{sup 2−} [opba = ortho-phenylenebis(oxamato)], second by reaction in situ with second metal [Co(II) or Ce(III)] and followed by a thermal treatment. The different number of impregnation–decomposition cycles (IDC) allows control of the nanoparticle size. X-ray diffraction shows the formation of mixture CeO{sub 2}–CuO and spinel copper cobaltite. Raman spectroscopy confirmed the formation of such phases. Transmission electron microscopy images revealed that spinel cobaltite particles (8 IDC) present a mean size of about 9 nm, whereas for the CeO{sub 2}–CuO phase the particle diameters are 4 nm (2 IDC) and 8 nm (6 IDC). For CeO{sub 2}–CuO the diffuse reflectance spectroscopy indicates a consistent red shift in band gap from 3.41 to 2.87 eV with increasing of particle size due to quantum confinement effect.

  2. On Metal Segregation of Bimetallic Nanocatalysts Prepared by a One-Pot Method in Microemulsions

    Directory of Open Access Journals (Sweden)

    Concha Tojo

    2017-02-01

    Full Text Available A comparative study on different bimetallic nanocatalysts prepared from microemulsions using a one-pot method has been carried out. The analysis of experimental observations, complemented by simulation studies, provides detailed insight into the factors affecting nanoparticle architecture: (1 The metal segregation in a bimetallic nanocatalysts is the result of the combination of three main kinetic parameters: the reduction rate of metal precursors (related to reduction standard potentials, the material intermicellar exchange rate (determined by microemulsion composition, and the metal precursors concentration; (2 A minimum difference between the reduction standard potentials of the two metals of 0.20 V is needed to obtain a core-shell structure. For values ∆ε0 smaller than 0.20 V the obtaining of alloys cannot be avoided, neither by changing the microemulsion nor by increasing metal concentration; (3 As a rule, the higher the film flexibility around the micelles, the higher the degree of mixture in the nanocatalyst; (4 A minimum concentration of metal precursors is required to get a core-shell structure. This minimum concentration depends on the microemulsion flexibility and on the difference in reduction rates.

  3. Ag-Cu Bimetallic Nanoparticles Prepared by Microemulsion Method as Catalyst for Epoxidation of Styrene

    Directory of Open Access Journals (Sweden)

    Hong-Kui Wang

    2012-01-01

    Full Text Available Ag/Cu bimetallic nanocatalysts supported on reticulate-like γ-alumina were prepared by a microemulsion method using N2H4·H2O as the reducing agent. The catalysts were activated by calcination followed with hydrogen reduction at 873K, and the properties were confirmed using various characterization techniques. Compared with metal oxides particles, Ag-Cu particles exhibited smaller sizes (<5 nm after calcination in H2 at 873K. XPS results indicated that the binding energies changed with the Ag/Cu ratios, suggesting that increasing the copper content gave both metals a greater tendency to lose electrons. Furthermore, Ag-Cu bimetallic nanoparticles supported on γ-alumina showed better catalytic activity on the epoxidation of styrene as compared with the corresponding monometallic silver or copper. The styrene oxide selectivity could reach 76.6% at Ag/Cu molar ratio of 3/1, while the maximum conversion (up to 94.6% appeared at Ag/Cu molar ratio of 1/1 because of the maximum interaction between silver and copper.

  4. One-step green synthesis of bimetallic Fe/Pd nanoparticles used to degrade Orange II.

    Science.gov (United States)

    Luo, Fang; Yang, Die; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

    2016-02-13

    To reduce cost and enhance reactivity, bimetallic Fe/Pd nanoparticles (NPs) were firstly synthesized using grape leaf aqueous extract to remove Orange II. Green synthesized bimetallic Fe/Pd NPs (98.0%) demonstrated a far higher ability to remove Orange II in 12h compared to Fe NPs (16.0%). Meanwhile, all precursors, e.g., grape leaf extract, Fe(2+) and Pd(2+), had no obvious effect on removing Orange II since less than 2.0% was removed. Kinetics study revealed that the removal rate fitted well to the pseudo-first-order reduction and pseudo-second-order adsorption model, meaning that removing Orange II via Fe/Pd NPs involved both adsorption and catalytic reduction. The remarkable stability of Fe/Pd NPs showed the potential application for removing azo dyes. Furthermore, Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed the changes in Fe/Pd NPs before and after reaction with Orange II. High Performance Liquid Chromatography-Mass Spectrum (HPLC-MS) identified the degraded products in the removal of Orange II, and finally a removal mechanism was proposed. This one-step strategy using grape leaf aqueous extract to synthesize Fe/Pd NPs is simple, cost-effective and environmentally benign, making possible the large-scale production of Fe/Pd NPs for field remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Structure analysis of bimetallic Co–Au nanoparticles formed by sequential ion implantation

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hua-jian [Hubei province Key Laboratory of Systems Science in Metallurgical Process, Wuhan University of Science and Technology, Wuhan 430081 (China); Wang, Yu-hua, E-mail: wangyuhua@wust.edu.cn [Hubei province Key Laboratory of Systems Science in Metallurgical Process, Wuhan University of Science and Technology, Wuhan 430081 (China); Zhang, Xiao-jian [Hubei province Key Laboratory of Systems Science in Metallurgical Process, Wuhan University of Science and Technology, Wuhan 430081 (China); Song, Shu-peng [State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081 (China); Chen, Hong; Zhang, Ke; Xiong, Zu-zhao; Ji, Ling-ling; Dai, Hou-mei; Wang, Deng-jing; Lu, Jian-duo; Wang, Ru-wu [Hubei province Key Laboratory of Systems Science in Metallurgical Process, Wuhan University of Science and Technology, Wuhan 430081 (China); Zheng, Li-rong [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

    2016-08-15

    Highlights: • Co–Au alloy Metallic nanoparticles (MNPs) are formed by ion implantation in silica glass. • The ion ranges of Au ions implantation process have been displayed to show the ion distribution. • EXAFS, AFM and TEM have been used to study the local structural information of imetallic nanoparticles. • With the increase of Au ion implantation, the local environments of Co ions are changed enormously. Three oscillations are determined. - Abstract: Co–Au alloy Metallic nanoparticles (MNPs) are formed by sequential ion implantation of Co and Au into silica glass at room temperature. The ion ranges of Au ions implantation process have been displayed to show the ion distribution. We have used the atomic force microscopy (AFM) and transmission electron microscopy (TEM) to investigate the formation of bimetallic nanoparticles. The extended X-ray absorption fine structure (EXAFS) has been used to study the local structural information of bimetallic nanoparticles. With the increase of Au ion implantation, the local environments of Co ions are changed enormously. Hence, three oscillations, respectively, Co–O, Co–Co and Co–Au coordination are determined.

  6. Highly active and durable platinum-lead bimetallic alloy nanoflowers for formic acid electrooxidation

    Science.gov (United States)

    Gong, Mingxing; Li, Fumin; Yao, Zhigang; Zhang, Suqi; Dong, Jingwen; Chen, Yu; Tang, Yawen

    2015-03-01

    The Pt84Pb16 (atomic ratio) bimetallic alloy nanoflowers (Pt84Pb16 BANFs) are synthesized by a simple one-pot hydrothermal reduction method that effectively enhance the dehydrogenation pathway of the formic acid oxidation reaction (FAOR) due to the ensemble effect and the electronic effect. As a result, the mass activity of Pt84Pb16 BANFs for the FAOR is 16.7 times higher than that of commercial Pt black at 0.3 V potential.The Pt84Pb16 (atomic ratio) bimetallic alloy nanoflowers (Pt84Pb16 BANFs) are synthesized by a simple one-pot hydrothermal reduction method that effectively enhance the dehydrogenation pathway of the formic acid oxidation reaction (FAOR) due to the ensemble effect and the electronic effect. As a result, the mass activity of Pt84Pb16 BANFs for the FAOR is 16.7 times higher than that of commercial Pt black at 0.3 V potential. Electronic supplementary information (ESI) available: Experimental details. See DOI: 10.1039/c4nr07375d

  7. Photochemical synthesis of mono and bimetallic nanoparticles and their use in catalysis

    Science.gov (United States)

    Pardoe, Andrea

    2011-07-01

    Nanomaterials have become a popular topic of research over the years because of their many important applications. It can be a challenge to stabilize the particles at a nanometer size, while having control over their surface features. Copper nanoparticles were synthesized photochemically using a photogenerated radical allowing spatial and temporal control over their formation. The synthesis was affected by the stabilizers used, which changed the size, dispersity, rate of formation, and oxidation rate. Copper nanoparticles suffer from their fast oxidation in air, so copper-silver bimetallic nanoparticles were synthesized in attempts to overcome the oxidation of copper nanoparticles. Bimetallic nanoparticles were synthesized, but preventing the oxidation of the copper nanoparticles proved difficult. One important application of nanoparticles that was explored here is in catalyzing organic reactions. Because of the fast oxidation of copper nanoparticles, silver nanoparticles were synthesized photochemically on different supports including TiO2 and hydrotalcite (HTC). Their catalytic efficiency was tested using alcohol oxidations. Different silver nanoparticle shapes (decahedra and plates) were compared with the spheres to see the different catalytic efficiencies.

  8. Oxidizing capacity of periodate activated with iron-based bimetallic nanoparticles.

    Science.gov (United States)

    Lee, Hongshin; Yoo, Ha-Young; Choi, Jihyun; Nam, In-Hyun; Lee, Sanghyup; Lee, Seunghak; Kim, Jae-Hong; Lee, Changha; Lee, Jaesang

    2014-07-15

    Nanosized zerovalent iron (nFe0) loaded with a secondary metal such as Ni or Cu on its surface was demonstrated to effectively activate periodate (IO4-) and degrade selected organic compounds at neutral pH. The degradation was accompanied by a stoichiometric conversion of IO4- to iodate (IO3-). nFe0 without bimetallic loading led to similar IO4- reduction but no organic degradation, suggesting the production of reactive iodine intermediate only when IO4- is activated by bimetallic nFe0 (e.g., nFe0-Ni and nFe0-Cu). The organic degradation kinetics in the nFe0-Ni(or Cu)/IO4- system was substrate dependent: 4-chlorophenol, phenol, and bisphenol A were effectively degraded, whereas little or no degradation was observed with benzoic acid, carbamazepine, and 2,4,6-trichlorophenol. The substrate specificity, further confirmed by little kinetic inhibition with background organic matter, implies the selective nature of oxidant in the nFe0-Ni(or Cu)/IO4- system. The comparison with the photoactivated IO4- system, in which iodyl radical (IO3•) is a predominant oxidant in the presence of methanol, suggests IO3• also as primary oxidant in the nFe0-Ni(or Cu)/IO4- system.

  9. Active site of bimetallic heterogeneous catalyst by atomic resolution aberration-corrected STEM

    Energy Technology Data Exchange (ETDEWEB)

    Hsiao, Chien-Nan, E-mail: 0209347@narlabs.org.tw; Lin, Chun-Ting

    2015-11-01

    Highlights: • Up to fifth order aberration coefficients of STEM had been compensated. • The core-shell structural catalyst was identified by Z-contrast image. • Atomic twinning in nanoparticle was revealed by aberration-corrected STEM. - Abstract: The localized defect of Au–Pd bimetallic heterogeneous nanoparticles catalyst was investigated using HRTEM and aberration-corrected HRSTEM. The phase plates were calculated from the aberration coefficients of the measured probe tableau for various outer tilt angle of the optical axis and the accuracy required for the compensation of the various residual aberration coefficients in order to achieve sub-angstrom resolution with the electron optics system was evaluated up to the fifth order aberrations. It is found that the interplanar spacing of the Au–Pd nanoparticle (1 1 1) planes observed along the [1 1 0] zone axis was approximately 0.24 nm measured by HRTEM. In addition, the HRSTEM HAADF image demonstrated that the twin boundaries on the surfaces of heterogeneous nanoparticles catalysts at atomic scale. These defects might be introduced during the growth to alleviate the internal stress caused by the 4.6% lattice mismatch of Au–Pd bimetallic system. Current research could be applied to the study of active sites in nanocatalysts.

  10. 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.

  11. Bimetallic PtxCoy nanoparticles with curved faces for highly efficient hydrogenation of cinnamaldehyde.

    Science.gov (United States)

    Gu, Yan; Zhao, Yonghui; Wu, Panpan; Yang, Bo; Yang, Nating; Zhu, Yan

    2016-06-07

    The control of the curved structure of bimetallic nanocrystals is a challenge, due to the rate differential for atom deposition and surface diffusion of alien atomic species on specific crystallographic planes of seeds. Herein, we report how to tune the degree of concavity of bimetallic PtxCoy concave nanoparticles using carboxylic acids as surfactants with an oleylamine system, leading to the specific crystallographic planes being exposed. The terminal carboxylic acids with a bridge ring or a benzene ring serving as structure regulators could direct the formation of curved faces with exposed high-index facets, and long-chain saturated fatty acids favored the production of curved faces with exposed low-index facets, while long-chain olefin acids alone benefited the formation of a flat surface with exposed low-index planes. Furthermore, these PtxCoy particles with curved faces displayed superior catalytic behaviour to cinnamaldehyde hydrogenation when compared with PtxCoy with flat faces. PtxCoy nanoparticles with curved faces exhibited over 6-fold increase in catalytic activity compared to PtxNiy nanoparticles with curved faces, and near 40-fold activity increase was observed in comparison with PtxFey nanoparticles with curved faces.

  12. Nanostructural Formation of Pd-Co Bimetallic Complex on HOPG Surfaces: XPS and AFM Studies

    Directory of Open Access Journals (Sweden)

    Lisandra Arroyo-Ramírez

    2009-01-01

    Full Text Available A new single source approach was developed to synthesize Pd-Co nanoparticles using a bimetallic compound, [Et3NH]2[CoPd2(μ-4-I-3,5-Me2pz4Cl4] (CoPd2, as a molecular precursor to obtain dispersed catalyst on highly ordered pyrolytic graphite (HOPG surface, in view of preparing oxygen reduction catalysts for low temperature fuel cells. X-ray photoelectron spectroscopy (XPS and atomic force microscopy (AFM techniques were employed to characterize the nanostructure formations and to determine the composition and morphology of the complex on the HOPG. Results of high resolution XPS analysis (HR-XPS revealed the binding energies corresponding to the atomic constituents of the precursor. When the precursor solution was placed on the surface of the HOPG, the bimetallic complex assumes a tubular structure and it appears that the surface of the HOPG offers a ground for the self-organization of nanostructural formations.

  13. Electrospun carbon nanofibers decorated with Ag-Pt bimetallic nanoparticles for selective detection of dopamine.

    Science.gov (United States)

    Huang, Yunpeng; Miao, Yue-E; Ji, Shanshan; Tjiu, Weng Weei; Liu, Tianxi

    2014-08-13

    Electrospun nanoporous carbon nanofibers (pCNFs) decorated with Ag-Pt bimetallic nanoparticles have been successfully synthesized by combining template carbonization and seed-growth reduction approach. Porous-structured polyacrylonitrile (PAN) nanofibers (pPAN) were first prepared by electrospinning PAN/polyvinylpyrrolidone (PVP) blend solution, followed by subsequent water extraction and heat treatment to obtain pCNFs. Ag-Pt/pCNFs were then obtained by using pCNFs as support for bimetallic nanoparticle loading. Thus, the obtained Ag-Pt/pCNFs were used to modify glassy carbon electrode (GCE) for selective detection of dopamine (DA) in the presence of uric acid (UA) and ascorbic acid (AA). This novel sensor exhibits fast amperometric response and high sensitivity toward DA with a wide linear concentration range of 10-500 μM and a low detection limit of 0.11 μM (S/N = 3), wherein the interference of UA and AA can be eliminated effectively.

  14. Catalytically Active Bimetallic Nanoparticles Supported on Porous Carbon Capsules Derived From Metal-Organic Framework Composites.

    Science.gov (United States)

    Yang, Hui; Bradley, Siobhan J; Chan, Andrew; Waterhouse, Geoffrey I N; Nann, Thomas; Kruger, Paul E; Telfer, Shane G

    2016-09-14

    We report a new methodology for producing monometallic or bimetallic nanoparticles confined within hollow nitrogen-doped porous carbon capsules. The capsules are derived from metal-organic framework (MOF) crystals that are coated with a shell of a secondary material comprising either a metal-tannic acid coordination polymer or a resorcinol-formaldehyde polymer. Platinum nanoparticles are optionally sandwiched between the MOF core and the shell. Pyrolysis of the MOF-shell composites produces hollow capsules of porous nitrogen-doped carbon that bear either monometallic (Pt, Co, and Ni) or alloyed (PtCo and PtNi) metal nanoparticles. The Co and Ni components of the bimetallic nanoparticles are derived from the shell surrounding the MOF crystals. The hollow capsules prevent sintering and detachment of the nanoparticles, and their porous walls allow for efficient mass transport. Alloyed PtCo nanoparticles embedded in the capsule walls are highly active, selective, and recyclable catalysts for the hydrogenation of nitroarenes to anilines.

  15. Seed germination and biochemical profile of Silybum marianum exposed to monometallic and bimetallic alloy nanoparticles.

    Science.gov (United States)

    Salman Khan, Muhammad; Zaka, Mehreen; Haider Abbasi, Bilal; Rahman, Latifur-; Shah, Afzal

    2016-12-01

    In recent years nanotechnology has become increasingly important in almost every field. The new and improved physical, chemical and biological properties of material at nanoscale have far reaching implications in the fields of science and technology. Nanoparticles' effect on various plant species must be investigated to develop a comprehensive toxicity profile for nanoparticles. The current study strives to evaluate the effects of nine types of metal nanoparticles including monometallic and bimetallic alloy nanoparticles [Ag, Au, Cu, AgCu (1:3), AgCu (3:1), AuCu (1:3), AuCu (3:1), AgAu (1:3), AgAu (3:1)] on seed germination, root and shoot growth and biochemical profile of Silybum marianum plant. Seed germination was greatly affected and increased significantly upon treatment with nanoparticles' suspensions and was recorded highest for Ag nanoparticle suspension. Metal nanoparticles also had a significant effect on the biochemical profile of S. marianum. For the first week, the effect on DPPH, total phenolics content, total flavonoids content, total protein content, peroxidase activity and superoxide dismutase activity was enhanced, but declined as the time progressed. Among the nanoparticles being used, the effect of Ag nanoparticle was mostly enhancing. The results obtained are significant in mapping the effects of different monometallic and bimetallic nanoparticles on medicinal plant species.

  16. XPS/STM study of model bimetallic Pd–Au/HOPG catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Bukhtiyarov, Andrey V., E-mail: avb@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva Ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Prosvirin, Igor P., E-mail: prosvirin@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva Ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Bukhtiyarov, Valerii I., E-mail: vib@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva Ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation)

    2016-03-30

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

  17. High strength bimetallic composite material fabricated by electroslag casting and characteristics of its composite interface

    Directory of Open Access Journals (Sweden)

    Tian-shun Dong

    2016-11-01

    Full Text Available Bimetallic composite material of bainitic steel and PD3 steel was produced with electroslag casting process, and element distribution of its composite interface was investigated by theoretical calculation and energy dispersive spectrometer (EDS. Results show that the tensile strength (1,450 MPa, hardness (HRC 41-47 and impact toughness (94.7J·cm-2 of bainitic steel were comparatively high, while its elongation was slightly low (4.0%. Tensile strength (1,100 MPa, hardness (>HRC 31 and elongation (7.72% of the interface were also relatively high, but its impact toughness was low at 20.4 J·cm-2. Results of theoretical calculation of the element distribution in the interface region were basically consistent with that of EDS. Therefore, electroslag casting is a practical process to produce bimetallic composite material of bainitic steel and PD3 steel, and theoretical calculation also is a feasible method to study element distribution of their interface.

  18. Electrocatalysis of fuel cells reaction on Pt and Pt-bimetallic anode catalysts: A selective review

    Directory of Open Access Journals (Sweden)

    Stamenković Vojislav

    2002-01-01

    Full Text Available In this review we selectively summarize recent progress, primarily from our laboratory, in the development of interrelationships between the kinetics of the fuel cells reactions and the structure/composition of anode catalysts. The focus is placed on two types of metallic surfaces: platinum single crystals and bimetallic surfaces based on Pt. In the first part it was illustrated that the hydcogen reaction is structure sensitive process, with Pt(110 being an order of magnitude more active than either of the atomically "flatter" (100 and (111 surfaces. The hydrogen reaction on Pt(hkl modified by pseudomorphic Pd (submonolayers shows the "volcano-like" behavior, having the maximum rate on Pt(111 modified by 1 ML of Pd. The Pt(111-Pd system is used to demonstrate how the energetics of intermediates formed in the hydrogen reaction is affected by interfacial bonding and energetic constraints produced between pseudomorphic Pd films and the Pt(111 substrate. In the second part it was shown that the oxidation of Ha in the presence of CO occurs concurrently with CO oxidation on Pt and Pt bimetallic surfaces. The Pt-Ru system is used to demonstrate that both the bifunctional effect and the ligand effect contribute to the influence of Ru on the CO oxidation rate and for Hz oxidation process in the presence of CO. The knowledge is then used to create the real-life catalyst with the catalytic activities which are, to the greatest extend possible similar to the tailor-made surface.

  19. Structural, electronic and adsorption properties of Rh(111)/Mo(110) bimetallic catalyst: A DFT study

    Science.gov (United States)

    Palotás, K.; Bakó, I.; Bugyi, L.

    2016-12-01

    Geometric and electronic characterizations of one monolayer rhodium with Nishiyama-Wassermann (NW) structure on Mo(110) substrate have been performed by density functional theory (DFT) calculations. In the NW structure the Rh atoms form a wavy structure propagating along the [001] direction, characterized by an amplitude of 0.26 Å in the [110] direction and by 0.10 Å in the [110] direction of the Mo(110) substrate. Strain and ligand effects operating in the rhodium film are distinguished and found to be manifested in the downward shift of the d-band center of the electron density of states (DOS) by 0.11 eV and 0.18 eV, respectively. The shift in the d-band center of Rh DOS predicts a decrease in the surface reactivity toward CO adsorption, which has been verified by detailed calculations of bond energies of CO located at on-top, bridge and hollow adsorption sites. The CO adsorption energies are decreased by about 35% compared to those reported for pure Rh(111), offering novel catalytic pathways for the molecule. An in-depth analysis of the charge transfer and the partial DOS characters upon CO adsorption on the NW-structured Rh(111)/Mo(110) bimetallic catalyst and on the pure Rh(111) surface sheds light on the bonding mechanism of CO and on the governing factors determining its lowered bond energy on the bimetallic surface.

  20. Bimetallic PtSn/C catalysts obtained via SOMC/M for glycerol steam reforming.

    Science.gov (United States)

    Pastor-Pérez, Laura; Merlo, Andrea; Buitrago-Sierra, Robison; Casella, Mónica; Sepúlveda-Escribano, Antonio

    2015-12-01

    A detailed study on the preparation of bimetallic PtSn/C catalysts using surface-controlled synthesis methods, and on their catalytic performance in the glycerol steam reforming reaction has been carried out. In order to obtain these well-defined bimetallic phases, techniques derived from Surface Organometallic Chemistry on Metals (SOMC/M) were used. The preparation process involved the reaction between an organometallic compound ((C4H9)4Sn) and a supported transition metal (Pt) in a H2 atmosphere. Catalysts with Sn/Pt atomic ratios of 0.2, 0.3, 0.5, and 0.7 were obtained, and characterized using several techniques: ICP, H2 chemisorption, TEM and XPS. These systems were tested in the glycerol steam reforming varying the reaction conditions (glycerol concentration and reaction temperature). The best performance was observed for the catalysts with the lowest tin contents (PtSn0.2/C and PtSn0.3/C). It was observed that the presence of tin increased the catalysts' stability when working under more severe reaction conditions.

  1. Light alkane (mixed feed selective dehydrogenation using bi-metallic zeolite supported catalyst

    Directory of Open Access Journals (Sweden)

    Zeeshan Nawaz

    2009-12-01

    Full Text Available Light alkanes are the important intermediates of many refinery processes and their catalytic dehydrogenation gives corresponding alkenes. The aim behind this experimentation is to investigate reaction behavior of mixed alkanes during direct catalytic dehydrogenation and emphasis has been given to enhance propene. Bi-metallic zeolite supported catalyst Pt-Sn/ZSM-5 was prepared by sequentional impregnation method and characterized by BET, EDS and XRD. Direct dehydrogenation reaction is highly endothermic and its conversion is thermodynamically limited. Results showed that the increase in temperature increases the conversion to some extent but there is no overall effect on selectivity of propene. Increase in time-on-stream (TOS remarkably improves propene selectivity at the expense of lower conversion. The performances of bi-metallic zeolite based catalyst largely affected by coke deposition. The presence of butane and ethane adversely affected propane conversion. Optimum propene selectivity is about 48 %, obtained at 600 oC and time-on-stream 10 h.

  2. Rational enantioselective design of chiral heterobimetallic single-chain magnets: synthesis, crystal structures and magnetic properties of oxamato-bridged M(II)Cu(II) chains (M=Mn, Co).

    Science.gov (United States)

    Ferrando-Soria, Jesús; Cangussu, Danielle; Eslava, Mercedes; Journaux, Yves; Lescouëzec, Rodrigue; Julve, Miguel; Lloret, Francesc; Pasán, Jorge; Ruiz-Pérez, Catalina; Lhotel, Elsa; Paulsen, Carley; Pardo, Emilio

    2011-10-24

    A new series of neutral oxamato-bridged M(II)Cu(II) chiral chains of general formula [MCuL(x)(S)(m)(H(2)O)(n)]·aS·bH(2)O [L(1)=(M)-1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (1a) and Co (1b); L(2)=(P)-1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (2a) and Co (2b)] and the analogous racemic chains of formula [MCuL(3)(S)(m)(H(2)O)(n)]·aS·bH(2)O [L(3)=1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (3a) and Co (3b)] have been prepared by reaction of the corresponding dianionic oxamatocopper(II) complex [Cu(L(x))](2-) with Mn(2+) or Co(2+) cations in either dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). Solid circular dichroism (CD) spectra of the bimetallic chain compounds were recorded to establish their chiral and enantiomeric nature. They exhibit maximum positive and negative Cotton effects, each pair of enantiomeric chains being non-superimposable mirror images. The crystal structures of the Mn(II)Cu(II) (1a-3a) and the Co(II)Cu(II) (1b and 2b) chain compounds were solved by single-crystal X-ray diffraction methods. Our attempts to obtain X-ray quality crystals of 3b were unsuccessful. The values of the shortest interchain Mn···Mn and Co···Co distances are indicative of a good isolation of neighbouring chains in the crystal lattice, which is caused by the bulky aromatic ligand. Although all the Mn(II)Cu(II) and Co(II)Cu(II) chains exhibit ferrimagnetic behaviour (-J(MnCu)=18.9-26.6 cm(-1) and -J(CoCu)=19.5-32.5 cm(-1)), only the enantiopure Co(II)Cu(II) chains (1b and 2b) show slow magnetic relaxation at low temperatures (T(B)=0.6-1.8 K), which is a characteristic of single-chain magnets (SCMs) and is related to the magnetic anisotropy of the high-spin Co(II) ion. Analysis of the SCM behaviour of 1b and 2b, based on Glauber's theory for an Ising one-dimensional system, shows a thermally activated mechanism for the magnetic relaxation (Arrhenius law dependence). The energy barriers (E(a)) to reverse the magnetisation direction are 8.2 (1b) and

  3. Cluster editing

    DEFF Research Database (Denmark)

    Böcker, S.; Baumbach, Jan

    2013-01-01

    . The problem has been the inspiration for numerous algorithms in bioinformatics, aiming at clustering entities such as genes, proteins, phenotypes, or patients. In this paper, we review exact and heuristic methods that have been proposed for the Cluster Editing problem, and also applications......The Cluster Editing problem asks to transform a graph into a disjoint union of cliques using a minimum number of edge modifications. Although the problem has been proven NP-complete several times, it has nevertheless attracted much research both from the theoretical and the applied side...

  4. Weighted Clustering

    CERN Document Server

    Ackerman, Margareta; Branzei, Simina; Loker, David

    2011-01-01

    In this paper we investigate clustering in the weighted setting, in which every data point is assigned a real valued weight. We conduct a theoretical analysis on the influence of weighted data on standard clustering algorithms in each of the partitional and hierarchical settings, characterising the precise conditions under which such algorithms react to weights, and classifying clustering methods into three broad categories: weight-responsive, weight-considering, and weight-robust. Our analysis raises several interesting questions and can be directly mapped to the classical unweighted setting.

  5. Cluster analysis

    CERN Document Server

    Everitt, Brian S; Leese, Morven; Stahl, Daniel

    2011-01-01

    Cluster analysis comprises a range of methods for classifying multivariate data into subgroups. By organizing multivariate data into such subgroups, clustering can help reveal the characteristics of any structure or patterns present. These techniques have proven useful in a wide range of areas such as medicine, psychology, market research and bioinformatics.This fifth edition of the highly successful Cluster Analysis includes coverage of the latest developments in the field and a new chapter dealing with finite mixture models for structured data.Real life examples are used throughout to demons

  6. Chemical Abundances in a Sample of Red Giants in the Open Cluster NGC 2420 from APOGEE

    CERN Document Server

    Souto, Diogo; Smith, Verne; Prieto, Carlos Allende; Pinsonneault, Marc; Zamora, Olga; García-Hernández, D Anibal; Bovy, Szabolcs Meszaros Jo; Pérez, Ana Elia García; Anders, Friedrich; Bizyaev, Dmitry; Carrera, Ricardo; Frinchaboy, Peter; Holtzman, Jon; Ivans, Inese; Majewski, Steve; Shetrone, Matthew; Sobeck, Jennifer; Pan, Kaike; Tang, Baitian; Villanova, Sandro; Geisler, Douglas

    2016-01-01

    NGC 2420 is a $\\sim$2 Gyr-old well-populated open cluster that lies about 2 kpc beyond the solar circle, in the general direction of the Galactic anti-center. Most previous abundance studies have found this cluster to be mildly metal-poor, but with a large scatter in the obtained metallicities for this open cluster. Detailed chemical abundance distributions are derived for 12 red-giant members of NGC 2420 via a manual abundance analysis of high-resolution (R = 22,500) near-infrared ($\\lambda$1.5 - 1.7$\\mu$m) spectra obtained from the Apache Point Observatory Galactic Evolution Experiment (APOGEE) survey. The sample analyzed contains 6 stars that are identified as members of the first-ascent red giant branch (RGB), as well as 6 members of the red clump (RC). We find small scatter in the star-to-star abundances in NGC 2420, with a mean cluster abundance of [Fe/H] = -0.16 $\\pm$ 0.04 for the 12 red giants. The internal abundance dispersion for all elements (C, N, O, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Co and Ni...

  7. Fuzzy Clustering

    DEFF Research Database (Denmark)

    Berks, G.; Keyserlingk, Diedrich Graf von; Jantzen, Jan

    2000-01-01

    A symptom is a condition indicating the presence of a disease, especially, when regarded as an aid in diagnosis.Symptoms are the smallest units indicating the existence of a disease. A syndrome on the other hand is an aggregate, set or cluster of concurrent symptoms which together indicate...... and clustering are the basic concerns in medicine. Classification depends on definitions of the classes and their required degree of participant of the elements in the cases' symptoms. In medicine imprecise conditions are the rule and therefore fuzzy methods are much more suitable than crisp ones. Fuzzy c......-mean clustering is an easy and well improved tool, which has been applied in many medical fields. We used c-mean fuzzy clustering after feature extraction from an aphasia database. Factor analysis was applied on a correlation matrix of 26 symptoms of language disorders and led to five factors. The factors...

  8. Catalytic Sorption of (Chloro)Benzene and Napthalene in Aqueous Solutions by Granular Activated Carbon Supported Bimetallic Iron and Palladium Nanoparticles

    Science.gov (United States)

    Adsorption of benzene, chlorobenzene, and naphthalene on commercially available granular activated carbon (GAC) and bimetallic nanoparticle (Fe/Pd) loaded GAC was investigated for the potential use in active capping of contaminated sediments. Freundlich and Langmuir linearizatio...

  9. Investigation of a Cu/Pd Bimetallic System Electrodeposited on Boron-Doped Diamond Films for Application in Electrocatalytic Reduction of Nitrate

    Directory of Open Access Journals (Sweden)

    Jorge T. Matsushima

    2012-01-01

    Full Text Available The Cu/Pd bimetallic system electrodeposited on boron-doped diamond (BDD films for application, as electrode material in the electrochemical reduction of nitrate was studied. The electrochemical behavior of Cu, Pd, and Cu/Pd bimetallic system was evaluated by cyclic voltammetry. From these results, the formation of the Cu/Pd composite was verified. In addition, Cu with different phases and a Cu/Pd phase in the composite were obtained. Morphological analysis by scanning electron microscopy (SEM revealed a homogeneous distribution of Cu/Pd bimetallic particles with intermediary dimensions compared to those observed in Cu or Pd electrodeposits separately. These composites were tested as electrocatalysts for nitrate reduction in Britton-Robinson buffer solution (pH 9. Electrochemical measurements showed that composites with higher Cu content displayed the best electrocatalytic activity for nitrate reduction, and the Cu/Pd phase in the bimetallic system served to improve the Cu adherence on BDD electrode.

  10. Catalytic Sorption of (Chloro)Benzene and Napthalene in Aqueous Solutions by Granular Activated Carbon Supported Bimetallic Iron and Palladium Nanoparticles

    Science.gov (United States)

    Adsorption of benzene, chlorobenzene, and naphthalene on commercially available granular activated carbon (GAC) and bimetallic nanoparticle (Fe/Pd) loaded GAC was investigated for the potential use in active capping of contaminated sediments. Freundlich and Langmuir linearizatio...

  11. Bimetallic Catalysts and Platinum Surfaces Studied by X-ray Absorption Spectroscopy and Scanning Tunnelling Microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Roenning, Magnus

    2000-07-01

    Bimetallic catalyst systems used in Fischer-Tropsch synthesis (Co-Re/Al{sub 2}O{sub 3}) and in the naphtha reforming process (Pt-Re/Al{sub 2}O{sub 3}) have been studied in situ using X-ray absorption spectroscopy (EXAFS). Additionally, the adsorption of ethene on platinum single crystal surfaces has been investigated using scanning tunnelling microscopy. In situ EXAFS at the cobalt K absorption edge have been carried out at 450{sup o}C on the hydrogen reduction of a rhenium-promoted Co{sub 3}O{sub 4}/Al{sub 2}O{sub 3} catalyst. Reductions carried out using 100% hydrogen and 5% hydrogen in helium gave different results. Whereas the reduction using dilute hydrogen leads to bulk-like metallic cobalt particles (hcp or fcc), reaction with pure hydrogen yields a more dispersed system with smaller cobalt metal particles (< 40 A). The results are rationalised in terms of different degrees of reoxidation of cobalt by the higher and lower concentrations of water generated during the reduction of cobalt oxide by 100% and 5% hydrogen, respectively. Additionally, in both reduction protocols a small fraction (3 -4 wt%) of the cobalt content is randomly dispersed over the tetrahedral vacancies of the alumina support. This dispersion occurs during reduction and not calcination. The cobalt in these sites cannot be reduced at 450 {sup o}C. The local environments about the rhenium atoms in Co-Re/{gamma}-A1{sub 2}O{sub 3} catalyst after different reduction periods have been studied by X-ray absorption spectroscopy. A bimetallic catalyst containing 4.6 wt% cobalt and 2 wt% rhenium has been compared with a corresponding monometallic sample with 2 wt% rhenium on the same support. The rhenium L{sub III} EXAFS analysis shows that bimetallic particles are formed after reduction at 450{sup o}C with the average particle size being 10-15 A. Rhenium is shown to be reduced at a later stage than cobalt. The fraction of cobalt atoms entering the support obstructs the access to the support for the

  12. Bimetallic Catalysts and Platinum Surfaces Studied by X-ray Absorption Spectroscopy and Scanning Tunnelling Microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Roenning, Magnus

    2000-07-01

    Bimetallic catalyst systems used in Fischer-Tropsch synthesis (Co-Re/Al{sub 2}O{sub 3}) and in the naphtha reforming process (Pt-Re/Al{sub 2}O{sub 3}) have been studied in situ using X-ray absorption spectroscopy (EXAFS). Additionally, the adsorption of ethene on platinum single crystal surfaces has been investigated using scanning tunnelling microscopy. In situ EXAFS at the cobalt K absorption edge have been carried out at 450{sup o}C on the hydrogen reduction of a rhenium-promoted Co{sub 3}O{sub 4}/Al{sub 2}O{sub 3} catalyst. Reductions carried out using 100% hydrogen and 5% hydrogen in helium gave different results. Whereas the reduction using dilute hydrogen leads to bulk-like metallic cobalt particles (hcp or fcc), reaction with pure hydrogen yields a more dispersed system with smaller cobalt metal particles (< 40 A). The results are rationalised in terms of different degrees of reoxidation of cobalt by the higher and lower concentrations of water generated during the reduction of cobalt oxide by 100% and 5% hydrogen, respectively. Additionally, in both reduction protocols a small fraction (3 -4 wt%) of the cobalt content is randomly dispersed over the tetrahedral vacancies of the alumina support. This dispersion occurs during reduction and not calcination. The cobalt in these sites cannot be reduced at 450 {sup o}C. The local environments about the rhenium atoms in Co-Re/{gamma}-A1{sub 2}O{sub 3} catalyst after different reduction periods have been studied by X-ray absorption spectroscopy. A bimetallic catalyst containing 4.6 wt% cobalt and 2 wt% rhenium has been compared with a corresponding monometallic sample with 2 wt% rhenium on the same support. The rhenium L{sub III} EXAFS analysis shows that bimetallic particles are formed after reduction at 450{sup o}C with the average particle size being 10-15 A. Rhenium is shown to be reduced at a later stage than cobalt. The fraction of cobalt atoms entering the support obstructs the access to the support for the

  13. A Preliminary Report on the Strength and Metallography of a Bimetallic Friction Stir Weld Joint Between AA6061 and MIL-DTL-46100E High Hardness Steel Armor

    Science.gov (United States)

    2012-11-26

    bimetallic friction stir weld joint between AA6061 and MIL-DTL-46100E High Hardness steel armor. ABSTRACT One half inch thick plates of 6061-T6 aluminum...alloy and High Hardness steel armor (MIL- STD-46100) were successfully joined by the friction stir welding (FSW) process using a tungsten-rhenium...4. TITLE AND SUBTITLE A preliminary report on the strength and metallography of a bimetallic friction stir weld joint between AA6061 and MIL-DTL

  14. CATALYSIS SCIENCE INITIATIVE: From First Principles Design to Realization of Bimetallic Catalysts for Enhanced Selectivity

    Energy Technology Data Exchange (ETDEWEB)

    MAVRIKAKIS, MANOS

    2007-05-03

    In this project, we have integrated state-of-the-art Density Functional Theory (DFT) models of heterogeneous catalytic processes with high-throughput screening of bimetallic catalytic candidates for important industrial problems. We have studied a new class of alloys characterized by a surface composition different from the bulk composition, and investigated their stability and activity for the water-gas shift reaction and the oxygen reduction reaction. The former reaction is an essential part of hydrogen production; the latter is the rate-limiting step in low temperature H2 fuel cells. We have identified alloys that have remarkable stability and activity, while having a much lower material cost for both of these reactions. Using this knowledge of bimetallic interactions, we have also made progress in the industrially relevant areas of carbohydrate reforming and conversion of biomass to liquid alkanes. One aspect of this work is the conversion of glycerol (a byproduct of biodiesel production) to synthesis gas. We have developed a bifunctional supported Pt catalyst that can cleave the carbon-carbon bond while also performing the water-gas shift reaction, which allows us to better control the H2:CO ratio. Knowledge gained from the theoretical metal-metal interactions was used to develop bimetallic catalysts that perform this reaction at low temperature, allowing for an efficient coupling of this endothermic reaction with other reactions, such as Fischer-Tropsch or methanol synthesis. In our work on liquid alkane production from biomass, we have studied deactivation and selectivity in these areas as a function of metal-support interactions and reaction conditions, with an emphasis on the bifunctionality of the catalysts studied. We have identified a stable, active catalyst for this process, where the selectivity and yield can be controlled by the reaction conditions. While complete rational design of catalysts is still elusive, this work demonstrates the power of

  15. Novel platinum–palladium bimetallic nanoparticles synthesized by Dioscorea bulbifera: anticancer and antioxidant activities

    Directory of Open Access Journals (Sweden)

    Ghosh S

    2015-12-01

    Full Text Available Sougata Ghosh,1 Rahul Nitnavare,1 Ankush Dewle,1 Geetanjali B Tomar,1 Rohan Chippalkatti,1 Piyush More,1 Rohini Kitture,2 Sangeeta Kale,2 Jayesh Bellare,3 Balu A Chopade4 1Institute of Bioinformatics and Biotechnology, University of Pune, 2Department of Applied Physics, Defense Institute of Advanced Technology, Pune, 3Department of Chemical Engineering, Indian Institute of Technology Bombay, Mumbai, 4Department of Microbiology, University of Pune, Pune, India Abstract: Medicinal plants serve as rich sources of diverse bioactive phytochemicals that might even take part in bioreduction and stabilization of phytogenic nanoparticles with immense therapeutic properties. Herein, we report for the first time the rapid efficient synthesis of novel platinum–palladium bimetallic nanoparticles (Pt–PdNPs along with individual platinum (PtNPs and palladium (PdNPs nanoparticles using a medicinal plant, Dioscorea bulbifera tuber extract (DBTE. High-resolution transmission electron microscopy revealed monodispersed PtNPs of size 2–5 nm, while PdNPs and Pt–PdNPs between 10 and 25 nm. Energy dispersive spectroscopy analysis confirmed 30.88%±1.73% elemental Pt and 68.96%±1.48% elemental Pd in the bimetallic nanoparticles. Fourier transform infrared spectra indicated strong peaks at 3,373 cm-1, attributed to hydroxyl group of polyphenolic compounds in DBTE that might play a key role in bioreduction in addition to the sharp peaks at 2,937, 1,647, 1,518, and 1,024 cm-1, associated with C–H stretching, N–H bending in primary amines, N–O stretching in nitro group, and C–C stretch, respectively. Anticancer activity against HeLa cells showed that Pt–PdNPs exhibited more pronounced cell death of 74.25% compared to individual PtNPs (12.6% or PdNPs (33.15%. Further, Pt–PdNPs showed an enhanced scavenging activity against 2,2-diphenyl-1-picrylhydrazyl, superoxide, nitric oxide, and hydroxyl radicals. Keywords: Dioscorea bulbifera, platinum nanoparticles

  16. Crystal and electronic structure study of AgAu and AgCu bimetallic alloy thin films by X-ray techniques

    Energy Technology Data Exchange (ETDEWEB)

    Ozkendir, O. Murat, E-mail: ozkendir@gmail.com [Mersin University, Faculty of Technology, Energy Systems Engineering, Tarsus (Turkey); Mersin University, Institute of Natural Science, Department of Nanotechnology and Advanced Materials, Mersin (Turkey); Cengiz, E. [Karadeniz Technical University, Faculty of Science, Department of Physics, Trabzon (Turkey); Yalaz, E. [Mersin University, Institute of Natural Science, Department of Nanotechnology and Advanced Materials, Mersin (Turkey); Söğüt, Ö.; Ayas, D.H. [Kahramanmaraş Sütçü İmam Üniversitesi, Faculty of Science and Letters, Department of Physics, Kahramanmaraş (Turkey); Thammajak, B. Nirawat [Synchrotron Light Research Institute (Public Organisation), 111 University Avenue, T. Suranaree, A. Muang, Nakhon Ratchasima 30000 (Thailand)

    2016-05-15

    Highlights: • Crystal and electronic properties of bimetallic AgCu and AgAu alloy thin films were studied. • Both AgCu and AgAu bimetallic samples were determined to have cubic crystal geometry. • Strong influence of Cu and Au atoms on the electronic structure of the Ag atoms were determined. - Abstract: Crystal and electronic structure properties of bimetallic AgAu and AgCu alloy thin films were investigated by X-ray spectroscopic techniques. The aim of this study is to probe the influence of Au or Cu atoms on the electronic behaviors of Ag ions in bimetallic alloy materials that yields different crystal properties. To identify the mechanisms causing crystal phase transitions, study were supported by the collected EXAFS (Extended X-ray Absorption Fine Structure) data. Crystal structures of both Cu and Au doped bimetallic Ag samples were determined mainly in cubic geometry with “Fm3m” space group. Through the Ag–Au and Ag–Cu molecular interactions during bimetallic alloy formations, highly overlapped electronic levels that supports large molecular band formations were observed with different ionization states. Besides, traces of the d–d interactions in Au rich samples were determined as the main interplay in the broad molecular bond formations. The exact atomic locations and types in the samples were determined by EXAFS studies and supported by the performed calculations with FEFF scientific code.

  17. Core/shell formation and surface segregation of multi shell icosahedral silver-palladium bimetallic nanostructures: A dynamic and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Hewage, Jinasena W., E-mail: jinasena@chem.ruh.ac.lk

    2016-05-01

    Core/shell formation and surface segregation of multi shell icosahedral bimetallic silver-palladium nanostructures with the size of 55 and 147 atoms were studied by using the Molecular Dynamics simulations, and calculating Helmholtz free energy changes in the penetration of palladium atoms from shell to core, core to shell transition of silver and melting temperatures by using statistical mechanical densities of states. In 55 atoms icosahedra, two core–shell motifs, Ag{sub 13}Pd{sub 42} and Pd{sub 13}Ag{sub 42} with their isomers Pd{sub 13}(Pd{sub 29}Ag{sub 13}) and Ag{sub 13}(Ag{sub 29}Pd{sub 13}) were considered. Similarly in 147 atoms icosahedra, all mutations corresponding to the occupations of either silver atoms or palladium atoms in the core, inner shell or outer shell and their isomers generated by interchanging thirteen core atoms with thirteen atoms of the other type in the inner and outer shells were considered. It is found that the palladium-core clusters are more stable than the silver-core clusters and cohesive energy increases with the palladium composition. Phase transition of each cluster was studied by means of constant volume heat capacity. The trend in variation of melting temperature is accordance with the energy trend. Helmholtz free energy changes in palladium penetration, core to shell transition of silver and in surface mixing and segregation revealed the thermodynamic stability of the formation of Pd{sub core}Ag{sub shell} structures especially at silver rich environment and the surface segregation of silver. - Highlights: • Nanostructures of Pd{sub m}Ag{sub n} clusters for m + n = 55 and 147 have been studied. • Structures favor the formation of palladium-core surrounded by silver shell. • Calculated thermodynamic parameters confirm the energetic results. • Core/shell formation is favored at concentration of silver. • Silver segregation on surface while palladium penetration to core is observed.

  18. Cluster forcing

    DEFF Research Database (Denmark)

    Christensen, Thomas Budde

    .g. sustainability or quality of life. The purpose of this paper is to explore how and to what extent public sector interventions that aim at forcing cluster development in industries can support sustainable development as defined in the Brundtland tradition and more recently elaborated in such concepts as eco......, Portugal and New Zealand have adopted the concept. Public sector interventions that aim to support cluster development in industries most often focus upon economic policy goals such as enhanced employment and improved productivity, but rarely emphasise broader societal policy goals relating to e...... to the automotive sector in Wales. Specifically, the paper evaluates the "Accelerates" programme initiated by the Welsh Development Agency and elaborates on how and to what extent the Accelerate programme supports the development of a sustainable automotive industry cluster. The Accelerate programme was set up...

  19. High-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles for phenol hydrogenation

    Science.gov (United States)

    Huang, Chao; Yang, Xu; Yang, Hui; Huang, Peiyan; Song, Huiyu; Liao, Shijun

    2014-10-01

    A high-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles (MSN), PdRu/MSN, was prepared by a facile impregnation-hydrogen reduction method. It was found that PdRu/MSN showed 5 times higher activity than that of Pd/MSN towards the liquid-phase hydrogenation of phenol. The catalysts were characterized comprehensively by multiple techniques, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature program reduction (TPR). It was revealed that adding Ru could effectively improve the Pd dispersion and promote the electronic interaction between the Pd and Ru, both of which contribute to enhancing the catalytic activity.

  20. FORMATION MECHANISM FOR THE NANOSCALE AMORPHOUS INTERFACE IN PULSE-WELDED AL/FE BIMETALLIC SYSTEM

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jingjing; Yu, Qian; Zhang, Zijiao; Xu, Wei; Sun, Xin

    2016-05-20

    Pulse or impact welding traditionally has been referred to as “solid-state” welding. By integrating advanced interface characterizations and diffusion calculations, we report that the nanoscale amorphous interface in the pulse-welded Al/Fe bimetallic system is formed by rapid heating and melting of a thin Al layer at the interface, diffusion of iron atoms in the liquid aluminum, and subsequent rapid quenching with diffused iron atoms in solution. This finding challenges the commonly held belief regarding the solid-state nature of the impact-based welding process for dissimilar metals. Elongated ultra-fine grains with high dislocation density and ultra-fine equiaxed grains also are observed in the weld interface vicinity on the steel and aluminum sides, respectively, which further confirms that melting and the resulted recrystallization occurred on the aluminum side of the interface.

  1. Using Mechanical Alloying to Create Bimetallic Catalysts for Vapor-Phase Carbon Nanofiber Synthesis

    Directory of Open Access Journals (Sweden)

    Laura Guevara

    2015-10-01

    Full Text Available Carbon nanofibers were generated over bimetallic catalysts in an atmospheric pressure chemical vapor deposition (APCVD reactor. Catalyst compositions of Fe 30 at%, Cu and Ni 30 at% and Cu were mechanically alloyed using high-energy ball milling over durations of 4, 8, 12, 16, and 20 h. The catalyst powders were then used to produce carbon nanofibers in ethylene and hydrogen (4:1 at temperatures of 500, 550, and 600 °C. The microstructures of the catalysts were characterized as a function of milling time as well as at deposition temperature. The corresponding carbon deposition rates were assessed and are correlated to the microstructural features of each catalyst. The milling process directly determines the performance of each catalyst toward carbon deposition, and both catalysts performed comparably to those made by traditional co-precipitation methods. Considerations in miscible and immiscible nanostructured alloy systems are discussed.

  2. Hydrogen storage cycling of MgH2 thin film nanocomposites catalyzed by bimetallic Cr Ti

    Science.gov (United States)

    Zahiri, Beniamin; Amirkhiz, Babak Shalchi; Mitlin, David

    2010-08-01

    We examine hydrogen sorption cycling of 1.5 μm thick magnesium thin films containing a bimetallic chromium titanium catalyst. At 200 °C these nanocomposites absorb 5 wt % hydrogen in several seconds, and desorb in 10-20 minutes. In several compositions, there is negligible hydrogenation kinetics or capacity degradation even at over 100 cycles. Equally importantly, the ternary films require minimal activation, achieving rapid magnesium hydride formation and decomposition from cycle one. Pressure-composition isotherms display well-known enthalpies of MgH2. Transmission electron microscopy analysis supports a hypothesis that such extreme kinetics is due to the presence of a nanodispersed Cr Ti phase in Mg matrix.

  3. Dual Wavelength Laser Writing and Measurement Methodology for High Resolution Bimetallic Grayscale Photomasks

    Science.gov (United States)

    Qarehbaghi, Reza

    Grayscale bimetallic photomasks consist of bi-layer thermal resists (Bismuth-on-Indium or Tin-on-Indium) which become controllably transparent when exposed to a focused laser beam as a function of the absorbed power changing from ~3OD (unexposed) to writing. This thesis investigates using two wavelength beams for mask writing (514.5nm) and OD measurement (457.9nm) separated from a multi-line Argon ion laser source: a Dual Wavelength Writing and Measurement System. The writing laser profile was modified to a top-hat using a beam shaper. Several mask patterns tested the creation of high resolution grayscale masks. Finally, for creation of 3D structures in photoresist, the mask transparency to resist thickness requirements was formulated and linear slope patterns were successfully created.

  4. Stability of the Shallow Axisymmetric Parabolic-Conic Bimetallic Shell by Nonlinear Theory

    Directory of Open Access Journals (Sweden)

    M. Jakomin

    2011-01-01

    Full Text Available In this contribution, we discuss the stress, deformation, and snap-through conditions of thin, axi-symmetric, shallow bimetallic shells of so-called parabolic-conic and plate-parabolic type shells loaded by thermal loading. According to the theory of the third order that takes into account the balance of forces on a deformed body, we present a model with a mathematical description of the system geometry, displacements, stress, and thermoelastic deformations. The equations are based on the large displacements theory. We numerically calculate the deformation curve and the snap-through temperature using the fourth-order Runge-Kutta method and a nonlinear shooting method. We show how the temperature of both snap-through depends on the point where one type of the rotational curve transforms into another.

  5. Surface-Bound Ligands Modulate Chemoselectivity and Activity of a Bimetallic Nanoparticle Catalyst

    KAUST Repository

    Vu, Khanh B.

    2015-04-03

    "Naked" metal nanoparticles (NPs) are thermodynamically and kinetically unstable in solution. Ligands, surfactants, or polymers, which adsorb at a particle\\'s surface, can be used to stabilize NPs; however, such a mode of stabilization is undesirable for catalytic applications because the adsorbates block the surface active sites. The catalytic activity and the stability of NPs are usually inversely correlated. Here, we describe an example of a bimetallic (PtFe) NP catalyst stabilized by carboxylate surface ligands that bind preferentially to one of the metals (Fe). NPs stabilized by fluorous ligands were found to be remarkably competent in catalyzing the hydrogenation of cinnamaldehyde; NPs stabilized by hydrocarbon ligands were significantly less active. The chain length of the fluorous ligands played a key role in determining the chemoselectivity of the FePt NP catalysts. (Chemical Presented). © 2015 American Chemical Society.

  6. Bi-Metallic Composite Structures With Designed Internal Residual Stress Field

    Science.gov (United States)

    Brice, Craig A.

    2014-01-01

    Shape memory alloys (SMA) have a unique ability to recover small amounts of plastic strain through a temperature induced phase change. For these materials, mechanical displacement can be accomplished by heating the structure to induce a phase change, through which some of the plastic strain previously introduced to the structure can be reversed. This paper introduces a concept whereby an SMA phase is incorporated into a conventional alloy matrix in a co-continuous reticulated arrangement forming a bi-metallic composite structure. Through memory activation of the mechanically constrained SMA phase, a controlled residual stress field is developed in the interior of the structure. The presented experimental data show that the memory activation of the SMA composite component significantly changes the residual stress distribution in the overall structure. Designing the structural arrangement of the two phases to produce a controlled residual stress field could be used to create structures that have much improved durability and damage tolerance properties.

  7. 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.

  8. 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.

  9. Glycerol conversion into value added chemicals over bimetallic catalysts in supercritical carbon dioxide

    Science.gov (United States)

    Hidayati, Luthfiana N.; Sudiyarmanto, Adilina, Indri B.

    2017-01-01

    Development of alternative energy from biomass encourage the experiments and production of biodiesel lately. Biodiesel industries widely expand because biodiesel as substitute of fossil fuel recognized as promising renewable energy. Glycerol is a byproduct of biodiesel production, which is resulted 10% wt average every production. Meanwhile, carbon dioxide is a gas that is very abundant amount in the atmosphere. Glycerol and carbon dioxide can be regarded as waste, possibly will produce value-added chemical compounds through chemically treated. In this preliminary study, conversion of glycerol and carbon dioxide using bimetallic catalyst Ni-Sn with various catalyst supports : MgO, γ-Al2O3, and hydrotalcite. Catalysts which have been prepared, then physically characterized by XRD, surface area and porosity analysis, and thermal gravity analysis. Catalytic test performance using supercritical carbon dioxide conditions. Furthermore, the products were analyzed by GC. The final product mostly contained of propylene glycol and glycerol carbonate.

  10. Transition from core-shell to Janus chemical configuration for bimetallic nanoparticles

    Science.gov (United States)

    Langlois, Cyril; Li, Z. L.; Yuan, Jun; Alloyeau, Damien; Nelayah, Jaysen; Bochicchio, Davide; Ferrando, Riccardo; Ricolleau, Christian

    2012-05-01

    In order to determine the possibilities to control the chemical configuration of bimetallic nanoparticles, we have considered CuAg nanoparticles synthesized by a physical route as a model in this study. The synthesis was made by pulsed laser deposition under ultra-high vacuum conditions, via a sequential deposition procedure. We show that the temperature of the substrate and the absolute quantity of Ag in a particle are the main parameters that drive the chemical configuration. To explain the transition from a core-shell configuration to a Janus configuration as a function of Ag quantity, we have conducted density-functional theory calculations and atomistic molecular dynamics simulations to investigate the stability of this system. The results are presented together with the experimental observations.

  11. Surface Plasmon Resonance from Bimetallic Interface in Au–Ag Core–Shell Structure Nanowires

    Directory of Open Access Journals (Sweden)

    Zhu Jian

    2009-01-01

    Full Text Available Abstract Transverse surface plasmon resonances (SPR in Au–Ag and Ag–Au core–shell structure nanowires have been investigated by means of quasi-static theory. There are two kinds of SPR bands resulting from the outer surface of wall metal and the interface between core and wall metals, respectively. The SPR corresponding to the interface, which is similar to that of alloy particle, decreases and shifts obviously with increasing the wall thickness. However, the SPR corresponding to the outer surface, which is similar to that of pure metal particle, increases and shifts slightly with increasing the wall thickness. A mechanism based on oscillatory surface electrons under coulombic attraction is developed to illuminate the shift fashion of SPR from bimetallic core–shell interface. The net charges and extra coulombic force in metallic wall affect the SPR energy and the shift fashion.

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

    Science.gov (United States)

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

    2014-12-01

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

  13. SULFUR-RESISTANT BIMETALLIC NOBLE METAL CATALYSTS FOR AROMATIC HYDROGENATION OF DIESEL FUEL

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Y zeolite supporting noble metal catalysts, as the important industrial catalysts for aromatics hydrogenation, have received increasing attention in recent years. Pd-M/Y bimetallic catalysts, where M is non-noble metal element, were prepared to investigate the effects of the addition of a second metal. Pd-M/Y catalysts were evaluated under the following conditions: H2 pressure 4.2 MPa, MHSV 4.0 h-1, sulfur content in feed 3000 μg/g. The microreactor results indicated that the second metal remarkably affects the hydrogenation activity of Pd/Y catalysts. Among them, Cr and W improve the sulfur resistance of Pd/Y, but La, Mn, Mo and Ag make the sulfur resistance worse and the second metals have no evident influence on product selectivity and acidic properties of the catalysts.

  14. Nanosystems: the use of nanoalloys, metallic, bimetallic, and magnetic nanoparticles in biomedical applications.

    Science.gov (United States)

    McNamara, Karrina; Tofail, Syed A M

    2015-11-14

    There is a growing interest in the use of nanosystems such as nanoalloys, bimetallic nanoparticles, metallic nanoparticles and magnetic nanoparticles in biomedical applications. These applications can be as diverse as hyperthermic treatments; targeted drug delivery; bio-imaging; cell labelling and gene delivery. The use of nanoalloys in these applications has received only limited attention due to the fact that there were many unanswered questions and concerns regarding nanoparticles and nanoalloys such as their stability over time, tendency to agglomerate, chemical activity, ease of oxidation, biocompatibility and cytotoxicity. In this chapter we survey current applications and advances in magnetic nanoparticles used in these biomedical applications so as to understand the materials properties that can pave the way for the use of nanoalloys as a potential alternative or improve solutions that are offered by current materials.

  15. Tryptophan-Assisted Synthesis Reduces Bimetallic Gold/Silver Nanoparticle Cytotoxicity and Improves Biological Activity

    Directory of Open Access Journals (Sweden)

    Igor O. Shmarakov

    2014-10-01

    Full Text Available Aiming to reduce the potential in vivo hepato-and nephrotoxicity of Ag/Au bimetallic nanoparticles (NPs stabilized by sodium dodecyl sulphate (SDS, an approach involving a simultaneous reduction of silver nitrate and tetrachlorauratic acid using tryptophan (Trp as a reducing/stabilizing agent was applied during NP synthesis. The obtained Ag/Au/Trp NPs (5–15 nm sized were able to form stable aggregates with an average size of 370–450 nm and were potentially less toxic than Ag/Au/SDS in relation to a mouse model system based on clinical biochemical parameters and oxidative damage product estimation. Ag/Au/Trp NPs were shown to exhibit anticancer activity in relation to a Lewis lung carcinoma model. The data generated from the present study support the fact that the use of tryptophan in NP synthesis is effective in attenuating the potential hepatotoxicity and nephrotoxicity of NPs during their in vivo application.

  16. Shape, Thermodynamics, Kinetics and Growth Mechanisms of Metal and Bimetallic Nanoparticles

    Science.gov (United States)

    Peng, Lingxuan

    Metal and bimetallic nanoparticles are of interest and are widely used in various applications because of their unique optical, electronic, and catalytic properties, which differ from those of their bulk counterparts. Better understanding of the thermodynamic and kinetic properties of nanoparticles and their underlying growth mechanisms can serve as a basis for improving reproducibility and rational design of nanoparticle syntheses. The primary objective of this dissertation was to study the structural-related thermodynamic and kinetic properties of nanoparticles via the combination of experimental and theoretical techniques and to further unravel their underlying growth mechanisms. In this dissertation, the structure and elemental distribution of colloidally-synthesized bimetallic nanoparticles were characterized via scanning/transmission electron microscopy (S/TEM) and energy dispersive X-ray spectroscopy (EDX). In colloidally-synthesized bimetallic Pt/Pd nanoparticles, smooth composition gradients from the particle centers to their surfaces and corner enrichment of Pt were observed experimentally. A growth model was developed to demonstrate that the smooth composition gradients within the particles were the result of the difference in the deposition rate constants of Pd and Pt, causing Pd to deposit faster than Pt. The deposition rate constant ratio between Pd and Pt increased with total Pd and Pt precursor concentration. The corner Pt enrichment was a result of local thermodynamic control at the corners. At the nanoparticle corner, a Lyapunov stable solution could be achieved when the chemical potential at the corner equals the external chemical potential in the solution. This stable solution leads to size-independent corner rounding in colloidal synthesized nanoparticles. Strain-induced segregation in bimetallic multiply twinned particles, namely decahedral (Dh) and icosahedral (Ic) particles, was analyzed by an analytic first-order expansion within a

  17. 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.

  18. Study of carbon-supported bimetallic PtCu nanoparticles by ASAXS

    Science.gov (United States)

    Bulat, N. V.; Avakyan, L. A.; Pryadchenko, V. V.; Srabionyan, V. V.; Belenov, S. V.; Bugaev, L. A.

    2017-05-01

    Bimetallic platinum-copper nanoparticles on carbon support are studied as a perspective electrochemical catalyst by anomalous small-angle X-ray scattering near the Pt absorption L3-edge. The simultaneous fitting of several diffraction patterns measured at different photon energies lead to a satisfactory agreement between experimental and model curves in the assumption of core-shell structure of the particles with Pt-rich shell and Cu-rich core. It is shown that the average size of as prepared nanoparticles is about 6 nm with distribution spread of about ±2 nm and with thickness of Pt-rich shell approximately 1.6 nm. After annealing at 350o C the average size of the particles increased by two times with additional enlargement of the Pt-rich shell thickness.

  19. Influential factors of 2-chlorobiphenyl reductive dechlorination by highly dispersed bimetallic nanoparticles

    Directory of Open Access Journals (Sweden)

    Jiang Junrong

    2016-01-01

    Full Text Available Highly dispersed Pd-Fe0 bimetallic nanoparticles were prepared in the presence of 40 kHz ultrasonic irradiation in order to enhance disparity and reactivity, and simultaneously avoid agglomeration. Influential factors of 2-chlorobiphenyl (2-Cl BP reductive dechlorination by highly dispersed Pd-Fe0 nanoparticles were investigated. Experimental results showed that highly dispersed Pd-Fe0 nanoparticles prepared in the in the presence of ultrasound could further improve the dechlorination efficiency of 2-Cl BP, meanwhile the biphenyl (BP formation rates increased obviously and increased from 47.4% (in the absence of ultrasound to 95.3% (in the presence of ultrasound within 300 min. The catalytic reductive dechlorination effciency of 2-Cl BP was dependent on Pd-Fe0 nanoparticles prepared methods, Pd-Fe0 nanoparticles dosage, Pd loading percentage over Fe0 and initial pH values

  20. Effects of Irregular Bimetallic Nanostructures on the Optical Properties of Photosystem I from Thermosynechococcus elongatus

    Directory of Open Access Journals (Sweden)

    Imran Ashraf

    2015-07-01

    Full Text Available The fluorescence of photosystem I (PSI trimers in proximity to bimetallic plasmonic nanostructures have been explored by single-molecule spectroscopy (SMS at cryogenic temperature (1.6 K. PSI serves as a model for biological multichromophore-coupled systems with high potential for biotechnological applications. Plasmonic nanostructures are fabricated by thermal annealing of thin metallic films. The fluorescence of PSI has been intensified due to the coupling with plasmonic nanostructures. Enhancement factors up to 22.9 and 5.1 are observed for individual PSI complexes coupled to Au/Au and Ag/Au samples, respectively. Additionally, a wavelength dependence of fluorescence enhancement is observed, which can be explained by the multichromophoric composition of PSI.