Science.gov

Sample records for photofragmented bimetallic clusters

  1. A technique for efficiently generating bimetallic clusters

    SciTech Connect

    Wagner, R.L.; Vann, W.D.; Castleman, A.W. , Jr.

    1997-08-01

    Reactivities of bimetallic clusters can be controlled by varying their composition, making them potentially valuable as catalysts and for use in elucidating the reactivities of such subnanoscale surfaces. A dual rod laser vaporization source coupled to a fast flow reactor is developed for the study of bimetallic clusters and their reactions. In order to establish the versatility of the technique, the results of studies are presented in which Nb/Al clusters are formed in two plasmas induced by the second harmonic (532 nm photons) of a single Nd:YAG laser and then detected by a quadrupole mass spectrometer. The beam from the laser is split and then focused onto each rod, allowing the mixing ratio within the cluster to vary by altering the laser fluence on each rod. With a low fluence on the Nb rod and a high fluence on the Al rod, an Al rich cluster distribution is formed, NbAl{sub m}{sup {minus}} (m=2{endash}20), and Al{sub m}{sup {minus}} (m=5{endash}31). By increasing the fluence on the Nb rod and decreasing the fluence on the Al rod, a Nb rich cluster distribution is formed, Nb{sub n}Al{sub m}{sup {minus}} (n=3{endash}8 and m=1{endash}3), Nb{sub n}OAl{sub m}{sup {minus}} (n=3{endash}8 and m=1{endash}5), and Nb{sub n}O{sup {minus}} (n=3{endash}8). Additional characterization is also performed on V/Al clusters. {copyright} {ital 1997 American Institute of Physics.}

  2. Spectroscopic Elucidation of First Steps of Supported Bimetallic Cluster Formation

    SciTech Connect

    Kulkarni, A.; Gates, B.C.

    2009-12-23

    Initial steps of bimetallic Ru-Os cluster formation on MgO in the presence of H{sub 2} are analyzed by EXAFS and IR spectroscopy. Ru-Os bond formation takes place after decarbonylation of Ru{sub 3} clusters and subsequently, at higher temperatures, of Os{sub 3} clusters to generate coordinative unsaturation.

  3. Formation of bimetallic nanoalloys by Au coating of size-selected Cu clusters

    NASA Astrophysics Data System (ADS)

    Yin, Feng; Wang, Zhi Wei; Palmer, Richard E.

    2012-10-01

    Bimetallic clusters display new characteristics that could not be obtained by varying either the size of pure metallic systems or the composition of bulk bimetals alone. Coating of pre-deposited clusters by vapour deposition is a typical synthesis process of bimetallic clusters. Here, we have demonstrated that hierarchical, gold cluster-decorated copper clusters as well as both heterogeneous and homogeneous Cu-Au bimetallic clusters (4.6 to 10.7 nm) can be prepared by coating pre-deposited, size-selected Cu5000 (4.6 ± 0.2 nm) with Au evaporation at various temperatures. These bimetallic clusters were analyzed by aberration-corrected scanning transmission electron microscopy and associated electron energy loss spectroscopy. The results indicate that the growth of bimetallic clusters is controlled by a competition between nucleation and diffusion of the coating Au atoms.

  4. Photodissociation and spectroscopy of gas phase bimetallic clusters

    SciTech Connect

    Duncan, M.A.

    1992-05-01

    Focus of the research program is the study of gas phase metal clusters for modeling fundamental interactions on metal surfaces. We characterize the chemical bonding between component atoms in clusters as well as the bonding in adsorption on cluster surfaces. Electronic spectra, vibrational frequencies and bond dissociation energies are measured for both neutral and ionized clusters with laser/mass spectrometry techniques. Small bimetallic cluster cations containing Bi/Cr, Bi/Fe, Sn/Bi, and Pb/Sb were photodissociated at various uv wavelengths. Silver dimer van der Waals complexes were produced with a series of rare gas atoms (Ar, Kr, Xe), and their vibrational frequencies and dissociation energies were obtained. (DLC)

  5. Photofragment Coincidence Imaging of Small I- (H2O)n Clusters Excited to the Charge-transfer-to-solvent State

    SciTech Connect

    Neumark, D. E. Szpunar, K. E. Kautzman, A. E. Faulhaber, and D. M.; Kautzman, K.E.; Faulhaber, A.E.; Faulhaber, A.E.

    2005-11-09

    The photodissociation dynamics of small I{sup -}(H{sub 2}O){sub n} (n = 2-5) clusters excited to their charge-transfer-to-solvent (CTTS) states have been studied using photofragment coincidence imaging. Upon excitation to the CTTS state, two photodissociation channels were observed. The major channel ({approx}90%) is a 2-body process forming neutral I + (H{sub 2}O){sub n} photofragments, and the minor channel is a 3-body process forming I + (H{sub 2}O){sub n-1} + H{sub 2}O fragments. Both process display translational energy (P(E{sub T})) distributions peaking at E{sub T} = 0 with little available energy partitioned into translation. Clusters excited to the detachment continuum rather than to the CTTS state display the same two channels with similar P(E{sub T}) distributions. The observation of similar P(E{sub T}) distributions from the two sets of experiments suggests that in the CTTS experiments, I atom loss occurs after autodetachment of the excited (I(H{sub 2}O){sub n}{sup -})* cluster, or, less probably, that the presence of the excess electron has little effect on the departing I atom.

  6. Photofragment coincidence imaging of small I-(H2O)n clusters excited to the charge-transfer-to-solvent state.

    PubMed

    Szpunar, David E; Kautzman, Kathryn E; Faulhaber, Ann Elise; Neumark, Daniel M

    2006-02-07

    The photodissociation dynamics of small I-(H2O)n(n=2-5) clusters excited to their charge-transfer-to-solvent (CTTS) states have been studied using photofragment coincidence imaging. Upon excitation to the CTTS state, two photodissociation channels were observed. The major channel (approximately 90%) is a two-body process forming neutral I+(H2O)n photofragments, and the minor channel is a three-body process forming I+(H2O)n-1+H2O fragments. Both processes display translational energy [P(ET)] distributions peaking at ET=0 with little available energy partitioned into translation. Clusters excited to the detachment continuum rather than to the CTTS state display the same two channels with similar P(ET) distributions. The observation of similar P(ET) distributions from the two sets of experiments suggests that in the CTTS experiments, I atom loss occurs after autodetachment of the excited [I(H2O)n-]* cluster or, less probably, that the presence of the excess electron has little effect on the departing I atom.

  7. Simulation of the interaction of bipartite bimetallic clusters with low-energy argon clusters

    NASA Astrophysics Data System (ADS)

    Shyrokorad, D. V.; Kornich, G. V.; Buga, S. G.

    2017-01-01

    Molecular-dynamics simulation of the evolution of bipartite bimetallic clusters consisting of 390 atoms during bombardment by Arn ( n = 1, 2, 13) clusters with initial energies from 1 eV to 1.4 keV is performed. Binary Cu-Au and Ni-Al clusters consisting of equal atomic fractions of corresponding elements were used as a target. As a result of simulation, the temperatures, changes in the potential energy, sputtering yields, and intensities of collision-stimulated displacement of atoms through the interface of monometallic parts of binary clusters, depending on the size and energy of incident particle, are obtained.

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

    PubMed

    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).

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  13. Photodissociation and spectroscopy of gas phase bimetallic clusters. Final report, September 15, 1990--September 14, 1993

    SciTech Connect

    Duncan, M.A.

    1993-12-31

    Focus is the study of gas phase metal clusters to evaluate their potential to model fundamental interactions on metal surfaces. Chemical bonding between component atoms in metal clusters and physisorption on cluster surfaces are studied. Electronic spectra, vibrational frequencies, and bond dissociation energies are measured for both neutral and ionized clusters using laser/mass spectrometry. Interest is on bimetallic cluster systems and how they compare to pure metal clusters. The following were studied: Bi/Cr, Bi/Fe, Pb/Sb, Ag{sub 2}-rare gas, Ag-Al, Ag-K, Ag-Na, Ag-Li, and Ag{sub 3}.

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

    NASA Astrophysics Data System (ADS)

    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.

  15. Preparation of regular arrays of bimetallic clusters with independent control of size and chemical composition.

    PubMed

    Marsault, M; Hamm, G; Wörz, A; Sitja, G; Barth, C; Henry, C R

    2008-01-01

    Regular arrays of bimetallic clusters have been prepared by atomic deposition, under UHV, on a nanostructured ultrathin alumina film. The alumina films are obtained by oxidation at 1000 K of a Ni3Al (111) surface. They present two regular hexagonal superstructures with lattice parameters of 2.4 and 4.1 nm. Pd clusters nucleate exclusively on the 4.1 nm superstructure forming regular arrays of clusters extending on the whole (1 cm2) substrate. Gold deposited on a previously formed Pd clusters array, condenses exclusively on the Pd clusters in forming a regular array of bimetallic AuPd clusters with a narrow size distribution. The size and the composition of the AuPd clusters can be controlled independently. Gold clusters nucleates also on the 4.1 nm superstructure but they can escape from the nucleation sites and coalesce with other gold clusters. By condensing Pd on the preformed Au clusters, PdAu clusters are formed together with pure Pd clusters nucleated on the free sites of the 4.1 nm superstructure of the alumina film.

  16. Density functional study of structural, electronic, and optical properties of small bimetallic ruthenium-copper clusters.

    PubMed

    Karagiannis, Efstathios E; Kefalidis, Christos E; Petrakopoulou, Ioanna; Tsipis, Constantinos A

    2011-05-01

    The structural, electronic, bonding, magnetic, and optical properties of bimetallic [Cu(n)Ru(m)](+/0/-) (n + m ≤ 3; n, m = 0-3) clusters were computed in the framework of the density functional theory (DFT) and time-dependent DFT (TD-DFT) using the full-range PBE0 nonlocal hybrid GGA functional combined with the Def2-QZVPP basis sets. Several low-lying states have been investigated and the stability of the ground state spinomers was estimated with respect to all possible fragmentation schemes. Molecular orbital and population analysis schemes along with computed electronic parameters illustrated the details of the bonding mechanisms in the [Cu(n Ru(m)](+/0/-) clusters. The TD-DFT computed UV-visible absorption spectra of the bimetallic clusters have been fully analyzed and assignments of all principal electronic transitions were made and interpreted in terms of contribution from specific molecular orbital excitations. Copyright © 2010 Wiley Periodicals, Inc.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  19. Molecular ion photofragment spectroscopy

    SciTech Connect

    Bustamente, S.W.

    1983-11-01

    A new molecular ion photofragment spectrometer is described which features a supersonic molecular beam ion source and a radio frequency octapole ion trap interaction region. This unique combination allows several techniques to be applied to the problem of detecting a photon absorption event of a molecular ion. In particular, it may be possible to obtain low resolution survey spectra of exotic molecular ions by using a direct vibrational predissociation process, or by using other more indirect detection methods. The use of the spectrometer is demonstrated by measuring the lifetime of the O/sub 2//sup +/(/sup 4/..pi../sub u/) metastable state which is found to consist of two main components: the /sup 4/..pi../sub 5/2/ and /sup 4/..pi../sub -1/2/ spin components having a long lifetime (approx. 129 ms) and the /sup 4/..pi../sub 3/2/ and /sup 4/..pi../sub 1/2/ spin components having a short lifetime (approx. 6 ms).

  20. Photodissociation and spectroscopy of gas phase bimetallic clusters. Annual progress report

    SciTech Connect

    Duncan, M.A.

    1992-05-01

    Focus of the research program is the study of gas phase metal clusters for modeling fundamental interactions on metal surfaces. We characterize the chemical bonding between component atoms in clusters as well as the bonding in adsorption on cluster surfaces. Electronic spectra, vibrational frequencies and bond dissociation energies are measured for both neutral and ionized clusters with laser/mass spectrometry techniques. Small bimetallic cluster cations containing Bi/Cr, Bi/Fe, Sn/Bi, and Pb/Sb were photodissociated at various uv wavelengths. Silver dimer van der Waals complexes were produced with a series of rare gas atoms (Ar, Kr, Xe), and their vibrational frequencies and dissociation energies were obtained. (DLC)

  1. Study of bimetallic Pd-Pt clusters in both free and supported phases

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    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.

  5. Bimetallic octahedral ruthenium-nickel carbido cluster complexes. Synthesis and structural characterization.

    PubMed

    Saha, Sumit; Zhu, Lei; Captain, Burjor

    2013-03-04

    The reaction of Ru5(CO)15(μ5-C) with Ni(COD)2 in acetonitrile at 80 °C affords the bimetallic octahedral ruthenium-nickel cluster complex Ru5Ni(NCMe)(CO)15(μ6-C), 3. The acetonitrile ligand in 3 can be replaced by CO and NH3 to yield Ru5Ni(CO)16(μ6-C), 4, and Ru5Ni(NH3)(CO)15(μ6-C), 5, respectively. Photolysis of compound 3 in benzene and toluene solvent yielded the η(6)-coordinated benzene and toluene Ru5Ni carbido cluster complexes Ru5Ni(CO)13(η(6)-C6H6)(μ6-C), 6, and Ru5Ni(CO)13(η(6)-C7H8)(μ6-C), 7, respectively. All five new compounds were structurally characterized by single-crystal X-ray diffraction analyses.

  6. Adsorption of carbon oxide on tetrahedral bimetallic gold-copper clusters

    NASA Astrophysics Data System (ADS)

    Gogol', V. V.; Pichugina, D. A.; Kuz'menko, N. E.

    2016-12-01

    The interaction between carbon oxide and [Au20-nCun]q clusters ( n = 0, 1, 19, 20 and q = 0, ±1) is studied by means of DFT/PBE in the scalar relativistic approximation. To establish the composition and structure of an adsorption site, isomers of bimetallic Au19Cu and AuCu19 particles with different positions of the heteroatom at an apex, edge, and face of the tetrahedral framework are considered. The optimized structures are used as the basis to determine the electronic properties of clusters (average bond energy per atom, difference of energies between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), ionization potential, electron affinity energy). The calculated parameters shrink as the copper content in clusters grows. Among the uncharged models, the highest CO adsorption energy is typical of Au19Cu, the heteroatom of which lies at a cluster's apex. The CO adsorption energy for cationic and anionic clusters grows in comparison to neutral clusters.

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

    PubMed

    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.

  8. Effect of Spin Multiplicity in O2 Adsorption and Dissociation on Small Bimetallic AuAg Clusters.

    PubMed

    García-Cruz, Raúl; Poulain, Enrique; Hernández-Pérez, Isaías; Reyes-Nava, Juan A; González-Torres, Julio C; Rubio-Ponce, A; Olvera-Neria, Oscar

    2017-08-17

    To dispose of atomic oxygen, it is necessary the O2 activation; however, an energy barrier must be overcome to break the O-O bond. This work presents theoretical calculations of the O2 adsorption and dissociation on small pure Aun and Agm and bimetallic AunAgm (n + m ≤ 6) clusters using the density functional theory (DFT) and the zeroth-order regular approximation (ZORA) to explicitly include scalar relativistic effects. The most stable AunAgm clusters contain a higher concentration of Au with Ag atoms located in the center of the cluster. The O2 adsorption energy on pure and bimetallic clusters and the ensuing geometries depend on the spin multiplicity of the system. For a doublet multiplicity, O2 is adsorbed in a bridge configuration, whereas for a triplet only one O-metal bond is formed. The charge transfer from metal toward O2 occupies the σ*O-O antibonding natural bond orbital, which weakens the oxygen bond. The Au3 ((2)A) cluster presents the lowest activation energy to dissociate O2, whereas the opposite applies to the AuAg ((3)A) system. In the O2 activation, bimetallic clusters are not as active as pure Aun clusters due to the charge donated by Ag atoms being shared between O2 and Au atoms.

  9. Bimetallic Catalysts.

    ERIC Educational Resources Information Center

    Sinfelt, John H.

    1985-01-01

    Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

  10. Bimetallic Catalysts.

    ERIC Educational Resources Information Center

    Sinfelt, John H.

    1985-01-01

    Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

  11. Intrinsic magnetic properties of bimetallic nanoparticles elaborated by cluster beam deposition.

    PubMed

    Dupuis, V; Khadra, G; Hillion, A; Tamion, A; Tuaillon-Combes, J; Bardotti, L; Tournus, F

    2015-11-14

    In this paper, we present some specific chemical and magnetic order obtained very recently on characteristic bimetallic nanoalloys prepared by mass-selected Low Energy Cluster Beam Deposition (LECBD). We study how the competition between d-atom hybridization, complex structure, morphology and chemical affinity affects their intrinsic magnetic properties at the nanoscale. The structural and magnetic properties of these nanoalloys were investigated using various experimental techniques that include High Resolution Transmission Electron Microscopy (HRTEM), Superconducting Quantum Interference Device (SQUID) magnetometry, as well as synchrotron techniques such as Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Magnetic Circular Dichroism (XMCD). Depending on the chemical nature of the nanoalloys we observe different magnetic responses compared to their bulk counterparts. In particular, we show how specific relaxation in nanoalloys impacts their magnetic anisotropy; and how finite size effects (size reduction) inversely enhance their magnetic moment.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Tl4Mg3 in TlxMg3 (x = 1-6) series: A bimetallic magic cluster for novel cluster assembled nanomaterials

    NASA Astrophysics Data System (ADS)

    Shah, Esha V.; Roy, Debesh R.

    2017-05-01

    The present study aims for the search of the outstanding stable clusters from a group III-alkaline earth cluster series. A detailed inspection on the stability and electronic properties of a series of bimetallic clusters, viz., TlxMg3 (x = 1-6) is carried out. B3LYP, a highly accepted hybrid functional is employed as an exchange-correlation functional. All the calculations are carried out under the density functional theory (DFT) framework. The jellium model is utilized to justify for the magic stability in certain clusters. The study points the out magic stability of Tl4Mg3 cluster as the evidence of the jellium shell closure.

  15. Probing the structural and electronic properties of bimetallic chromium-gold clusters CrmAun(m+n≤6): comparison with pure chromium and gold clusters.

    PubMed

    Lu, Peng; Liu, Guang-Hua; Kuang, Xiao-Yu

    2014-08-01

    Bimetallic chromium-gold CrmAun(m+n≤6) clusters are systematically investigated using the density functional theory at PW91P86 level with LanL2TZ basis set to understand the evolution of various structural, electronic, magnetic, and energetic properties as a function of size (m+n) and composition (m/n) of the system. Theoretical results show a logical evolution of the properties depending on the size and the composition of the system. Cr m clusters clearly prefer 3D structures while Au n clusters favor planar configurations. The geometry of the bimetallic Cr m Au n clusters mainly depends on their composition, i.e., clusters enriched in Cr atoms prefer 3D structures while increasing Au contents promotes planar configurations. The stability is maximized when the composition of binary Cr m Au n clusters is nearly balanced. Meanwhile, the number of hetero Cr-Au bonds and charge transfer from Cr to Au are maximized for clusters with m≈n. The most probable dissociation channels of the Cr m Au n clusters are calculated and analyzed. Natural population analysis reveals that Au atoms tend to be negatively charged while Cr atoms tend to be positively charged. Combined with the trend that Au atoms favor the surface/edges/vertices and Cr atoms tend to be inside, the outer part of the cluster tends to be negatively charged, and the inner part tends to be positively charged.

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

    PubMed

    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.

  17. Photodissociation of ozone at 276nm by photofragment imaging and high resolution photofragment translational spectroscopy

    SciTech Connect

    Blunt, D.A.; Suits, A.G.

    1996-11-01

    The photodissociation of ozone at 276 nm is investigated using both state resolved ion imaging and high-resolution photofragment translational spectroscopy. Ion images from both [3+1] and [2+1] resonance enhanced multiphoton ionization of the O({sup 1}D) photofragment are reported. All images show strong evidence of O({sup 1}D) orbital alignment. Photofragment translation spectroscopy time-of-flight spectra are reported for the O{sub 2} ({sup 1}{Delta}{sub g}) photofragment. Total kinetic energy release distributions determined form these spectra are generally consistent with those distributions determined from imaging data. Observed angular distributions are reported for both detection methods, pointing to some unresolved questions for ozone dissociation in this wavelength region.

  18. Reduced oxide sites and surface corrugation affecting the reactivity, thermal stability, and selectivity of supported Au-Pd bimetallic clusters on SiO2/Si(100).

    PubMed

    Gross, Elad; Sorek, Elishama; Murugadoss, Arumugam; Asscher, Micha

    2013-05-21

    The morphology and surface elemental composition of Au-Pd bimetallic nanoclusters are reported to be sensitive to and affected by reduced silicon defect sites and structural corrugation on SiO2/Si(100), generated by argon ion sputtering under ultrahigh vacuum (UHV) conditions. Metastable structures of the bimetallic clusters, where Au atoms are depleted from the top surface upon annealing, are stabilized by the interaction with the reduced silica sites, as indicated from CO temperature programmed desorption (TPD) titration measurements. Acetylene conversion to ethylene and benzene has been studied as a probe reaction, revealing the modification of selectivity and reactivity enhancement in addition to improved thermal stability on substrates rich in reduced-silica sites. These observations suggest that these unique sites play an important role in anchoring thermodynamically metastable conformations of supported Au-Pd bimetallic catalysts and dictate their high-temperature activity.

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

    NASA Astrophysics Data System (ADS)

    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 (<1 nm). Our results show that after deposition completely different structures, electronic properties and chemical reactivity of dispersed CrW2O9 clusters on ultrathin films are observed compared with that on the thick MgO surface. On the thick MgO(001) surface, adsorbed CrW2O9 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 CrW2O9 clusters keep the cyclic structures and the geometries are similar to that of gas-phase [CrW2O9]-. Interestingly, we predicted the occurrence of a net transfer of one electron by direct electron tunneling from the MgO/Ag(001) films to CrW2O9 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 CrW2O9/MgO/Ag(001) system, indicating a potentially good bimetallic oxide for better catalytic 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.

  20. Effect of Alkali Metal Atoms Doping on Structural and Nonlinear Optical Properties of the Gold-Germanium Bimetallic Clusters.

    PubMed

    Li, Xiaojun; Li, Shuna; Ren, Hongjiang; Yang, Juxiang; Tang, Yongqiang

    2017-07-17

    A new series of alkali-based complexes, AM@GenAu (AM = Li, Na, and K), have been theoretically designed and investigated by means of the density functional theory calculations. The geometric structures and electronic properties of the species are systematically analyzed. The adsorption of alkali metals maintains the structural framework of the gold-germanium bimetallic clusters, and the alkali metals prefer energetically to be attached on clusters' surfaces or edges. The high chemical stability of Li@Ge12Au is revealed by the spherical aromaticity, the hybridization between the Ge atoms and Au-4d states, and delocalized multi-center bonds, as well as large binding energies. The static first hyperpolarizability (βtot) is related to the cluster size and geometric structure, and the AM@GenAu (AM = Na and K) clusters exhibit the much larger βtot values up to 13050 a.u., which are considerable to establish their strong nonlinear optical (NLO) behaviors. We hope that this study will promote further application of alkali metals-adsorbed germanium-based semiconductor materials, serving for the design of remarkable and tunable NLO materials.

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

    NASA Astrophysics Data System (ADS)

    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

  2. Effect of Alkali Metal Atoms Doping on Structural and Nonlinear Optical Properties of the Gold-Germanium Bimetallic Clusters

    PubMed Central

    Li, Xiaojun; Li, Shuna; Ren, Hongjiang; Yang, Juxiang; Tang, Yongqiang

    2017-01-01

    A new series of alkali-based complexes, AM@GenAu (AM = Li, Na, and K), have been theoretically designed and investigated by means of the density functional theory calculations. The geometric structures and electronic properties of the species are systematically analyzed. The adsorption of alkali metals maintains the structural framework of the gold-germanium bimetallic clusters, and the alkali metals prefer energetically to be attached on clusters’ surfaces or edges. The high chemical stability of Li@Ge12Au is revealed by the spherical aromaticity, the hybridization between the Ge atoms and Au-4d states, and delocalized multi-center bonds, as well as large binding energies. The static first hyperpolarizability (βtot) is related to the cluster size and geometric structure, and the AM@GenAu (AM = Na and K) clusters exhibit the much larger βtot values up to 13050 a.u., which are considerable to establish their strong nonlinear optical (NLO) behaviors. We hope that this study will promote further application of alkali metals-adsorbed germanium-based semiconductor materials, serving for the design of remarkable and tunable NLO materials. PMID:28714906

  3. Equilibrium geometries, stabilities, and electronic properties of the bimetallic M2-doped Au(n) (M = Ag, Cu; n = 1-10) clusters: comparison with pure gold clusters.

    PubMed

    Zhao, Ya-Ru; Kuang, Xiao-Yu; Zheng, Bao-Bing; Li, Yan-Fang; Wang, Su-Juan

    2011-02-10

    The density functional method with relativistic effective core potential has been employed to investigate systematically the geometrical structures, relative stabilities, growth-pattern behaviors, and electronic properties of small bimetallic M(2)Au(n) (M = Ag, Cu; n = 1-10) and pure gold Au(n) (n ≤ 12) clusters. The optimized geometries reveal that M(2) substituted Au(n+2) clusters and one Au atom capped M(2)Au(n-1) structures are dominant growth patterns of the stable alloyed M(2)Au(n) clusters. The calculated averaged atomic binding energies, fragmentation energies, and the second-order difference of energies as a function of the cluster size exhibit a pronounced even-odd alternation phenomenon. The analytic results exhibit that the planar structure Ag(2)Au(4) and Cu(2)Au(2) isomers are the most stable geometries of Ag(2)Au(n) and Cu(2)Au(n) clusters, respectively. In addition, the HOMO-LUMO gaps, charge transfers, chemical hardnesses and polarizabilities have been analyzed and compared further.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  7. Extending cluster description to bimetallic nanowires: The ideal solid solution alloy case

    NASA Astrophysics Data System (ADS)

    Maras, E.; Braems, I.; Berthier, F.

    2011-12-01

    We present a comprehensive study of the equilibrium properties of two codeposited species for an alloy that forms an ideal solution, on a one-dimensional chain. By use of a cluster description we provide exact formulae of the coverages, the total density of clusters, the cluster size distribution, and the chemical composition of each cluster. These analytical results, that are proved to be in agreement with Monte Carlo simulations, strongly differ from the ones derived in the mean-field framework. Indeed, we show by depicting the codeposit at the macroscopic, mesoscopic, and atomic scales, that its features are to be related to the chemical heterogeneities at the edges of the clusters.

  8. The Electronic Structure of Metallic and Bimetallic Clusters of IRON-57 with Chromium, TIN-119 and Platinum.

    NASA Astrophysics Data System (ADS)

    Nagarathna, H. M.

    Rare gas matrix isolation techniques have been used in conjunction with Mossbauer spectroscopy to study the bimetallic clusters of ('57)Fe with Cr, ('119)Sn and Pt. Various molecules have been identified by concentration and temperature dependence studies and also with the aid of Monte Carlo calculations. The iron-tin system is studied using both ('57)Fe and ('119)Sn Mossbauer isotopes. The Mossbauer parameters of FeCr, FeSn and FePt heteronuclear diatomic molecules and Sn(,2) homonuclear diatomic molecules isolated in argon at 4.2 K are obtained very accurately and used to determine their electronic ground states. In addition to diatomic molecules, the larger clusters have also been characterized using Mossbauer spectroscopy and their relevance to bulk alloys is discussed. SCF-X(alpha)-SW molecular orbital calculations are performed on Fe(,2), FeCr, Sn(,2), FeSn and FePt diatomic molecules to determine their electronic ground states by looking at the calculations which agreed with the measured Mossbauer hyperfine parameters. The most probable electronic ground state for Fe(,2) is determined to be a ('7)(SIGMA)(,g) and for FeCr a ('7)(SIGMA) or ('7)(DELTA) indicating a ferromagnetic coupling between the atoms. The calculations indicated a need for a smaller value of the quadrupole moment of the ('57)Fe nucleus. For Sn(,2) a ('3)(SIGMA)(,g) is the most probable ground state and for FeSn a ('7)(DELTA). The calculations showed a ('5)(SIGMA) state as the most probable electronic ground state for FePt. The X(alpha)-SW calculations are found to be very useful in understanding the nature of chemical bonding between the atoms in the above molecules. Antimony metal clusters are also studied using ('121)Sb Mossbauer spectroscopy and extended Huckel molecular orbital calculations. A good correlation is observed between the experimental and calculated data.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    Cheng, Daojian; Wang, Wenchuan

    2012-04-07

    The composition-dependent equilibrium structure and thermal stability of Pd-Pt clusters with the size of 55 atoms, and CO, O, OH, and O(2) 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 Pd(43)Pt(12) 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 Pd(43)Pt(12) TS-cluster possesses the weakest CO, O, OH, and O(2) adsorption strength, compared to the Pt(55), Pd(55), and Pd(13)Pt(42) 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. This journal is © The Royal Society of Chemistry 2012

  13. Structural and Magnetic Evolution of Bimetallic MnAu Clusters Driven by Asymmetric Atomic Migration

    SciTech Connect

    Wei, Xiaohui; Zhou, Rulong; Lefebvre, Williams; He, Kai; Le Roy, Damien; Skomski, Ralph; Li, Xingzhong; Shield, Jeffrey E; Kramer, Matthew J; Chen, Shuang; Zeng, Xiao Cheng; Sellmyer, David J

    2014-03-12

    The nanoscale structural, compositional, and magnetic properties are examined for annealed MnAu nanoclusters. The MnAu clusters order into the L10 structure, and monotonic size-dependences develop for the composition and lattice parameters, which are well reproduced by our density functional theory calculations. Simultaneously, Mn diffusion forms 5 Å nanoshells on larger clusters inducing significant magnetization in an otherwise antiferromagnetic system. The differing atomic mobilities yield new cluster nanostructures that can be employed generally to create novel physical properties.

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

    SciTech Connect

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

    2016-09-07

    Here, we report the atomic, electronic, and magnetic structures of small Zr{sub m}Co{sub n} (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 Zr{sub 2}Co{sub 2} (for tetramer), Zr{sub 3}Co{sub 3} (for hexamer), and Zr{sub 4}Co{sub 4} (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 Zr{sub m}Co{sub n} (m + n = 2, 4, 6, and 8) clusters has also been studied. The electronic structures of Zr{sub m}Co{sub n} clusters with and without adsorbed hydrogen are described in terms of density of states spectra and charge density contours.

  15. First principles study of bimetallic Ni13-nAgn nano-clusters (n = 0-13): Structural, mixing, electronic, and magnetic properties

    NASA Astrophysics Data System (ADS)

    Datta, Soumendu; Raychaudhuri, A. K.; Saha-Dasgupta, Tanusri

    2017-04-01

    Using spin polarized density functional theory based calculations, combined with ab initio molecular dynamics simulation, we carry out a systematic investigation of the bimetallic Ni13-nAgn nano-clusters, for all compositions. This includes prediction of the geometry, mixing behavior, and electronic properties. Our study reveals a tendency towards the formation of a core-shell like structure, following the rule of putting Ni in a high coordination site and Ag in a low coordination site. Our calculations predict negative mixing energies for the entire composition range, indicating mixing to be favored for the bimetallic small sized Ni-Ag clusters, irrespective of the compositions. The magic composition with the highest stability is found for the NiAg12 alloy cluster. We investigate the microscopic origin of a core-shell like structure with negative mixing energy, in which the Ni-Ag inter-facial interaction is found to play a role. We also study the magnetic properties of the Ni-Ag alloy clusters. The Ni dominated magnetism consists of parallel alignment of Ni moments while the tiny moments on Ag align in anti-parallel to Ni moments. The hybridization with the Ag environment causes reduction of Ni moment.

  16. A density functional theory study of the adsorption of bimetallic Fe n Pt m clusters on defective graphene: structural, electronic, and magnetic properties

    NASA Astrophysics Data System (ADS)

    Xu, Duo; Zhao, Jingxiang; Wang, Xuanzhang

    2013-04-01

    Recent studies have suggested that graphene can serve as an excellent support material for the synthesis of advanced metal nanoparticle-graphene electrocatalysts. Compared with single-metal systems, rational design of bimetallic nanostructures with various compositions can provide more attractive opportunities to enhance their functionalities because of the novel electronic and magnetic properties. In this study, we have studied the adsorption of a series of bimetallic Fe n Pt m clusters ( n + m ≤ 4) on defective graphene with monovacancy by performing density functional theory calculations. Particular attention is paid to addressing the structural stability and exploring the effects of Fe n Pt m clusters anchoring on the electronic and magnetic properties of defective graphene. The results reveal that all studied Fe n Pt m clusters can be stably adsorbed on defective graphene, with large binding energies ranging from 6.44 (for Fe2Pt2) to 7.94 eV (for Fe2Pt). Moreover, the functionalized defective graphenes exhibit semiconducting or half-metallic nature, which is dependent on the values of n and m. Meanwhile, most of decorated defective graphenes exhibit nonzero magnetic moments, contributed mainly by the adsorbed clusters. In addition, these composites of Fe n Pt m /graphenes possess high chemical reactivity toward O2. The elongation of the O-O bonds of the adsorbed O2 molecules indicates that they can be used as oxidative catalysts.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  19. Formation of Fe-Os, Fe-Ru, and Fe-Co bimetallic particles by thermal decomposition of heteropolynuclear clusters supported on a partially dehydroxylated magnesia

    SciTech Connect

    Choplin, A.; Huang, L.; Theolier, A.; Gallezot, P.; Basset, J.M.; Siriwardane, U.; Shore, S.G.; Mathieu, R.

    1986-07-09

    The authors wish to report here that with H/sub 2/FeOs/sub 3/(CO)/sub 13/, H/sub 2/FeRu/sub 3/(VO)/sub 13/, and HFeCo/sub 3/(CO)/sub 12/ supported on a partially hydroxylated magnesia, it is possible to obtain, after H/sub 2/ treatment at 400/sup 0/C, very small bimetallic particles, having the same bulk composition as that of the starting heteropolynuclear precursor cluster. This conclusion is based on high spatial resolution analytical microscopy.

  20. Nucleation and growth mechanism of Pd/Pt bimetallic clusters in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles as studied by in situ X-ray absorption spectroscopy.

    PubMed

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

    2005-11-24

    We report in situ X-ray absorption spectroscopy (XAS) investigations on the formation of palladium-platinum (Pd/Pt) bimetallic clusters at the early stage within the water-in-oil microemulsion system of water/AOT/n-heptane. The reduction of palladium and platinum ions and the formation of corresponding clusters are monitored as a function of dosage of reducing agent, hydrazine (N(2)H(5)OH). Upon successive addition of the reducing agent, hydrazine (N(2)H(5)OH), five distinguishable steps are observed in the formation process of Pd/Pt clusters at the early stage. Both in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis for both the Pd K-edge and Pt L(III)-edge revealed the formation of Pd/Pt bimetallic clusters. A corresponding structural model is proposed for each step to provide a detailed insight into the nucleation and growth mechanism of Pd/Pt bimetallic clusters. We also discussed the atomic distribution of Pd and Pt atoms in Pd/Pt bimetallic clusters based on the calculated XAS structural parameters.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

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

    2015-01-01

    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. PMID:26508471

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Systematic study of the chemical ordering in bimetallic Gold-Gold nanoparticles and the adsorption process of methyl thiol molecules on Gold-55 clusters

    NASA Astrophysics Data System (ADS)

    Barron-Escobar, Hector

    In this thesis we have investigated the structural evolution and their effect on the electronic and magnetic properties of bimetallic Au-Ag nanoalloys when the chemical ordering takes place, as well as the study of the adsorption of methyl-thiol molecules on Au55 cluster by using density functional theory (DFT) calculations within the generalized gradient approximation (GGA) as implemented in the SIESTA code. From different highly symmetric geometries we explored the structural evolution of all possible non-equivalent configurations at different Au-Ag concentrations for bimetallic nanoparticles (NPs) of 4, 6, 7 and 13 atoms. The most favorable structures for each cluster were obtained comparing their energetic stability through the calculation of their excess energy, linking the structure with specific features of their HOMO-LUMO gap end their total spin as the mixing takes place in each cluster. We found structural transitions from tri-dimensional geometries into planar as well as high spin values for tri-dimensional clusters up to 7 atoms. Distorted structures were obtained in almost all the 13-atom clusters. This has an important impact in their electronic and magnetic properties since the distortion highly determines the HOMO-LUMO gap and the total spin values. From all the 13-atom clusters, the most stable structures were the decahedra and the buckled bi-planar (BBP). We have also investigated the adsorption process of methyl-thiol molecules on Au55 NPs by calculating the adsorption energy for different trial configurations of SCH3-Au 55 system. Different adsorption modes were considered using the Ih symmetry of the Au cluster and taking into account the molecule orientation, as well as the rotation of the CH3 group of the molecule. Upon the adsorption we found that the molecule prefers to be adsorbed in the bridge sites, independently of their initial configuration. The atomic arrangement of the Au cluster as well as the bond lengths between Au atoms and S

  5. Tunable vacuum ultraviolet photofragment excitation spectroscopy of OCS

    NASA Astrophysics Data System (ADS)

    Pibel, Charles D.; Ohde, Kyoko; Yamanouchi, Kaoru

    1994-07-01

    Photofragment excitation (PHOFEX) spectroscopy of OCS in the vacuum ultraviolet (VUV) has been carried out using tunable VUV excitation of jet-cooled OCS, followed by ultraviolet laser induced fluorescence (LIF) detection of the S (1S) photofragment via the S (3D°1-1S) transition. The PHOFEX spectrum near 154 nm is better resolved than previous absorption spectra, and new features are visible. The LIF spectrum of the S (1S) photofragment may be successfully modeled using the product recoil anisotropy (β=1.8±0.2) and CO (v,J) product state distribution previously measured for photodissociation of OCS at 157 nm [Strauss et al., J. Chem. Phys. 90, 5364 (1989)].

  6. Electronic Spectroscopy of Trapped PAH Photofragments

    NASA Astrophysics Data System (ADS)

    Joblin, Christine; Bonnamy, Anthony

    2016-06-01

    The PIRENEA set-up combines an ion cyclotron resonance cell mass spectrometer with cryogenic cooling in order to study the physical and chemical properties of polycyclic aromatic hydrocarbons (PAHs) of astrophysical interest. In space, PAHs are submitted to UV photons that lead to their dissociation. It is therefore of interest to study fragmentation pathways and search for species that might be good interstellar candidates because of their stability. Electronic spectroscopy can bring major insights into the structure of species formed by photofragmentation. This is also a way to identify new species in space as recently illustrated in the case of C60^+. In PIRENEA, the trapped ions are not cold enough, and thus we cannot use complexation with rare gas in order to record spectroscopy, as was nicely performed in the work by Campbell et al. on C60^+. We are therefore using the dissociation of the trapped ions themselves instead, which requires in general a multiple photon scheme. This leads to non-linear effects that affect the measured spectrum. We are working on improving this scheme in the specific case of the photofragment obtained by H-loss from 1-methylpyrene cation (CH_3-C16H9^+). A recent theoretical study has shown that a rearrangement can occur from 1-pyrenemethylium cation (CH_2-C16H9^+) to a system containing a seven membered ring (tropylium like pyrene system). This study also reports the calculated electronic spectra of both isomers, which are specific enough to distinguish them, and as a function of temperature. We will present experiments that have been performed to study the photophysics of these ions using the PIRENEA set-up and a two-laser scheme for the action spectroscopy. J. Montillaud, C. Joblin, D. Toublanc, Astron. & Astrophys. 552 (2013), id.A15 E.K. Campbell, M. Holz, D. Gerlich, and J.P. Maier, Nature 523 (2015), 322-323 F. Useli-Bacchitta, A. Bonnamy, G. Malloci, et al., Chem. Phys. 371 (2010), 16-23; J. Zhen, A. Bonnamy, G. Mulas, C

  7. Preferential segregation of Pd atoms in the Ag-Pd bimetallic cluster: Density functional theory and molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Kim, Hyun You; Kim, Hyoung Gyu; Ryu, Ji Hoon; Lee, Hyuck Mo

    2007-06-01

    Classical molecular dynamics simulations of the coalescence between an Ag cluster composed of 135 atoms and a Pd cluster of 16 atoms were performed at 500K . All Pd atoms penetrated into the Ag cluster and preferentially segregated at the subsurface layer. The density functional theory calculations revealed that the center site is the most stable position for Pd atoms. However, the energy barrier for further penetration of Pd atoms located at the subsurface was too high to overcome, and thus a metastable structure with Pd atoms segregated at the subsurface did not evolve.

  8. Structure, magnetism, and dissociation energy of small bimetallic cobalt-chromium oxide cluster cations: A density-functional-theory study

    NASA Astrophysics Data System (ADS)

    Pham, Hung Tan; Cuong, Ngo Tuan; Tam, Nguyen Minh; Lam, Vu Dinh; Tung, Nguyen Thanh

    2016-01-01

    We study CoxCryOm+ (x + y = 2, 3 and 1 ≤ m ≤ 4) clusters by means of density-functional-theory calculations. It is found that the clusters grow preferentially through maximizing the number of metal-oxygen bonds with a favor on Cr sites. The size- and composition-dependent magnetic behavior is discussed in relation with the local atomic magnetic moments. While doped species show an oscillatory magnetic behavior, the total magnetic moment of pure cobalt and chromium oxide clusters tends to enhance or reduce as increasing the oxygen content, respectively. The dissociation energies for different evaporation channels are also calculated to suggest the stable patterns, as fingerprints for future photofragmentation experiments.

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

    NASA Astrophysics Data System (ADS)

    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).

  10. Methane Activation Mediated by a Series of Cerium-Vanadium Bimetallic Oxide Cluster Cations: Tuning Reactivity by Doping.

    PubMed

    Ma, Jia-Bi; Meng, Jing-Heng; He, Sheng-Gui

    2016-04-18

    The reactions of cerium-vanadium cluster cations Cex Vy Oz (+) with CH4 are investigated by time-of-flight mass spectrometry and density functional theory calculations. (CeO2 )m (V2 O5 )n (+) clusters (m=1,2, n=1-5; m=3, n=1-4) with dimensions up to nanosize can abstract one hydrogen atom from CH4 . The theoretical study indicates that there are two types of active species in (CeO2 )m (V2 O5 )n (+) , V[(Ot )2 ](.) and [(Ob )2 CeOt ](.) (Ot and Ob represent terminal and bridging oxygen atoms, respectively); the former is less reactive than the latter. The experimentally observed size-dependent reactivities can be rationalized by considering the different active species and mechanisms. Interestingly, the reactivity of the (CeO2 )m (V2 O5 )n (+) clusters falls between those of (CeO2 )2-4 (+) and (V2 O5 )1-5 (+) in terms of C-H bond activation, thus the nature of the active species and the cluster reactivity can be effectively tuned by doping. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Photofragment Translational Spectroscopy of Propargyl Radicals at 248 nm

    SciTech Connect

    Goncher, S.J.; Moore, D.T.; Sveum, N.E.; Neumark, D.M.

    2007-12-21

    The photodissociation of propargyl radical, C{sub 3}H{sub 3}, and its perdeuterated isotopolog was investigated using photofragment translational spectroscopy. Propargyl radicals were produced by 193 nm photolysis of allene entrained in a molecular beam expansion, and then photodissociated at 248 nm. photofragment time-of-flight spectra were measured at a series of laboratory angles using electron impact ionization coupled to a mass spectrometer. Data for ion masses corresponding to C{sub 3}H{sub 2}{sup +}, C{sub 3}H{sup +}, C{sub 3}{sup +}, and the analogous deuterated species show that both H and H{sub 2} loss occur. The translational energy distributions for these processes have average values = 5.7 and 15.9 kcal/mol, respectively, and are consistent with dissociation on the ground state following internal conversion, with no exit barrier for H loss but a tight transition state for H{sub 2} loss. The translational energy distribution for H atom loss is similar to that in previous work on propargyl in which the H atom, rather than the heavy fragment, was detected. The branching ratio for H loss/H{sub 2} loss was determined to be 97.6/2.4 {+-} 1.2, in good agreement with RRKM results.

  12. Mechanism of formation oxygenated compounds from CO + H[sub 2] reaction over SiO[sub 2]-supported Ru-Co bimetallic carbonyl cluster-derived catalysts

    SciTech Connect

    Feng-Shou Xiao Jilin Univ., Changchun ); Fukuoka, A.; Ichikawa, M. )

    1992-11-01

    The catalytic performance in CO hydrogenation over Ru, Ru-Co, and Co carbonyl cluster-derived catalysts has been investigated, and it was found that the activity and selectivity for oxygenated products on a series of Ru-Co/SiO[sub 2] catalysts are much higher than those on Ru[sub 3]/SiO[sub 2] and Co[sub 4]/SiO[sub 2] catalysts. The mechanism of oxygenated formation on these Ru-Co/SiO[sub 2] catalysts has been investigated by in situ infrared, mass, and X-ray photoelectron spectroscopies. The IR spectra of reaction of CO + H[sub 2] with Ru-Co/SiO[sub 2] catalysts show a band appearing at 1584 cm[sup [minus]1], which has a good relationship to the activity and selectivity for oxygenates in CO hydrogenation. The adsorption of CO on reduced Ru-Co/SiO[sub 2] catalysts prepared from Ru-Co bimetallic carbonyl clusters exhibits a band at 1680 cm[sup [minus]1] shifting to 1640 cm[sup [minus]1] with [sup 13]CO, which is assigned to the C- and O-ended CO chemisorbed on Ru-Co/SiO[sub 2] catalysts. The chemical trapping of 1584 cm[sup [minus]1] adspecies shows that the 1584 cm[sup [minus]1] species reacts with H[sub 2] to produce CH[sub 4] and CH[sub 3]OH, and the addition of D[sub 2] to 1584 cm[sup [minus]1] species results in the formation of CHD[sub 3] and CHD[sub 2]OD. With the increase of reaction time and temperature, the author finds the bands at 1555 and 1440-1470 cm[sup [minus]1], while the 1584 cm[sup [minus]1] band gradually decreases on Ru-Co/SiO[sub 2] catalysts. XPS spectra demonstrate that the Ru and Co sites on the surface of Ru-Co/SiO[sub 2] catalysts are in the chemical state of Ru[sup 0] and Co[sup 2[minus

  13. Bimetallic cages

    NASA Astrophysics Data System (ADS)

    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.

  14. Bimetallic cages.

    PubMed

    Fournier, René; Afzal-Hussain, Sabeen

    2013-02-07

    We report the results of density functional theory for 39 clusters A(x)B(y) (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.

  15. Reaction mechanism studies of unsaturated molecules using photofragment translational spectroscopy

    SciTech Connect

    Longfellow, C.A. |

    1996-05-01

    A number of molecules have been studied using the technique of photofragment translational spectroscopy. In Chapter One a brief introduction to the experimental technique is given. In Chapter Two the infrared multiphoton dissociation (IRMPD) of acetic acid is discussed. Carbon dioxide and methane were observed for the first time as products from dissociation under collisionless conditions. Chapter Three relates an IRMPD experiment of hexafluoropropene. The predominant channel produces CFCF{sub 3} or C{sub 2}F{sub 4} and CF{sub 2}, with the heavier species undergoing further dissociation to two CF{sub 2} fragments. In Chapter Four the ultraviolet (UV) dissociation of hexafluoropropene is investigated. Chapter Five explores the IRMPD of octafluoro-1-butene and octafluoro-2-butene.

  16. Photofragment translational spectroscopy of three body dissociations and free radicals

    SciTech Connect

    North, Simon William

    1995-04-01

    This dissertation describes several three-body dissociations and the photodissociation of methyl radicals studied using photofragment translational spectroscopy. The first chapter provides an introduction to three body dissociation, examines current experimental methodology, and includes a discussion on the treatment of photofragment translational spectroscopy data arising from three-body fragmentation. The ultraviolet photodissociation of azomethane into two methyl radicals and nitrogen is discussed in chapter 2. Chapter 3 describes the photodissociation of acetone at 248 nm and 193 nm. At 248 nm the translational energy release from the initial C-C bond cleavage matches the exit barrier height and a comparison with results at 266 nm suggests that T> is invariant to the available energy. A fraction of the nascent CH3CO radicals spontaneously dissociate following rotational averaging. The T> for the second C-C bond cleavage also matches the exit barrier height. At 193 nm the experimental data can be successfully fit assuming that the dynamics are analogous to those at 248 nm. A simplified model of energy partitioning which adequately describes the experimental results is discussed. Experiments on acetyl halides provide additional evidence to support the proposed acetone dissociation mechanism. A value of 17.0±1.0 kcal/mole for the barrier height, CH3CO decomposition has been determined. The photodissociation of methyl radical at 193 nm and 212.8 nm is discussed in the chapter 5. The formation of CH2(1Al) and H (2S) was the only single photon dissociation pathway observed at both wavelengths.

  17. Complete Measurement of S(1D2) Photofragment Alignment from Abel-Invertible Ion Images

    NASA Astrophysics Data System (ADS)

    Rakitzis, T. Peter; Samartzis, Peter C.; Kitsopoulos, Theofanis N.

    2001-09-01

    A novel method to measure directly the photofragment alignment from Abel-invertible two-dimensional ion images, as a function of photofragment recoil velocity, is demonstrated for S(1D2) atoms from the photodissociation of carbonyl sulfide at 223 nm. The results are analyzed in terms of coherent and incoherent contributions from two dissociative states, showing that the phase differences of the asymptotic wave functions of the fast and slow recoil-velocity channel are approximately π/2 and 0, respectively.

  18. Pulsed laser photofragment emission for detection of mercuric chloride

    NASA Astrophysics Data System (ADS)

    Hoops, Alexandra A.; Reichardt, Thomas A.

    2006-08-01

    The viability of pulsed laser photofragment emission (PFE) is evaluated for the in situ measurement of vapor-phase mercuric chloride (HgCl2) concentration in combustion flue gas. Dispersed emissions from both the Hg (63P1) and HgCl (B2Σ+) photoproducts are presented, and the dependence of the HgCl2 PFE signal originating from Hg (63P1) on the collisional environment is examined for buffer-gas mixtures of N2, O2, and CO2. Integrated PFE intensity measurements as a function of buffer gas pressure support the assumption that the primary effect of the relevant flue gas constituents is to quench emission from Hg (63P1). The quenching rate constants for PFE from HgCl2 were measured to be 1.37 (±0.16)×105 Torr-1 s-1 for N2, 9.35 (±0.25)×106 Torr-1 s-1 for O2, and 1.49 (±0.29)×106 Torr-1 s-1 for CO2. These values are in good accord with literature values for the quenching of Hg (63P1). The emission cross section for Hg (63P1) generated by photodissociation of HgCl2 in 760 Torr N2 is found to be 1.0 (±0.2)×10-25 m2 by comparing the PFE signal to N2 Raman scattering.

  19. Fluorescence Emission and Excitation Spectra of Photo-Fragmented Nitrobenzene.

    NASA Astrophysics Data System (ADS)

    Lue, Christopher J.; Tanjaroon, Chakree; Johnson, J. Bruce; Allen, Susan D.; Reeve, Scott W.

    2012-06-01

    Upon absorption of a UV photon, nitrobenzene readily dissociates into C_6H_5, NO_2, C_6H_5NO, O, C_6H_5O, and NO through three different channels. We have recorded high resolution emission and excitation spectra of the NO resulting from photo-fragmented nitrobenzene using a pulsed picosecond tunable laser and a nanosecond dye laser. Specifically, the lasers probed the A^2Σ^+→ X^2π(1/2,3/2) NO band system between 225-260 nm using an one or two color process. In a one color process, the same energy (wavelength) photon is used to dissociate nitrobenzene and excite NO. In a two color process, photons of a particular energy are used to dissociate the nitrobenzene while photons of a different energy are used to probe the resultant NO. We have determined the rotational and vibrational temperatures of the nascent NO. And, we have examined the effect of the relative timing of the two photons on the fluorescence spectra to extract information about the photodissociation dynamics. Lin, M.-F.; Lee, Y. T.; Ni, C.-K.; Xu, S. and Lin, M. C. J. Chem. Phys., AIP, 2007, 126.

  20. Photofragment image analysis using the Onion-Peeling Algorithm

    NASA Astrophysics Data System (ADS)

    Manzhos, Sergei; Loock, Hans-Peter

    2003-07-01

    With the growing popularity of the velocity map imaging technique, a need for the analysis of photoion and photoelectron images arose. Here, a computer program is presented that allows for the analysis of cylindrically symmetric images. It permits the inversion of the projection of the 3D charged particle distribution using the Onion Peeling Algorithm. Further analysis includes the determination of radial and angular distributions, from which velocity distributions and spatial anisotropy parameters are obtained. Identification and quantification of the different photolysis channels is therefore straightforward. In addition, the program features geometry correction, centering, and multi-Gaussian fitting routines, as well as a user-friendly graphical interface and the possibility of generating synthetic images using either the fitted or user-defined parameters. Program summaryTitle of program: Glass Onion Catalogue identifier: ADRY Program Summary URL:http://cpc.cs.qub.ac.uk/summaries/ADRY Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Licensing provisions: none Computer: IBM PC Operating system under which the program has been tested: Windows 98, Windows 2000, Windows NT Programming language used: Delphi 4.0 Memory required to execute with typical data: 18 Mwords No. of bits in a word: 32 No. of bytes in distributed program, including test data, etc.: 9 911 434 Distribution format: zip file Keywords: Photofragment image, onion peeling, anisotropy parameters Nature of physical problem: Information about velocity and angular distributions of photofragments is the basis on which the analysis of the photolysis process resides. Reconstructing the three-dimensional distribution from the photofragment image is the first step, further processing involving angular and radial integration of the inverted image to obtain velocity and angular distributions. Provisions have to be made to correct for slight distortions of the image, and to

  1. An investigation of polarized atomic photofragments using the ion imaging technique

    SciTech Connect

    Bracker, A.S.

    1997-12-01

    This thesis describes measurement and analysis of the recoil angle dependence of atomic photofragment polarization (atomic v-J correlation). This property provides information on the electronic rearrangement which occurs during molecular photodissociation. Chapter 1 introduces concepts of photofragment vector correlations and reviews experimental and theoretical progress in this area. Chapter 2 described the photofragment ion imaging technique, which the author has used to study the atomic v-J correlation in chlorine and ozone dissociation. Chapter 3 outlines a method for isolating and describing the contribution to the image signal which is due exclusively to angular momentum alignment. Ion imaging results are presented and discussed in Chapter 4. Chapter 5 discusses a different set of experiments on the three-fragment dissociation of azomethane. 122 refs.

  2. Biosensors Incorporating Bimetallic Nanoparticles.

    PubMed

    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.

  3. Biosensors Incorporating Bimetallic Nanoparticles

    PubMed Central

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

    2015-01-01

    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. PMID:28344262

  4. Laser Photofragment Spectroscopy of Carbon-Hydrogen Ion and Positively Charged Silicon-Dihydrogen

    NASA Astrophysics Data System (ADS)

    Whitham, Christopher James

    Available from UMI in association with The British Library. Requires signed TDF. Laser photofragment studies have been carried out on the molecular ions, CH^+ and SiH_2^+. The experiments involved irradiating a mass selected fast-ion-beam of the parent molecular ion with tunable dye laser radiation and the subsequent detection of photofragment ions. For CH^+, C^+ photofragments were detected following the excitation from X^1Sigma^+ ground state levels to rotationally quasibound levels of the A ^1Pi state. Frequencies and linewidths of the resonances were measured for ^{12}CH^+, ^{13}CH^+ and CD^+. The data is used in the evaluation of various models of the dissociation dynamics involving tunnelling through a rotational barrier in the effective potential curve and coupling to other electronic states via non-adiabatic interactions. A new electronic band system has been proposed for the dense region of photofragment lines around 540 nm. This involves excitation of transitions between bound triplet levels just below the first two dissociation limits C^+(^2P) + H and C(^3P) + H^+ . C^+ fragments are detected following radiative decay into the near-threshold continua above the C^+(^2 P) + H limit. For SiH_2^+, high resolution single mode photofragment spectra have been recorded for Sigma sub-bands of the A-B_1-X^2A _1 system. For one band at 18,380 cm^{-1} a rotationally dependent branching into the two channels, Si^+ and SiH^+, seems to occur. In addition a band system consisting of simple rotational branches has been observed in both photofragment channels right across the wavenumber region scanned (16,500-18,700 cm^{-1}). These are believed to originate from transitions between highly excited bending levels of the X and A states.

  5. Velocity map imaging of HBr photodissociation in large rare gas clusters.

    PubMed

    Fedor, J; Kocisek, J; Poterya, V; Votava, O; Pysanenko, A; Lipciuc, M L; Kitsopoulos, T N; Fárník, M

    2011-04-21

    We have implemented the velocity map imaging technique to study clustering in the pulsed supersonic expansions of hydrogen bromide in helium, argon, and xenon. The expansions are characterized by direct imaging of the beam velocity distributions. We have investigated the cluster generation by means of UV photodissociation and photoionization of HBr molecules. Two distinct features appear in the hydrogen atom photofragment images in the clustering regime: (i) photofragments with near zero kinetic energies and (ii) "hot" photofragments originating from vibrationally excited HBr molecules. The origin of both features is attributed to the fragment caging by the cluster. We discuss the nature of the formed clusters based on the change of the photofragment images with the expansion parameters and on the photoionization mass spectra and conclude that single HBr molecule encompassed with rare gas "snowball" is consistent with the experimental observations.

  6. Velocity map imaging of HBr photodissociation in large rare gas clusters

    SciTech Connect

    Fedor, J.; Kocisek, J.; Poterya, V.; Votava, O.; Pysanenko, A.; Farnik, M.; Lipciuc, M. L.; Kitsopoulos, T. N.

    2011-04-21

    We have implemented the velocity map imaging technique to study clustering in the pulsed supersonic expansions of hydrogen bromide in helium, argon, and xenon. The expansions are characterized by direct imaging of the beam velocity distributions. We have investigated the cluster generation by means of UV photodissociation and photoionization of HBr molecules. Two distinct features appear in the hydrogen atom photofragment images in the clustering regime: (i) photofragments with near zero kinetic energies and (ii) ''hot'' photofragments originating from vibrationally excited HBr molecules. The origin of both features is attributed to the fragment caging by the cluster. We discuss the nature of the formed clusters based on the change of the photofragment images with the expansion parameters and on the photoionization mass spectra and conclude that single HBr molecule encompassed with rare gas ''snowball'' is consistent with the experimental observations.

  7. Synthesis of monodispersed bimetallic palladium-copper nanoscale colloids

    SciTech Connect

    Bradley, J.S.; Hill, E.W.; Klein, C. ); Chaudret, B.; Duteil, A. )

    1993-03-01

    Bimetallic clusters have been the subject of many studies of the surface chemistry and catalytic properties of metal crystallites on solid supports. Mixtures of palladium acetate and copper acetate were refluxed in 2-ethoxyethanol in the presence of poly(vinylpyrrolidone) to give 40-[angstrom] alloy nanoclusters. TEM and EDAX analysis showed that the particles were homogeneously bimetallic and crystalline, with a composition determined by the ratio of the metal acetates used. Carbon monoxide adsorbed on the colloidal particles binds reversibly to both metals. 9 refs., 3 figs.

  8. Enhanced sensitivity in H photofragment detection by two-color reduced-Doppler ion imaging

    NASA Astrophysics Data System (ADS)

    Epshtein, Michael; Portnov, Alexander; Kupfer, Rotem; Rosenwaks, Salman; Bar, Ilana

    2013-11-01

    Two-color reduced-Doppler (TCRD) and one-color velocity map imaging (VMI) were used for probing H atom photofragments resulting from the ˜243.1 nm photodissociation of pyrrole. The velocity components of the H photofragments were probed by employing two counterpropagating beams at close and fixed wavelengths of 243.15 and 243.12 nm in TCRD and a single beam at ˜243.1 nm, scanned across the Doppler profile in VMI. The TCRD imaging enabled probing of the entire velocity distribution in a single pulse, resulting in enhanced ionization efficiency, as well as improved sensitivity and signal-to-noise ratio. These advantages were utilized for studying the pyrrole photodissociation at ˜243.1 and 225 nm, where the latter wavelength provided only a slight increase in the H yield over the self-signal from the probe beams. The TCRD imaging enabled obtaining high quality H+ images, even for the low H photofragment yields formed in the 225 nm photolysis process, and allowed determining the velocity distributions and anisotropy parameters and getting insight into pyrrole photodissociation.

  9. Enhanced sensitivity in H photofragment detection by two-color reduced-Doppler ion imaging

    SciTech Connect

    Epshtein, Michael; Portnov, Alexander; Kupfer, Rotem; Rosenwaks, Salman; Bar, Ilana

    2013-11-14

    Two-color reduced-Doppler (TCRD) and one-color velocity map imaging (VMI) were used for probing H atom photofragments resulting from the ∼243.1 nm photodissociation of pyrrole. The velocity components of the H photofragments were probed by employing two counterpropagating beams at close and fixed wavelengths of 243.15 and 243.12 nm in TCRD and a single beam at ∼243.1 nm, scanned across the Doppler profile in VMI. The TCRD imaging enabled probing of the entire velocity distribution in a single pulse, resulting in enhanced ionization efficiency, as well as improved sensitivity and signal-to-noise ratio. These advantages were utilized for studying the pyrrole photodissociation at ∼243.1 and 225 nm, where the latter wavelength provided only a slight increase in the H yield over the self-signal from the probe beams. The TCRD imaging enabled obtaining high quality H{sup +} images, even for the low H photofragment yields formed in the 225 nm photolysis process, and allowed determining the velocity distributions and anisotropy parameters and getting insight into pyrrole photodissociation.

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

    PubMed

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

    2005-05-15

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2005-05-01

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

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

    PubMed

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

    2005-05-15

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

  14. Global minimum structures, stability and electronic properties of small NixSny (x + y ≤ 5) bimetallic clusters; a DFT study

    NASA Astrophysics Data System (ADS)

    Sosa-Hernández, Elisa Marina; Montejano-Carrizales, Juan Martin; Alvarado-Leyva, Pedro Gilberto

    2016-10-01

    We report DFT calculations about the global minimum structures, stability and electronic properties of small free Ni x Sn y nanoalloys ( x + y ≤ 5), by using the free SIESTA code. Our results show that the optimized structures of these binary nanoalloys prefer geometries with high coordination and show significant variations as compared to lower energies structures of the pure clusters. The excess energy reveals a favorable mixing of the constituent atoms for all the clusters studied here. The electronic behavior is analyzed through the ionization potential, electron affinity and hardness.

  15. Self-assembled hetero-bimetallic coordination cage and cation-clusters with micro(2)-Cl bridging using a flexible two-arm ferrocene amide linker.

    PubMed

    Wei, Kai-Ju; Ni, Jia; Xie, Yong-Shu; Liu, Yangzhong; Liu, Qing-Liang

    2007-08-21

    One flexible, discrete coordination cage [Cu(2)(3-BPFA)(4)(H(2)O)(2)](ClO(4))(4).4CH(3)OH (), and two cation-clusters with micro(2)-Cl bridging [Ni(2)(micro-Cl)(3-BPFA)(4)(H(2)O)(2)](ClO(4))(3) () and [Co(2)(micro-Cl)(3-BPFA)(4)(H(2)O)(2)](ClO(4))(4).4CH(3)OH (), containing the ferrocenyl functionality were prepared via coordination-driven self-assembly and Cl-anion template from Cu(II), Ni(II) and Co(II) salts and a flexible two-arm molecule 1,1-bis[(3-pyridylamino)carbonyl]ferrocene (3-BPFA).

  16. Partial dissociative emission cross sections and product state distributions of the resulting photofragments

    NASA Astrophysics Data System (ADS)

    Picconi, David; Grebenshchikov, Sergy Yu.

    2016-12-01

    This paper relates the partial cross section of a continuous optical emission into a given scattering channel of the lower electronic state to the photofragment population. This allows one to infer partial emission cross sections 'non-optically' from product state distributions; in computations, explicit construction of exact scattering states is therefore avoided. Applications to the emission spectra of NaI, CO2, and pyrrole are given. It is also demonstrated that a similar relationship holds between partial cross sections of dissociative photoionization and distributions of ionic fragments over final product channels.

  17. On factors controlling activity of submonolayer bimetallic catalysts: Nitrogen desorption

    SciTech Connect

    Guo, Wei; Vlachos, Dionisios G.

    2014-01-07

    We model N{sub 2} desorption on submonolayer bimetallic surfaces consisting of Co clusters on Pt(111) via first-principles density functional theory-based kinetic Monte Carlo simulations. We find that submonolayer structures are essential to rationalize the high activity of these bimetallics in ammonia decomposition. We show that the N{sub 2} desorption temperature on Co/Pt(111) is about 100 K higher than that on Ni/Pt(111), despite Co/Pt(111) binding N weaker at low N coverages. Co/Pt(111) has substantially different lateral interactions than single metals and Ni/Pt. The lateral interactions are rationalized with the d-band center theory. The activity of bimetallic catalysts is the result of heterogeneity of binding energies and reaction barriers among sites, and the most active site can differ on various bimetallics. Our results are in excellent agreement with experimental data and demonstrate for the first time that the zero-coverage descriptor, used until now, for catalyst activity is inadequate due not only to lacking lateral interactions but importantly to presence of multiple sites and a complex interplay of thermodynamics (binding energies, occupation) and kinetics (association barriers) on those sites.

  18. Line space theory of Resonant Four-Wave Mixing: New prospects for all-optical studies of photofragment states

    NASA Astrophysics Data System (ADS)

    Kouzov, A. P.; Radi, P. P.

    2017-04-01

    Based on the line-space quantum formalism, the potential of Resonant Four-Wave Mixing spectroscopy as a new tool to study rotational and translational anisotropy of photofragments produced by absorption of plane-polarized photons is theoretically addressed. Synergy of the flexible polarization setup, fine quantum state resolution and of the possibility to study translational recoil distributions, makes the tool unsurpassed among the all-optical means to interrogate the photofragment states. It allows to directly separate signals induced by the rotational anisotropy which remain silent in the most of laser-induced fluorescence responses and thus opens new ways to study rotational helicity, a crucial signature of the photolysis pathway.

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

    PubMed

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

    2015-11-01

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

  20. Photofragment slice imaging studies of pyrrole and the Xe⋯pyrrole cluster

    NASA Astrophysics Data System (ADS)

    Rubio-Lago, L.; Zaouris, D.; Sakellariou, Y.; Sofikitis, D.; Kitsopoulos, T. N.; Wang, F.; Yang, X.; Cronin, B.; Devine, A. L.; King, G. A.; Nix, M. G. D.; Ashfold, M. N. R.; Xantheas, S. S.

    2007-08-01

    The photolysis of pyrrole has been studied in a molecular beam at wavelengths of 250, 240, and 193.3nm, using two different carrier gases, He and Xe. A broad bimodal distribution of H-atom fragment velocities has been observed at all wavelengths. Near threshold at both 240 and 250nm, sharp features have been observed in the fast part of the H-atom distribution. Under appropriate molecular beam conditions, the entire H-atom lo iable index in order to predict the changes in the highest occupied molecular orbital eigenvalue due to doping.

  1. Preparation and characterization of dendrimer-templated Ag-Cu bimetallic nanoclusters.

    PubMed

    Li, Guoping; Luo, Yunjun

    2008-01-07

    Ag-Cu bimetallic nanoclusters with different shapes were prepared by a co-complexation method in the presence of PAMAM dendrimers. Small and evenly sized spherical Ag-Cu bimetallic nanoparticles were obtained with N2H4.H2O as the reducing agent, and long rod-shaped bimetallic nanoclusters were prepared with NaBH4 as the reducing agent. The mechanisms of formation of Ag-Cu bimetallic nanolusters with different shapes were discussed. The different shapes of the cluster were likely caused by the differences in the reduction rate of metal ions with NaBH4 and N2H4.H2O. Structure characterization by TEM, UV-vis spectra, EDX, and TGA showed that, in the presence of PAMAM dendrimers, Ag-Cu alloy bimetallic nanorods were obtained with NaBH4 reduction, and Ag-Cu bimetallic nanoparticles were prepared with N2H4.H2O as the reducing agent.

  2. Detection of mercuric chloride by photofragment emission using a frequency-converted fiber amplifier

    NASA Astrophysics Data System (ADS)

    Hoops, Alexandra A.; Reichardt, Thomas A.; Kliner, Dahv. A. V.; Koplow, Jeffrey P.; Moore, Sean W.

    2007-07-01

    A real-time, noninvasive approach for detecting trace amounts of vapor-phase mercuric chloride (HgCl2) in combustion flue gas is demonstrated using a near-infrared pulsed fiber amplifier that is frequency converted to the ultraviolet. Excitation of the HgCl2(1∏1u ← 1∑1g+) transition at 213 nm generates 253.7 nm emission from the Hg (63P1) photoproduct that is proportional to the concentration of HgCl2. A measured quadratic dependence of the HgCl2 photofragment emission (PFE) signal on the laser irradiance indicates that the photodissociation process involves two-photon excitation. Additionally, low concentrations of HgCl2 are detected with the PFE approach in an environment characteristic of coal-fired power-plant flue gas using this compact solid-state laser source. A detection limit of 0.7 ppb is extrapolated from these results.

  3. A cryogenically cooled photofragment fluorescence instrument for measuring stratospheric water vapor

    NASA Technical Reports Server (NTRS)

    Weinstock, Elliot M.; Schwab, James J.; Nee, Jan Bai; Schwab, M. J.; Anderson, James G.

    1990-01-01

    An instrument developed for high-resolution daytime measurements of water vapor in the stratosphere using the technique of photofragment fluorescence is examined. A detailed description of all aspects of the instrument, as well as the results of its first two flights, are presented. The main areas of concern were optical baffling, cryogen transfer, water vapor measurement without contamination, and a dual path absorption measurement. Results of the second flight test indicate that the problems of instrument and gondola contamination, identified in the first flight test, were solved. A signal-to-noise ratio of about 50:1 for 10 sec of averaging throughout the stratosphere is achieved, as well as an altitude resolution of better than 100 m.

  4. Detection of mercuric chloride by photofragment emission using a frequency-converted fiber amplifier.

    PubMed

    Hoops, Alexandra A; Reichardt, Thomas A; Kliner, Dahv A V; Koplow, Jeffrey P; Moore, Sean W

    2007-07-01

    A real-time, noninvasive approach for detecting trace amounts of vapor-phase mercuric chloride (HgCl(2)) in combustion flue gas is demonstrated using a near-infrared pulsed fiber amplifier that is frequency converted to the ultraviolet. Excitation of the HgCl(2) ([see text]) transition at 213 nm generates 253.7 nm emission from the Hg (6(3)P(1)) photoproduct that is proportional to the concentration of HgCl(2). A measured quadratic dependence of the HgCl(2) photofragment emission (PFE) signal on the laser irradiance indicates that the photodissociation process involves two-photon excitation. Additionally, low concentrations of HgCl(2) are detected with the PFE approach in an environment characteristic of coal-fired power-plant flue gas using this compact solid-state laser source. A detection limit of 0.7 ppb is extrapolated from these results.

  5. Preparation of Pt/Rh bimetallic colloidal particles in polymer solutions using borohydride-reduction.

    PubMed

    Harada, Masafumi; Einaga, Hisahiro

    2007-04-15

    Colloidal dispersions of Pt/Rh bimetallic particles have been synthesized by the reduction of Pt(IV)/Rh(III) ionic solutions by using borohydride-reduction in the presence of poly(N-vinyl-2-pyrrolidone). The size and the structure of the synthesized particles have been examined by transmission electron micrograph (TEM) and extended X-ray absorption fine structure (EXAFS). We have succeeded in producing the bimetallic Pt/Rh particles with an average diameter of 2.8 nm in polymer solutions by the stepwise addition of sodium borohydride aqueous solution. The distribution of different metallic species in a particle tended to be "cluster-in-cluster" structure, in contrast to the bimetallic particle with an average diameter of 1.4 nm synthesized by alcohol-reduction which have a core-shell structure.

  6. A first-principles study of Pt-Ni bimetallic cluster adsorption on the anatase TiO2 (1 0 1) surface: Probing electron effect of Ni in TiO2 (1 0 1)-bimetallic cluster (Pt-Ni) on the adsorption and dissociation of methanol

    NASA Astrophysics Data System (ADS)

    Liu, Feila; Xiao, Peng; Uchaker, Evan; He, Huichao; Zhou, Ming; Zhou, Xin; Zhang, Yunhuai

    2014-10-01

    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 Pt4 and Pt3Ni on the anatase TiO2 (1 0 1) surface. Two stable Pt3Ni adsorptions with considerable adsorption energies on the anatase TiO2 (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 Pt3Ni clusters. The 2cO (3cO)-PtNi-5cTi conformation of the adsorbed Pt3Ni on the anatase TiO2 (1 0 1) surface provides a more feasible model for electron injection through the Pt3Ni/TiO2 interface. The reactivity of Pt3Ni/TiO2 is superior to Pt4/TiO2 and effectively manifests itself in the eased decomposition of Osbnd H bonds derived by methanol and alleviative CO adsorption.

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

    PubMed

    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.

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

    PubMed

    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.

  9. Chemical- or Radiation-Assisted Selective Dealloying in Bimetallic Nanoclusters

    NASA Astrophysics Data System (ADS)

    Mattei, G.; Marchi, G. De; Maurizio, C.; Mazzoldi, P.; Sada, C.; Bello, V.; Battaglin, G.

    2003-02-01

    A selective dealloying in bimetallic nanoclusters prepared by ion implantation has been found upon thermal annealing in oxidizing atmosphere or irradiation with light ions. In the first process, the incoming oxygen interacts preferentially with copper promoting Cu2O formation, therefore extracting copper from the alloy. In the second process the irradiation with Ne ions promotes a preferential extraction of Au from the alloy, resulting in the formation of Au-enriched “satellite” nanoparticles around the original AuxCu1-x cluster.

  10. Detection of mercuric chloride by photofragment emission using a frequency-converted fiber amplifier

    SciTech Connect

    Hoops, A.A.; Reichardt, T.A.; Kliner, D.A.V.; Koplow, J.P.; Moore, S.W.

    2007-07-15

    A real-time, noninvasive approach for detecting trace amounts of vapor-phase mercuric chloride (HgCl{sub 2}) in combustion flue gas is demonstrated using a near-infrared pulsed fiber amplifier that is frequency converted to the ultraviolet. Excitation of the HgCl{sub 2} (1{Pi}1{sub u}{l_arrow} 1{Sigma}1g+) transition at 213 nm generates 253.7 nm emission from the Hg (6{sup 3}P{sub 1}) photoproduct that is proportional to the concentration of HgC1{sub 2}. A measured quadratic dependence of the HgCl{sub 2} photofragment emission (PFE) signal on the laser irradiance indicates that the photodissociation process involves two-photon excitation. Additionally, low concentrations of HgCl{sub 2} are detected with the PFE approach in an environment characteristic of coal-fired power-plant flue gas using this compact solid-state laser source. A detection limit of 0.7 ppb is extrapolated from these results.

  11. Bimetallic nanoparticles for arsenic detection.

    PubMed

    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.

  12. Structural transformation of Au-Pd bimetallic nanoclusters on thermal heating and cooling: a dynamic analysis.

    PubMed

    Liu, H B; Pal, U; Perez, R; Ascencio, J A

    2006-03-23

    Classical molecular dynamics simulation is used for structural thermodynamic and dynamic analysis of Au-Pd bimetallic clusters. It is observed that the Pd-core/Au-shell structure is the most stable, and can be formed through annealing of other structures such as Au-core/Pd-shell, eutecticlike, or solid solution. Depending on the starting temperature and initial composition, three-layer icosahedral nanorod, face-centered cubic (fcc) nanorod, and fcc cluster can be obtained on slow cooling. The three-layer icosahedral nanorod structure is not as stable as the Pd-core/Au-shell decahedron; however it is more stable than the solid-solution decahedron structure up to 400 K. Our findings provide valuable insight into catalysis using Au-Pd and other similar bimetallic clusters.

  13. Laser deposition of bimetallic island films

    NASA Astrophysics Data System (ADS)

    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.

  14. Structure and dynamics of graphite-supported bimetallic nanoclusters

    NASA Astrophysics Data System (ADS)

    Huang, Shi-Ping; Mainardi, Daniela S.; Balbuena, Perla B.

    2003-11-01

    Molecular dynamics simulations are used to analyze the structure and dynamics of isolated bimetallic nanoclusters of 343 (Cu-Ni) and 1000 atoms (Cu-Ni and Pt-Au) deposited on a graphite substrate. The metal-metal interactions are modeled with the many-body Sutton-Chen potential, and a Lennard-Jones potential is used to describe the metal-carbon interactions. The nanocluster melting temperature is determined from caloric and heat capacity curves, and the atomic distribution is studied layer-by-layer as a function of temperature in a direction perpendicular to the substrate plane. Changes in the nanocluster shape as temperature increases are monitored through deformation parameters that show clear evidence of structural and melting transitions as well as of atomic surface diffusion in the cluster. Dynamic properties such as atomic and whole-cluster diffusion, and the motion of the metal atoms at the interface metal/graphite are characterized as a function of temperature.

  15. Homogeneous Pt-bimetallic Electrocatalysts

    SciTech Connect

    Wang, Chao; Chi, Miaofang; More, Karren Leslie; Markovic, Nenad; Stamenkovic, Vojislav

    2011-01-01

    Alloying has shown enormous potential for tailoring the atomic and electronic structures, and improving the performance of catalytic materials. Systematic studies of alloy catalysts are, however, often compromised by inhomogeneous distribution of alloying components. Here we introduce a general approach for the synthesis of monodispersed and highly homogeneous Pt-bimetallic alloy nanocatalysts. Pt{sub 3}M (where M = Fe, Ni, or Co) nanoparticles were prepared by an organic solvothermal method and then supported on high surface area carbon. These catalysts attained a homogeneous distribution of elements, as demonstrated by atomic-scale elemental analysis using scanning transmission electron microscopy. They also exhibited high catalytic activities for the oxygen reduction reaction (ORR), with improvement factors of 2-3 versus conventional Pt/carbon catalysts. The measured ORR catalytic activities for Pt{sub 3}M nanocatalysts validated the volcano curve established on extended surfaces, with Pt{sub 3}Co being the most active alloy.

  16. Development of a linear-type double reflectron for focused imaging of photofragment ions from mass-selected complex ions

    NASA Astrophysics Data System (ADS)

    Okutsu, Kenichi; Nakashima, Yuji; Yamazaki, Kenichiro; Fujimoto, Keita; Nakano, Motoyoshi; Ohshimo, Keijiro; Misaizu, Fuminori

    2017-05-01

    An ion imaging apparatus with a double linear reflectron mass spectrometer has been developed, in order to measure velocity and angular distributions of mass-analyzed fragment ions produced by photodissociation of mass-selected gas phase complex ions. The 1st and the 2nd linear reflectrons were placed facing each other and controlled by high-voltage pulses in order to perform the mass-separation of precursor ions in the 1st reflectron and to observe the focused image of the photofragment ions in the 2nd reflectron. For this purpose, metal meshes were attached on all electrodes in the 1st reflectron, whereas the mesh was attached only on the last electrode in the 2nd reflectron. The performance of this apparatus was evaluated using imaging measurement of Ca+ photofragment ions from photodissociation reaction of Ca+Ar complex ions at 355 nm photoexcitation. The focused ion images were obtained experimentally with the double linear reflectron at the voltages of the reflection electrodes close to the predictions by ion trajectory simulations. The velocity and angular distributions of the produced Ca+ ([Ar] 4p1, 2P3/2) ion were analyzed from the observed images. The binding energy D0 of Ca+Ar in the ground state deduced in the present measurement was consistent with those determined theoretically and by spectroscopic measurements. The anisotropy parameter β of the transition was evaluated for the first time by this instrument.

  17. The parity-adapted basis set in the formulation of the photofragment angular momentum polarization problem: the role of the Coriolis interaction.

    PubMed

    Shternin, Peter S; Vasyutinskii, Oleg S

    2008-05-21

    We present a theoretical framework for calculating the recoil-angle dependence of the photofragment angular momentum polarization taking into account both radial and Coriolis nonadiabatic interactions in the diatomic/linear photodissociating molecules. The parity-adapted representation of the total molecular wave function has been used throughout the paper. The obtained full quantum-mechanical expressions for the photofragment state multipoles have been simplified by using the semiclassical approximation in the high-J limit and then analyzed for the cases of direct photodissociation and slow predissociation in terms of the anisotropy parameters. In both cases, each anisotropy parameter can be presented as a linear combination of the generalized dynamical functions fK(q,q',q,q') of the rank K representing contribution from different dissociation mechanisms including possible radial and Coriolis nonadiabatic transitions, coherent effects, and the rotation of the recoil axis. In the absence of the Coriolis interactions, the obtained results are equivalent to the earlier published ones. The angle-recoil dependence of the photofragment state multipoles for an arbitrary photolysis reaction is derived. As shown, the polarization of the photofragments in the photolysis of a diatomic or a polyatomic molecule can be described in terms of the anisotropy parameters irrespective of the photodissociation mechanism.

  18. Segregation and phase dynamics in supported bimetallic nanoparticles

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

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

    2017-07-28

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  1. Generalizing segregation and chemical ordering in bimetallic nanoclusters through atomistic view points

    NASA Astrophysics Data System (ADS)

    Reyes-Nava, J. A.; Rodríguez-López, J. L.; Pal, U.

    2009-10-01

    We predict general trends for surface segregation in binary metal clusters based on the difference between the atomic properties of the constituent elements. The energetically most favorable site for a guest atom on a pure metal cluster is determined considering the attractive and repulsive contributions of the cohesive energy of an atom in the cluster. It is predicted that for adjacent elements in a period of the periodic table, the bimetallic system would be more stable if the component with smallest valence electron density is placed on the surface. On the other hand, in bimetallic clusters built with elements of only one group, the trend to be in the volume (of the atomic component with smaller core density) will be higher for that cluster with atomic components most separated in the group. Such chemical ordering trends in the lowest energy configurations of Pt-Au, Pt-Pd, and Pt-Ni binary alloy clusters are verified for their 561 atom systems through a simulated annealing process. Some of our atomistic predictions are verified through quantum mechanical calculations.

  2. Platinum indium bimetallic in silicalite: Preparation, characterization and use in the vinylcyclohexene transformation

    SciTech Connect

    Meriaudeau, P.; Thangaraj, A.; Naccache, C.

    1996-12-31

    The discovery of bimetallic catalysts such as Pt-Re, Pt-Ir, Pt-Sn has been a major improvement in the reforming process. The metal support was chlorinated alumina. Another generation of reforming catalysts consisted of Pt supported on non acid zeolite, KL zeolite being preferred. Recently a patent from Mobil (1) claimed for the reforming of C{sub 6}-C{sub 8} n-alkanes a catalyst constituted by platinum on an indium silicalite; these solids are able to reform n-octane into ethylbenzene (EBZ) and styrene (STY). PtIn/silicalite catalysts were reinvestigated and the high performances of this type of material attributed to the existence of small PtIn clusters as well to the shape selectivity of the silicalite (2a). Also, it has been shown that PtIn bimetallic clusters supported on NaY zeolite was active and selective in the dehydrogenation of light alkanes but these materials suffered from fast deactivation (2b). In this work, we have extended the studies of the dehydrogenation-dehydrocyclisation of alkanes over PtIn bimetallic supported on silicalite to the reaction of vinylcyclohexene (VCHx) over these materials.

  3. Reductive dechlorination of trichloroethylene by iron bimetallics

    SciTech Connect

    Orth, R.G.; Dauda, T.; McKenzie, D.E.

    1998-07-01

    Reductive dechlorination using a zero valence metal such as iron has seen an increase in interest with the extension of iron dechlorination to in-situ treatment of ground water. Studies to increase the rate of dechlorination and the long term stability have lead many to examine the use of bimetallic iron systems. Results are shown for bimetallic iron systems of Cu, Sn, Ni, Ag, Au, and Pd. All of these bimetallic couples form a galvanic couple which increase corrosion rates and the production of hydrogen. Increased rates of reaction normalized to surface area were observed for all the couples. The reaction rates were found to depended on surface area and surface coverage of the iron. The results of studies in deuterium oxide indicate that the pathways changed as the bimetallic is changed and that the pathway in all cases could be a combination of dehydrohalgenation and sequential dechlorination. Degradation of DNAPL TCE by iron was found to be zero order and the type of product observed was different from that observed for TCE dissolved in water.

  4. Temperature-dependent Evolution of the Oxidation State of Cobalt and Platinum in Co{sub 1-x}Pt{sub x} Bimetallic Clusters under H{sub 2} and CO + H{sub 2} Atmosphere.

    SciTech Connect

    Yang, Bing; Khadra, Ghassan; Tuaillon-Combes, Juliette; Tyo, Eric; Seifert, Sonke; Chen, Xinqi; Dupuis, Veronique; Vajda, Stefan

    2016-09-29

    Co1-xPtx clusters of 2.9-nm size with a range of atomically precise Pt/Co atomic ratios (x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the mass-selected low-energy cluster beam deposition (LECBD) technique and soft-landed onto an amorphous alumina thin film prepared by atomic layer deposition (ALD). Utilizing ex situ X-ray photoemission spectroscopy (XPS), the oxidation state of the as-made clusters supported on Al2O3 was determined after both a 1-h-long exposure to air and aging for several weeks while exposed to air. Next, the aged duster samples were characterized by grazing-incidence X-ray absorption spectroscopy (GIXAS) and then pretreated with diluted hydrogen and further exposed to the mixture of diluted CO and H-2 up to 225 degrees C at atmospheric pressure, and the temperature-dependent evolutions of the particle size/shape and the oxidation states of the individual metal components within the dusters were monitored using in situ grazing-incidence small-angle X-ray scattering and X-ray absorption spectroscopy (GISAXS/GIXAS). The changes in the oxidation states of Co and Pt exhibited a nonlinear dependence on the Pt/Co atomic ratio of the dusters. For example, a low Pt/Co ratio (x <= 0.5) facilitates the formation of Co(OH)(2), whereas a high Pt/Co ratio (x = 0.75) stabilizes the Co3O4 composition instead through the formation of a Co-Pt core-shell structure where the platinum shell inhibits the reduction of cobalt in the core of the Co1-xPtx alloy dusters. The obtained results indicate methods for optimizing the composition and structure of binary alloy clusters for catalysis.

  5. Stainless Steel to Titanium Bimetallic Transitions

    SciTech Connect

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

    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.

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

    PubMed

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

    2010-03-07

    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@Au(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.

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

    SciTech Connect

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

    2010-01-01

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

  8. Photofragmentation of I2-ṡArn clusters: Observation of metastable isomeric ionic fragments

    NASA Astrophysics Data System (ADS)

    Vorsa, Vasil; Campagnola, Paul J.; Nandi, Sreela; Larsson, Mats; Lineberger, W. C.

    1996-08-01

    We report the 790 nm photofragmentation of mass-selected I-2ṡArn clusters, n=1 to 27. We determine the I-+I caging efficiency as a function of the number of solvent Ar atoms and compare these results with I-2 in CO2 clusters. Caging is much less effective with Ar. In addition to ``normal'' caged photoproducts (I-2ṡArm, where mphotofragments, where the I-2 bond has not reformed. These metastable species comprise ˜55% of the photofragment yield for precursor clusters for n≥14 and have lifetimes ≳5 μs. This unusual photofragment exists either as a trapped excited electronic state or as a solvent-separated pair at an internuclear separation of ˜5.5 Å. The photofragmentation data also exhibit the existence of two distinct isomeric forms of the precursor I-2ṡArn, for n≤14. These forms are evaporatively distinct in that one isomer displays highly nonstatistical fragmentation, probably arising from a cluster in which the I-2 resides on the surface, rather than in the interior. The photofragmentation distribution of the other form exhibits statistical behavior, consistent with the evaporation of an I-2 solvated inside the cluster.

  9. Signatures of a conical intersection in photofragment distributions and absorption spectra: Photodissociation in the Hartley band of ozone

    SciTech Connect

    Picconi, David; Grebenshchikov, Sergy Yu.

    2014-08-21

    Photodissociation of ozone in the near UV is studied quantum mechanically in two excited electronic states coupled at a conical intersection located outside the Franck-Condon zone. The calculations, performed using recent ab initio PESs, provide an accurate description of the photodissociation dynamics across the Hartley/Huggins absorption bands. The observed photofragment distributions are reproduced in the two electronic dissociation channels. The room temperature absorption spectrum, constructed as a Boltzmann average of many absorption spectra of rotationally excited parent ozone, agrees with experiment in terms of widths and intensities of diffuse structures. The exit channel conical intersection contributes to the coherent broadening of the absorption spectrum and directly affects the product vibrational and translational distributions. The photon energy dependences of these distributions are strikingly different for fragments created along the adiabatic and the diabatic paths through the intersection. They can be used to reverse engineer the most probable geometry of the non-adiabatic transition. The angular distributions, quantified in terms of the anisotropy parameter β, are substantially different in the two channels due to a strong anticorrelation between β and the rotational angular momentum of the fragment O{sub 2}.

  10. Measuring the Quenching of no Fluorescence Produced from the Excitation of Photo-Fragmented Nitrobenzene Using a Picosecond Laser.

    NASA Astrophysics Data System (ADS)

    Lue, Christopher J.; Tanjaroon, Chakree; Johnson, J. Bruce; Reeve, Scott W.; Allen, Susan D.

    2013-06-01

    The military is interested in using spectroscopic methods to detect nitroaromatic compounds related to explosives. Upon absorption of a UV photon, nitrobenzene can dissociate into C_6H_5O and NO. Wynn, et al. have shown that looking at NO fluorescence from the photodissociated nitrobenzene could be a possible detection method. However, the fluorescence can easily be quenched by molecular oxygen and other constituents in air. We have measured fluorescence lifetimes of the nascent NO resulting from photo-fragmented nitrobenzene using a pulsed picosecond tunable laser (pulse width ≈15 ps) by means of a two-color process. In the two-color process, photons of a particular energy dissociated the nitrobenzene while photons of a different energy probed the A^2Σ^+← X^2Π_{(1/2,3/2)} NO band system between 225-260 nm. We have performed the measurements with different background pressures of He, N_2, and air. We present the results of these measurements which indicate considerable quenching of the NO fluorescence due to oxygen. Wynn, C. M.; Palmacci, S.; Kunz, R. R.; and Rothschild, M.Opt. Express, OSA, 2010, 18, 5399-5406

  11. Intermediate photofragment distributions as probes of non-adiabatic dynamics at conical intersections: application to the Hartley band of ozone.

    PubMed

    Picconi, David; Grebenshchikov, Sergy Yu

    2015-11-21

    Quantum dynamics at a reactive two-state conical intersection lying outside the Franck-Condon zone is studied for a prototypical reaction of ultraviolet photodissociation of ozone in the Hartley band. The focus is on the vibrational distributions in the two electronic states at intermediate interfragment distances near the intersection. Such intermediate distributions of strongly interacting photofragments contain unique information on the location and shape of the conical intersection. Multidimensional Landau-Zener modeling provides a framework to reverse engineer the molecular geometry-dependent Massey parameter of the intersection from the intermediate distributions. The conceptual approach is demonstrated for the intermediate O-O bond stretch distributions which become strongly inverted on adiabatic passage through the intersection. It is further demonstrated that intermediate distributions can be reconstructed from the photoemission spectrum of the dissociating molecule. The illustration, given using quantum mechanical calculations of resonance Raman profiles for ozone, completes a practicable cycle of conversion of intermediate distributions into topographic features of the conical intersection.

  12. Measurement of Br photofragment orientation and alignment from HBr photodissociation: Production of highly spin-polarized hydrogen atoms

    SciTech Connect

    Rakitzis, T. Peter; Samartzis, P.C.; Toomes, R.L.; Kitsopoulos, Theofanis N.

    2004-10-15

    The orientation and alignment of the {sup 2}P{sub 3/2} and {sup 2}P{sub 1/2} Br photofragments from the photodissociation of HBr is measured at 193 nm in terms of a{sub q}{sup (k)}(p) parameters, using slice imaging. The A {sup 1}{pi} state is excited almost exclusively, and the measured a{sub q}{sup (k)}(p) parameters and the spin-orbit branching ratio show that the dissociation proceeds predominantly via nonadiabatic transitions to the a {sup 3}{pi} and 1 {sup 3}{sigma}{sup +} states. Conservation of angular momentum shows that the electrons of the nascent H atom cofragments (recoiling parallel to the photolysis polarization) are highly spin polarized: about 100% for the Br({sup 2}P{sub 1/2}) channel, and 86% for the Br({sup 2}P{sub 3/2}) channel. A similar analysis is demonstrated for the photodissociation of HCl.

  13. Internal energy dependence of the photodissociation dynamics of O3(-) using cryogenic photoelectron-photofragment coincidence spectroscopy.

    PubMed

    Shen, Ben B; Benitez, Yanice; Lunny, Katharine G; Continetti, Robert E

    2017-09-07

    Photoelectron-photofragment coincidence (PPC) spectra of ozonide, O3(-), were measured at 388 nm (Ehν = 3.20 eV) using a newly constructed cryogenic octopole accumulation trap coupled to a PPC spectrometer. The photoelectron spectra reveal three processes consisting of a stable photodetachment channel, and two distinct photodissociation pathways yielding (1) O2 + O(-) or (2) O + O2(-). The first photodissociation pathway is observed in the PPC spectra by photodetachment of the O(-) product by a second photon, and produces electronically excited O2((1)Δg). The O2(-) product of the second photodissociation pathway undergoes autodetachment for O2(-)((2)Πg, v″ > 4), a process greatly enhanced by vibrational excitation of the precursor O3(-). Cooling anions thermalized at 300 K to <17 K in a cryogenic octopole accumulation trap essentially turns off this autodetachment pathway. The product kinetic energy distribution in coincidence with the autodetached electrons from O2(-)(v″ = 4) exhibits resolved features consistent with bend (ν2), asymmetric stretch (ν3) and a stretching combination band (ν1 + ν3) in the intermediate electronic state, illustrating the insights that can be gained from kinematically complete measurements. These results are discussed in the context of the low-lying excited states of O3(-).

  14. Bimetallic redox synergy in oxidative palladium catalysis.

    PubMed

    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

  15. PD/MG BIMETALLIC CORROSION CELLS FOR DECHLORINATING PCBS

    EPA Science Inventory

    Two dissimilar metals immersed in a conducting solution develop different corrosion potentials forming a bimetallic corrosion cell. Enhanced corrosion of an active metal like Mg combined with catalytic hydrogenation properties of a noble metal like Pd in such bimetallic cells can...

  16. PD/MG BIMETALLIC CORROSION CELLS FOR DECHLORINATING PCBS

    EPA Science Inventory

    Two dissimilar metals immersed in a conducting solution develop different corrosion potentials forming a bimetallic corrosion cell. Enhanced corrosion of an active metal like Mg combined with catalytic hydrogenation properties of a noble metal like Pd in such bimetallic cells can...

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

    PubMed

    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.

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

    SciTech Connect

    Not Available

    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.

  19. Mass-analyzed velocity map imaging of doubly charged photofragments from C70

    NASA Astrophysics Data System (ADS)

    Katayanagi, Hideki; Mitsuke, Koichiro

    2011-10-01

    The velocity distributions of the fragments produced by dissociative photoionization of C70 have been measured at several photon energies in the extreme UV region, by using a flight-time resolved velocity map imaging (VMI) technique combined with a high-temperature molecular beam and synchrotron radiation. Average kinetic energy release was estimated for the six reaction steps of consecutive C2 emission, starting from C702+ → C682+ + C2 to C602+→ C582+ + C2. The total kinetic energy generated in each step shows a general tendency to increase with increasing hν, except for the first and fifth steps. This propensity reflects statistical redistributions of the excess energy in the transition states for the above fragmentation mechanism. Analysis based on the finite-heat-bath theory predicts the detectable minimum cluster sizes at the end of the C2-emission decay chain. They accord well with the minimum sizes of the observed ions, if the excess energy in the primary C702+ is assumed to be smaller by ˜15 eV than the maximum available energy. The present VMI experiments reveal remarkably small kinetic energy release in the fifth step, in contradiction to theoretical predictions, which suggests involvement of other fragmentation mechanisms in the formation of C602+.

  20. Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH +allene reaction

    NASA Astrophysics Data System (ADS)

    Raman, Arjun S.; Justine Bell, M.; Lau, Kai-Chung; Butler, Laurie J.

    2007-10-01

    These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH2CCH2OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl +CH2CCH2OH photofragments, a spin-orbit branching ratio for Cl(P1/22):Cl(P3/22) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH2CCH2OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH2CCH2OH radical intermediate to the three most important product channels for the OH +allene reaction expected from this radical intermediate: formaldehyde+C2H3, H +acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH3 product channel. We compare our results to a previous theoretical study of the O +allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates.

  1. Earth abundant bimetallic nanoparticles for heterogeneous catalysis

    NASA Astrophysics Data System (ADS)

    Senn, Jonathan F., Jr.

    Polymer exchange membrane fuel cells have the potential to replace current fossil fuel-based technologies in terms of emissions and efficiency, but CO contamination of H2 fuel, which is derived from steam methane reforming, leads to system inefficiency or failure. Solutions currently under development are bimetallic nanoparticles comprised of earth-abundant metals in different architectures to reduce the concentration of CO by PROX during fuel cell operation. Chapter One introduces the Pt-Sn and Co-Ni bimetallic nanoparticle systems, and the intermetallic and core-shell architectures of interest for catalytic evaluation. Application, theory, and studies associated with the efficacy of these nanoparticles are briefly reviewed. Chapter Two describes the concepts of the synthetic and characterization methods used in this work. Chapter Three presents the synthetic, characterization, and catalytic findings of this research. Pt, PtSn, PtSn2, and Pt 3Sn nanoparticles have been synthesized and supported on gamma-Al2O3. Pt3Sn was shown to be an effective PROX catalyst in various gas feed conditions, such as the gas mixture incorporating 0.1% CO, which displayed a light-off temperatures of ˜95°C. Co and Ni monometallic and CoNi bimetallic nanoparticles have been synthesized and characterized, ultimately leading to the development of target Co Ni core-shell nanoparticles. Proposed studies of catalytic properties of these nanoparticles in preferential oxidation of CO (PROX) reactions will further elucidate the effects of different crystallographic phases, nanoparticle-support interactions, and architecture on catalysis, and provide fundamental understanding of catalysis with nanoparticles composed of earth abundant metals in different architectures.

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

    PubMed

    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.

  3. A photoactive bimetallic framework for direct aminoformylation ...

    EPA Pesticide Factsheets

    A bimetallic catalyst, AgPd@g-C3N4, was synthesized by immobilizing silver and palladium nanoparticles over the surface of graphitic carbon nitride (g-C3N4) and its utility was demonstrated for the concerted aminoformylation of aromatic nitro compounds under visible light conditions. The entwined AgPd@g-C3N4 catalyst was very effective in exploiting formic acid as a source of hydrogen and acting as a formylating agent under photochemical conditions. Prepared for submission to Royal Society of Chemistry (RSC) journal, Green Chemistry

  4. A photoactive bimetallic framework for direct aminoformylation ...

    EPA Pesticide Factsheets

    A bimetallic catalyst, AgPd@g-C3N4, was synthesized by immobilizing silver and palladium nanoparticles over the surface of graphitic carbon nitride (g-C3N4) and its utility was demonstrated for the concerted aminoformylation of aromatic nitro compounds under visible light conditions. The entwined AgPd@g-C3N4 catalyst was very effective in exploiting formic acid as a source of hydrogen and acting as a formylating agent under photochemical conditions. Prepared for submission to Royal Society of Chemistry (RSC) journal, Green Chemistry

  5. Identification of Photofragments from One-Color Resonantly-Enhanced (˜{A}-˜{X}) Multi-Photon Photodissociation of Acetylene

    NASA Astrophysics Data System (ADS)

    Jiang, Jun; Muthike, Angelar K.; Field, Robert W.

    2017-06-01

    One-color (212-220 nm) multi-photon photodissociation of acetylene, resonantly enhanced by the ˜{A}(S_1)-˜{X} transition, gives rise to strong photofragment fluorescence signals in the visible and near UV regions. In this work, fluorescence signals from the photofragments, generated with three intermediate S_1 levels (trans 3^4, trans 3^5, and cis 3^16^1), are studied, both in the flow cell and supersonic jet conditions. In the flow cell (˜3 torr), the dispersed fluorescence (DF) spectra of the photofragments are obtained. For all three S_1 levels, we observe C_2 Swan band (d^3Π_g-a^3Π_u) and C_2 Deslandres-d'Azambuja band (C^1Π_g-A^1Π_u) emissions, with the former approximately four times more intense than the latter. In the supersonic jet condition (collision-free), fluorescence time-traces at selected wavelength regions are analyzed. We confirm the presence of the two C_2 emission bands and their relative intensity observed in the DF spectra. In the supersonic jet condition, we also observe long lifetime visible fluorescence signal (>3 μs lifetime), which is likely due to emissions from C_2H fragment, based on previous vacuum UV photolysis studies of acetylene. The photodissociation mechanism is inferred, based on our analysis of the flow cell DF spectra and the fluorescence time-traces obtained in the supersonic jet condition. The C_2H fragment is likely generated from one-photon photodissociation of S_1 acetylene, and an additional photon dissociates the C_2H fragment into the C_2 C and d states.

  6. Vibrational spectroscopic studies of adsorbates on bimetallic surfaces. Doctoral thesis

    SciTech Connect

    Kuhn, W.K.

    1992-12-01

    In this work, well-defined bimetallic surfaces have been studied using carbon monoxide adsorption in conjunction with infrared reflection absorption spectroscopy (IRAS). These studies have indicated that for CO adsorbed on Cu overlayers, the bond between the CO and the Cu adatoms is comprised of both pi-back-donation and polarization interaction components. The sum of the contributions from these effects determines the observed bond strength with the observed CO stretching frequency being determined by the relative contributions of the components. In addition, it was determined that IR spectra of adsorbed CO show a remarkable sensitivity to surface structure. Three-dimensional Cu clusters, well-ordered two dimensional Cu islands and isolated Cu atoms are distinctively characterized by their CO IR peaks. In addition, both disorder-order and order-order transitions are observed for the metal overlayers on the single crystal metal substrates. It was also observed that localized segregation and ordering of mixed Co and S overlayers on a Mo(110) substrate occurs upon annealing.

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

    SciTech Connect

    Chunshan, Song; Kirby, S.; Schmidt, E.

    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.

  8. BIMETALLIC LITHIUM BOROHYDRIDES TOWARD REVERSIBLE HYDROGEN STORAGE

    SciTech Connect

    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.

  9. 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.

    PubMed

    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.

  10. Neutral bimetallic transition metal phenoxyiminato catalysts and related polymerization methods

    DOEpatents

    Marks, Tobin J [Evanston, IL; Rodriguez, Brandon A [Evanston, IL; Delferro, Massimiliano [Chicago, IL

    2012-08-07

    A catalyst composition comprising a neutral bimetallic diphenoxydiiminate complex of group 10 metals or Ni, Pd or Pt is disclosed. The compositions can be used for the preparation of homo- and co-polymers of olefinic monomer compounds.

  11. Bimetallic Microswimmers Speed Up in Confining Channels

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    PubMed Central

    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.

  14. Thermal stability of bimetallic Au/Fe nanoparticles in silica matrix

    SciTech Connect

    Pannu, Compesh Singh, Udai B. Hooda, Sonu Kabiraj, D. Avasthi, D. K.

    2014-04-24

    Thin silica film containing Au and Fe bimetallic nanoparticles were prepared by atom beam cosputtering. The samples were annealed at different temperatures from 400 to 800° C to study the thermal stability of bimetallic nanoparticles using X ray diffraction. It is observed that at 800° C strong structural rearrangement took place leading to thermal decomposition of bimetallic nanoparticles.

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

    PubMed

    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. Stabilization of Au at edges of bimetallic PdAu nanocrystallites.

    PubMed

    Yudanov, Ilya V; Neyman, Konstantin M

    2010-05-21

    Density functional calculations were performed to study the distribution of Au atoms in bimetallic PdAu nanoparticles. A series of Pd(79-n)Au(n) clusters of truncated octahedral shape with different content of Au ranging from n = 1 to 60 was used to model such bimetallic nanosystems. Segregation of Au to the particle surface is found to be thermodynamically favorable. The most stable sites for Au substitution are located at the edges of the PdAu nanoclusters. The stabilization at the edges is rationalized by their higher flexibility for surface relaxation which minimizes the strain induced by larger atomic radius of Au as compared to Pd. This stabilization of Au at the edges indicates the possibility to synthesize PdAu particles with Pd atoms located mainly on the facets, and edges "decorated" by Au atoms. Such nanocrystallites are expected to exhibit peculiar catalytic properties and, being thermodynamically stable, should be prone to retaining their initial shape under catalytic conditions.

  17. Sulphur adsorption and effects of sulphur poisoning on RhCu bimetallic surfaces

    NASA Astrophysics Data System (ADS)

    Foord, J. S.; Reynolds, A. E.

    1985-04-01

    Sulphur adsorption on Cu covered Rh(111) surfaces, prepared as models of "bimetallic cluster" catalysts, was studied and the effects of preadsorbed sulphur on the chemisorption of CO and C 2H 2 on Rh(111)-Cu surfaces examined. In the initial stages of the interaction of sulphur with the metal, strongly bound adsorbate overlayers are formed, while epitaxial sulphide growth takes place at higher sulphur exposures. Sulphur adsorbs indiscriminately on the two components in the bimetallic interface during overlayer formation; preferential formation of Rh 2S 3 is observed, however, at higher sulphur loadings. Sulphur overlayers block the chemisorption of CO and C 2H 2 although blocking is not complete at sulphur concentrations below 8.0 × 10 18 atoms m -2. The extent of adsorption of C 2H 2 falls much more rapidly with increased sulphur coverage than does CO chemisorption, showing that C 2H 2 adsorption requires the larger ensemble size of Rh atoms. Sulphur produces a weakening of the CO adsorption bond by 29 kJ mol -1 but has no effect on the energetics of ethylidyne decomposition.

  18. Dodecanethiol-protected copper/silver bimetallic nanoclusters and their surface properties.

    PubMed

    Ang, T P; Chin, W S

    2005-12-01

    Dodecanethiol-protected copper/silver bimetallic nanoclusters were prepared by a liquid-phase method using different copper to silver feed ratios. The morphology and size of the prepared nanoclusters were analyzed with X-ray diffraction (XRD) and transmission electron microscopy (TEM), while their spectroscopic and surface properties were characterized by infrared (IR) and X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), and 13C cross-polarization magic angle spinning NMR (13C CPMAS NMR). TEM analysis indicated that all the bimetallic clusters prepared are approximately 4-6 nm in size. On the other hand, the results of XRD, XPS, and Fourier transform infrared (FTIR) spectroscopy suggested that the surfaces of the alloy nanoclusters are mostly enriched with the less noble metal copper atoms. This surface enrichment of copper may be attributed to a galvanic exchange process during preparation, and the extent of enrichment is directly related to the copper feed ratio used. Interestingly, DSC studies showed two melting transitions in some of these alloy samples, suggesting different packing behavior of the dodecanethiol chains onto the heterogeneously intercalated silver- and copper-rich surfaces.

  19. Degradation of chlorofluorocarbons using granular iron and bimetallic irons.

    PubMed

    Jeen, Sung-Wook; Lazar, Snezana; Gui, Lai; Gillham, Robert W

    2014-03-01

    Degradation of trichlorofluoromethane (CFC11) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113) by granular iron and bimetallic (nickel- or palladium-enhanced) irons was studied in flow-through column tests. Both compounds were rapidly degraded, following pseudo-first-order kinetics with respect to the parent compounds. The average pseudo-first-order rate constants for CFC11 were similar among different materials, except for palladium-enhanced iron (PdFe), in which the rate of degradation was about two times faster than for the other materials. In the case of CFC113, the rate constants for bimetallic irons were about two to three times greater than for the regular iron material. The smaller than expected differences in degradation rate constants of chlorofluorocarbons (CFCs) between regular iron and bimetallic irons suggested little, if any, catalytic effect of the bimetallic materials in the initial degradation step. Subsequent degradation steps involved catalytic hydrogenation, however, playing a significant role in further degradation of reaction intermediates. The degradation intermediates and final products of CFC11 and CFC113 suggested that degradation proceeded through hydrogenolysis and α/β-elimination in the presence of regular iron (Fe) and nickel-enhanced iron (NiFe). Even though there is only minor benefit in the use of bimetallic iron in terms of degradation kinetics of the parent CFCs, enhanced degradation rates of intermediates such as chlorotriflouroethene (CTFE) in subsequent reaction steps could be beneficial.

  20. High-resolution Rydberg tagging time-of-flight measurements of atomic photofragments by single-photon vacuum ultraviolet laser excitation

    SciTech Connect

    Jones, Brant; Zhou Jingang; Yang Lei; Ng, C. Y.

    2008-12-15

    By coupling a comprehensive tunable vacuum ultraviolet (VUV) laser system to a velocity-mapped ion imaging apparatus, we show that high-resolution high-n Rydberg tagging time-of-flight (TOF) measurements of nascent atomic photofragments formed by laser photodissociation can be made using single-photon VUV laser photoexcitation. To illustrate this single-photon Rydberg tagging TOF method, we present here the results of the VUV laser high-n Rydberg tagging TOF measurements of O({sup 3}P{sub 2}) and S({sup 3}P{sub 2}) formed in the photodissociation of SO{sub 2} and CS{sub 2} at 193.3 and 202.3 nm, respectively. These results are compared to those obtained by employing the VUV laser photoionization time-sliced velocity-mapped ion imaging technique. The fact that the kinetic energy resolutions achieved in the VUV laser high-n Rydberg tagging TOF measurements of O and S atoms are found to be higher than those observed in the VUV laser photoionization, time-sliced velocity-mapped ion imaging studies show that the single-photon VUV laser high-n Rydberg tagging TOF method is useful and complementary to state-of-the-art time-sliced velocity-mapped ion imaging measurements of heavier atomic photofragments, such as O and S atoms. Furthermore, the general agreement observed between the VUV laser high-n Rydberg tagging TOF and velocity-mapped ion imaging experiments supports the conclusion that the lifetimes of the tagged Rydberg states of O and S atoms are sufficiently long to allow the reliable determination of state-resolved UV photodissociation cross sections of SO{sub 2} and CS{sub 2} by using the VUV laser high-n Rydberg tagging TOF method.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Bimetallic strip for low temperature use

    DOEpatents

    Bussiere, Jean F.; Welch, David O.; Suenaga, Masaki

    1981-01-01

    There is provided a class of mechanically pre-stressed structures, suitably bi-layer strips comprising a layer of group 5 transition metals in intimate contact with a layer of an intermetallic compound of said transition metals with certain group 3A, 4A or 5A metals or metalloids suitably gallium, indium, silicon, germanium, tin, arsenic or antimony. The changes of Young's modulus of these bi-layered combinations at temperatures in the region of but somewhat above absolute zero provides a useful means of sensing temperature changes. Such bi-metallic strips may be used as control strips in thermostats, in direct dial reading instruments, or the like. The structures are made by preparing a sandwich of a group 5B transition metal strip between the substantially thicker strips of an alloy between copper and a predetermined group 3A, 4A or 5A metal or metalloid, holding the three layers of the sandwich in intimate contact heating the same, cooling the same and removing the copper alloy and then removing one of the two thus formed interlayer alloys between said transition metal and the metal previously alloyed with copper.

  3. Synthesis of bimetallic nanoshells by an improved electroless plating method.

    PubMed

    Liu, J B; Dong, W; Zhan, P; Wang, S Z; Zhang, J H; Wang, Z L

    2005-03-01

    In the Letter, we demonstrate an improved electroless plating method for the synthesis of bimetallic shell particles. The procedure involves a combination of surface reaction, seeding growth, and removal of supporting cores. We modified ammonical AgNO3 in ethanol with a controlled amount of HCHO in the seeding process and a uniform and relatively dense coverage of silver nanoparticle seeds on colloid cores was achieved. Following the second kind of metal plating, we extended this method to prepare continuous bimetallic core-shell and hollow particles with a submicrometer diameter. The morphologies of the bimetallic Cu/Ag and Pt/Ag particles were studied with transmission electron microscopy and scanning electron microscopy, and their crystallinity and chemical composition were confirmed by X-ray diffraction. The prepared materials may be of applied value in areas such as catalysis, optics, and plasmonics.

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

    SciTech Connect

    Chen, Jingguan

    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.

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  8. Shape control of bimetallic nanocatalysts through well-designed colloidal chemistry approaches.

    PubMed

    Gu, Jun; Zhang, Ya-Wen; Tao, Franklin Feng

    2012-12-21

    Synthesis of bimetallic nanomaterials with well controlled shape is an important topic in heterogeneous catalysis, low-temperature fuel cell technology, and many other fields. Compared with monometallic counterparts, bimetallic nanocatalysts endow scientists with more opportunities to optimize the catalytic performance by modulating the charge transfer between different metals, local coordination environment, lattice strain and surface element distribution. Considering the current challenges in shape controlled synthesis of bimetallic nanocatalysts, this tutorial review highlights some significant achievements in preparing bimetallic alloy, core-shell and heterostructure nanocrystals with well-defined morphologies, summarizes four general routes and some key factors of the bimetallic shape control scenarios, and provides some general ideas on how to design synthetic strategies to control the shape and exposing facets of bimetallic nanocrystals. The composition and shape dependent catalytic behaviours of bimetallic nanocrystals are reviewed as well.

  9. A photoactive bimetallic framework for direct aminoformylation of nitroarenes

    EPA Pesticide Factsheets

    A bimetallic catalyst, AgPd@g-C3N4, synthesized by reducing silver and palladium salts over graphitic carbon nitride (g-C3N4), enables the concerted reductive formylation of aromatic nitro compounds under photo-chemical conditions using formic acid, which serves the dual role of a hydrogen source and a formylating agent.This dataset is associated with the following publication:Baig, R.B.N., S. Verma, M. Nadagouda , and R. Varma. A photoactive bimetallic framework for direct aminoformylation of nitroarenes. GREEN CHEMISTRY. Royal Society of Chemistry, Cambridge, UK, 18(4): 1019-1022, (2016).

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Development of bi-metallic Fe-Bi nanocomposites: synthesis and characterization.

    PubMed

    Mattei, J G; Pelletier, F; Ciuculescu, D; Lecante, P; Amiens, C; Casanove, M J

    2012-11-01

    We investigate the formation of bi-metallic particles in the Fe-Bi system, well known as totally immiscible in the bulk, using a large combination of structural and element-sensitive techniques, well-adapted to the nanoscale. The synthesis approach makes use of the kinetics of decomposition of the different precursors to achieve a controlled sequential growth of the different elements. Different ligands have also been used in order to limit the size and ensure dispersion of the synthesized particles. Our results give evidence for the presence of body-centered cubic ferromagnetic iron nanograins together with larger bismuth crystallites. Interestingly, while the iron particles remain very small, the resistance to oxidation of the Fe-Bi nanocomposites highly depends on the stabilizing ligand used in the synthesis. The presence of both metals, Fe and Bi, in a single cluster has been clearly revealed in the oxidation resistant composite synthesized using the HMDS ligand.

  13. Laser IR fragmentation of molecular clusters: the role of channels for energy input and relaxation, the influence of surroundings, and the dynamics of fragmentation

    NASA Astrophysics Data System (ADS)

    Makarov, G. N.

    2017-06-01

    The results of research into the infrared (IR) laser fragmentation of molecular clusters by resonant vibrational excitation of their constituent molecules are presented with special attention given to the role of cluster environment, the energy input and relaxation channels, and dynamical aspects. For this purpose, the results of experiments with free homogeneous and mixed molecular clusters and of experiments with clusters inside or on the surface of large inert gas clusters are analyzed, the laser excitation pulses varying in wavelength and duration. Data on the character and rate of cluster fragmentation, and on the intramolecular and intracluster vibrational energy relaxation times in clusters are discussed. Results of an investigation into the structure and dynamics of molecular clusters and atomic-molecular complexes obtained by IR photodissociation spectroscopy and the spectroscopy of photofragments are analyzed. Methods for generating heterogeneous molecular clusters, for size-selecting clusters. and for studying the IR dissociation and IR fragmentation of clusters are also briefly considered.

  14. Spectroscopy at metal cluster surfaces. Annual report, Year 2

    SciTech Connect

    Duncan, M.A.

    1995-08-01

    The focus of our research program is the study of gas phase metal clusters to evaluate their potential to model fundamental interactions present on metal surfaces. To do this, we characterize the chemical bonding present between the component atoms in metal clusters as well as the bonding exhibited by ``physisorption`` on cluster surfaces. Electronic spectra, vibrational frequencies and bond neutral and ionized clusters with a variety of laser/mass spectrometry techniques. We are particularly interested in bimetallic cluster systems, and how their properties compare to those of corresponding pure metal clusters.

  15. Charge distribution and Fermi level in bimetallic nanoparticles.

    PubMed

    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.

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

    PubMed

    Blosi, Magda; Ortelli, Simona; Costa, Anna Luisa; Dondi, Michele; Lolli, Alice; Andreoli, Sara; Benito, Patricia; Albonetti, Stefania

    2016-07-08

    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.

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

    PubMed Central

    Blosi, Magda; Ortelli, Simona; Costa, Anna Luisa; Dondi, Michele; Lolli, Alice; Andreoli, Sara; Benito, Patricia; Albonetti, Stefania

    2016-01-01

    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. PMID:28773672

  18. Bimetallic alloy electrocatalysts with multilayered platinum-skin surfaces

    DOEpatents

    Stamenkovic, Vojislav R.; Wang, Chao; Markovic, Nenad M.

    2016-01-26

    Compositions and methods of preparing a bimetallic alloy having enhanced electrocatalytic properties are provided. The composition comprises a PtNi substrate having a surface layer, a near-surface layer, and an inner layer, where the surface layer comprises a nickel-depleted composition, such that the surface layer comprises a platinum skin having at least one atomic layer of platinum.

  19. Lattice measurement and alloy compositions in metal and bimetallic nanoparticles.

    PubMed

    Tsen, S-C Y; Crozier, P A; Liu, J

    2003-12-01

    A new reliable method for determining the lattice spacings of metallic and bimetallic nanoparticles in phase contrast high resolution electron microscopy (HREM) images was developed. In this study, we discuss problems in applying HREM techniques to single metal (Pt and Au) and bimetallic (AuPd) nanoparticles of unknown shapes and random orientations. Errors arising from particle tilt and edge effects are discussed and analysis criteria are presented to reduce these errors in measuring the lattice parameters of nanoparticles. The accuracy of an individual particle lattice measurement is limited by an effective standard deviation which depends on the size of the individual nanoparticle. For example, the standard deviation for 20-30 A Pt or Au nanoparticles is about 1.5%. To increase the accuracy in determining the lattice spacings of nanoparticles, statistical methods have to be used to obtain the average lattice spacing of an ensemble of nanoparticles. We measured approximately 100 nanoparticles with sizes in the range of 20-30 A and found that the mean lattice spacing can be determined to within 0.2%. By applying Vegard's law to the AuPd bimetallic systems we successfully detected the presence of alloying. For 30 A nanoparticles, the estimated ultimate error in determining the composition of the AuPd alloy is about 3% provided that at least 100 particles are measured. Finally, the challenges in determining the presence of more than one alloy phases in bimetallic nanoparticle systems were also discussed.

  20. A photoactive bimetallic framework for direct aminoformylation of nitroarenes

    EPA Science Inventory

    A bimetallic catalyst, AgPd@g-C3N4, was synthesized by immobilizing silver and palladium nanoparticles over the surface of graphitic carbon nitride (g-C3N4) and its utility was demonstrated for the concerted aminoformylation of aromatic nitro compounds under visible light conditi...

  1. A photoactive bimetallic framework for direct aminoformylation of nitroarenes

    EPA Science Inventory

    A bimetallic catalyst, AgPd@g-C3N4, was synthesized by immobilizing silver and palladium nanoparticles over the surface of graphitic carbon nitride (g-C3N4) and its utility was demonstrated for the concerted aminoformylation of aromatic nitro compounds under visible light conditi...

  2. Hydroxylation of Benzene via CH Activation Using Bimetallic ...

    EPA Pesticide Factsheets

    A photoactive bimetallic CuAg@g-C3N4 catalyst system has been designed and synthesized by impregnating copper and silver nanoparticles over the graphitic carbon nitride surface. Its application has been demonstrated in the hydroxylation of benzene under visible light. Prepared for submission to American Chemical Society (ACS) journal, ACS Sustainable Chemistry & Engineering.

  3. Lithium-tellurium bimetallic cell has increased voltage

    NASA Technical Reports Server (NTRS)

    Cairns, E. J.; Rogers, G. L.; Shimotake, H.

    1968-01-01

    Lithium-tellurium secondary cell with a fused lithium halide electrolyte, tested in the temperature range 467 degrees to 500 degrees C, showed improvement over the sodium bismuth cell. The voltage of this bimetallic cell was increased by using the more electropositive anode material, lithium, and the more electronegative cathode material, tellurium.

  4. Self-discharge in bimetallic cells containing alkali metal

    NASA Technical Reports Server (NTRS)

    Foster, M. S.; Hesson, J. C.; Shimotake, H.

    1969-01-01

    Theoretical analysis of thermally regenerative bimetallic cells with alkali metal anodes shows a relation between the current drawn and the rate of discharge under open-circuit conditions. The self-discharge rate of the cell is due to the dissolution and ionization of alkali metal atoms in the fused-salt electrolyte

  5. Crystalline structure-dependent growth of bimetallic nanostructures.

    PubMed

    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.

  6. Cyclic carbonate synthesis catalysed by bimetallic aluminium-salen complexes.

    PubMed

    Clegg, William; Harrington, Ross W; North, Michael; Pasquale, Riccardo

    2010-06-18

    The development of bimetallic aluminium-salen complexes [{Al(salen)}(2)O] as catalysts for the synthesis of cyclic carbonates (including the commercially important ethylene and propylene carbonates) from a wide range of terminal epoxides in the presence of tetrabutylammonium bromide as a cocatalyst is reported. The bimetallic structure of one complex was confirmed by X-ray crystallography. The bimetallic complexes displayed exceptionally high catalytic activity and in the presence of tetrabutylammonium bromide could catalyse cyclic carbonate synthesis at atmospheric pressure and room temperature. Catalyst-reuse experiments demonstrated that one bimetallic complex was stable for over 60 reactions, though the tetrabutylammonium bromide decomposed in situ by a retro-Menschutkin reaction to form tributylamine and had to be regularly replaced. The mild reaction conditions allowed a full analysis of the reaction kinetics to be carried out and this showed that the reaction was first order in aluminium complex concentration, first order in epoxide concentration, first order in carbon dioxide concentration (except when used in excess) and unexpectedly second order in tetrabutylammonium bromide concentration. Further kinetic experiments demonstrated that the tributylamine formed in situ was involved in the catalysis and that addition of butyl bromide to reconvert the tributylamine into tetrabutylammonium bromide resulted in inhibition of the reaction. The reaction kinetics also indicated that no kinetic resolution of racemic epoxides was possible with this class of catalysts, even when the catalyst was derived from a chiral salen ligand. However, it was shown that if enantiomerically pure styrene oxide was used as substrate, then enantiomerically pure styrene carbonate was formed. On the basis of the kinetic and other experimental data, a catalytic cycle that explains why the bimetallic complexes display such high catalytic activity has been developed.

  7. Hydrogen storage in bimetallic Ti-Al sub-nanoclusters supported on graphene.

    PubMed

    Ramos-Castillo, C M; Reveles, J U; Cifuentes-Quintal, M E; Zope, R R; de Coss, R

    2017-08-09

    Recent studies suggest that graphene decorated with light metal atoms is a feasible alternative for the design of the next generation of hydrogen storage systems, that is, materials which require a gravimetric content of at least 7.5 wt%, and an adsorption energy of 0.2-0.6 eV per H2. We present a first principles study of hydrogen adsorption in titanium, and bimetallic Ti5-xAlx (x = 1-3) and Ti7-xAlx (x = 1-4) clusters supported on graphene. Our results for Ti5, Ti4Al, Ti7, and Ti6Al show that doping titanium clusters with small amounts of aluminum does not influence the cluster stability on graphene, but that notably, it enhances its hydrogen gravimetric content up to 3.2-3.6 wt%. A further increment of the aluminum concentration was found to reduce the cluster stability and to favor hydrogen desorption, as shown by our calculations for supported Ti3Al2, Ti2Al3, TiAl4 and Ti5Al2. An analysis of atomic charges and density of states reveals the role of charge transfer and orbital interactions in the stability of hydride and dihydrogen complexes in the studied systems. Our results support the hypothesis that a controlled introduction of small metal clusters to graphene is a feasible way to enhance its hydrogen gravimetric content, and it opens up the possibility of investigating other binary TMx-Ay (TM = transition metal and A = main group) clusters supported on graphene as promising candidates for hydrogen storage.

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Catalytic reduction of N2O by CO over PtlAu-m clusters: A first-principles study

    NASA Astrophysics Data System (ADS)

    Mi, Hong; Wei, Shi-Hao; Duan, Xiang-Mei; Pan, Xiao-Yin

    2015-09-01

    Based on the density functional theory, we investigate negatively charged clusters , which show significant catalytic properties in the simultaneous removal of N2O and CO. We find that in these clusters, the platinum atom acts as the adsorption center for N2O, the gold and Pt atoms act as electron donors during the reaction, and the charge transfers from the bimetallic cluster to the N2O molecule. As the proportion of Au in the cluster increases, the d band center shifts down further away from the Fermi level, meanwhile more charge is transferred to the N2O molecule, resulting in weaker N-O bond strength. Therefore bimetallic cluster shows better catalytic properties than the other clusters, especially pure Pt4- and Au4- clusters. This means that there is a synergetic effect between the Pt and Au atoms in the negatively charged bimetallic clusters. Our results help to reveal the mechanism of bimetallic clusters as excellent catalysts. Project supported by the National Natural Science Foundation of China (Grants Nos. 10804058, 11174164, and 11275100), the Science Foundation of Zhejiang Province, China (Grant No. Y607546), and the K. C. Wong Magna Foundation in Ningbo University, China.

  10. UV PHOTODESORPTION OF METHANOL IN PURE AND CO-RICH ICES: DESORPTION RATES OF THE INTACT MOLECULE AND OF THE PHOTOFRAGMENTS

    SciTech Connect

    Bertin, Mathieu; Doronin, Mikhail; Philippe, Laurent; Jeseck, Pascal; Michaut, Xavier; Fillion, Jean-Hugues; Romanzin, Claire; Ligterink, Niels; Linnartz, Harold

    2016-02-01

    Wavelength-dependent photodesorption rates have been determined using synchrotron radiation for condensed pure and mixed methanol ice in the 7–14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10{sup −5} molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower (<10{sup −6} molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH{sub 3}OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH{sub 3}, OH, H{sub 2}CO, and CH{sub 3}O/CH{sub 2}OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH{sub 3}O, therefore, opening new gas phase chemical routes for the formation of complex molecules.

  11. Fluorescence Excitation Spectra of Photo-Fragmented Nitrobenzene Using a Picosecond Laser: Potential Evidence for no Produced by Two Distinct Channels.

    NASA Astrophysics Data System (ADS)

    Lue, Christopher J.; Tanjaroon, Chakree; Johnson, J. Bruce; Reeve, Scott W.; Allen, Susan D.

    2013-06-01

    Upon absorption of a UV photon, nitrobenzene can dissociate into C_6H_5O and NO through two different mechanisms. Evidence for these mechanisms was obtained from velocity map imaging (VMI) studies and theoretical calculations. VMI experiments showed NO produced with two distinct rotational distributions, which the calculations explained as a fast and a slow channel for NO production. We have recorded high resolution fluorescence excitation spectra of the NO resulting from photo-fragmented nitrobenzene using a pulsed picosecond tunable laser (pulse width ≈ 15 ps) by means of a two-color process. In the two-color process, photons of a particular energy dissociated the nitrobenzene while photons of a different energy probed the A^2Σ^+← X^2Π_{(1/2,3/2)} NO band system between 225-260 nm. This laser system allowed us to vary the delay between the photolysis and excitation pulses. At longer delays (>1 ns), we observed an increase in the population of NO, which may be evidence that at least two photolysis channels produce NO. We present the spectra we recorded at various photolysis/probe delays ranging from 0.025 to 1.5 ns. The spectral subtraction method we used to observe the production increase is introduced. Hause, M. L.; Herath, N.; Zhu, R.; Lin, M. C. and Suits, A. G. Nat Chem, Nature Publishing Group, 2011, 3, 932-937

  12. UV Photodesorption of Methanol in Pure and CO-rich Ices: Desorption Rates of the Intact Molecule and of the Photofragments

    NASA Astrophysics Data System (ADS)

    Bertin, Mathieu; Romanzin, Claire; Doronin, Mikhail; Philippe, Laurent; Jeseck, Pascal; Ligterink, Niels; Linnartz, Harold; Michaut, Xavier; Fillion, Jean-Hugues

    2016-02-01

    Wavelength-dependent photodesorption rates have been determined using synchrotron radiation for condensed pure and mixed methanol ice in the 7-14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10-5 molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower (<10-6 molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH3OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH3, OH, H2CO, and CH3O/CH2OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH3O, therefore, opening new gas phase chemical routes for the formation of complex molecules.

  13. Structural Characterization of Bimetallic Nanocrystal Electrocatalysts

    SciTech Connect

    Cullen, David A

    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. Extended X-ray absorption fine structure of bimetallic nanoparticles

    PubMed Central

    2011-01-01

    Summary 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. PMID:21977436

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

    DOEpatents

    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.

  16. Bimetallic reactivity. On the use of oxadiazoles as binucleating ligands.

    PubMed

    Incarvito, C; Rheingold, A L; Qin, C J; Gavrilova, A L; Bosnich, B

    2001-03-12

    Two (1,3,4)-oxadiazole ligands have been prepared. In one case the oxadiazole ring is flanked by two o-aniline groups, and in the other case it is an extension of the first where the amines are condensed with 2-picolyl groups. A monometallic copper(II) complex of the former has been prepared, and its crystal structure was determined. A number of bimetallic copper(II), cobalt(II), and nickel(II) complexes of the di-deprotonated latter ligand were prepared and isolated. The crystal structure of the cobalt(II) complex bearing two acetate bridges is reported. The work demonstrates that the seldom-employed oxadiazole ring can be used effectively for generating bimetallic complexes.

  17. Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

    NASA Astrophysics Data System (ADS)

    Murillo, Luis E.

    Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are

  18. Dynamic critical temperature in MnIIFeIII bimetallic oxalates

    NASA Astrophysics Data System (ADS)

    Huang, Jinhua; Shi, Xiaoling; Song, Zhaoyuan; Shi, Yingguo

    2017-08-01

    MnIIFeIII bimetallic oxalates are described by a spin-5/2 Blume-Capel (BC) model on a layered honeycomb structure. The effects of the interlayer coupling, the single-ion anisotropy and the oscillating magnetic field on the dynamic critical temperature of the compounds are studied by a effective-field method based on Glauber-type stochastic dynamic. Dynamic phase diagrams are presented in the DA /|J1 |- T /|J1 | and T /|J1 |-h0 /|J1 | planes, and the first-order phase transition lines and the critical end point are found. Compensated magnetization regions have also been plotted and the compounds exhibit an uncompensated magnetization in the antiferromagnetic phase. In particular, a two-compensation-temperature phenomenon has also been observed in MnIIFeIII bimetallic oxalates.

  19. Centrifugally cast bimetallic pipe for offshore corrosion resistant pipelines

    SciTech Connect

    Yoshitake, A.; Torigoe, T.

    1994-12-31

    Centrifugally cast bimetallic pipes and fittings have been developed for the use of offshore oil and gas production. The metallurgical properties, mechanical properties, and corrosion properties of centrifugal a cast bimetallic pipe with outside metal of API 5L X52 to X65 internally clad with alloy 825 and 625 are discussed. First, molten steel for outer pipe is introduced into a rotating metallic mold. During the solidification of the outer pipe (carbon steel), the temperature of the pipe inside is monitored. After the solidification of the outer pipe, and when a certain temperature is reached, then a corrosion resistant alloy such as Alloy 825 or 625 for inside layer is poured. By controlling the casting conditions and selecting suitable flux, sound metallurgical bonded bimetallic pipe is produced with a minimum mixing layer at the interface also keeping a homogeneous outside wall thickness along the pipe length. The weld joints of the pipe are also evaluated from the view points of weldability, mechanical strength, fracture toughness, and corrosion resistance properties. The welding method applied was basically TIG welding (GTAW). COD tests at {minus}10 C are applied to the welds to investigate fracture toughness of the weld joints. Huey test according to ASTM A262C is carried out on the root of the welds as the corrosion test. As a result, the weld joint using filler wire of alloy625 from root to cover pass has proved a very reliable method from the point of view of mechanical and corrosion resistance properties. These centrifugally cast bimetallic pipes and fittings have been widely used for riser pipes, template process lines, top side and subsea manifolds, and flow bends for christmas trees in the North Sea.

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

    SciTech Connect

    Song, Chunshan; Schobert, H.H.

    1993-02-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that 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 the development of novel bimetallic dispersed catalysts for temperature-programmed liquefaction. The ultimate goal of the present research is to develop novel catalytic hydroliquefaction process using highly active dispersed catalysts. The primary objective of this research is to develop novel bimetallic dispersed catalysts from organometallic molecular that can be used in low precursors concentrations (< 1 %) but exhibit high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. The major technical approaches are, first, to prepare the desired heteronuclear organometallic molecules as catalyst precursors that contain covalently bound, two different metal atoms and sulfur in a single molecule. Such precursors will generate finely dispersed bimetallic catalysts such as Fe-Mo, Co-Mo and Ni-Mo binary sulfides upon thermal decomposition. The second major technical approach is to perform the liquefaction of coals unpregnated with the organometallic precursors under temperature-programmed conditions, where the programmed heat-up serves as a step for both catalyst activation and coal pretreatment or preconversion. Two to three different complexes for each of the Fe-Mo, Co-Mo, and Ni-Mo combinations will be prepared. Initial catalyst screening tests will be conducted using a subbituminous coal and a bituminous coal. Effects of coal rank and solvents will be examined with the selected bimetallic catalysts which showed much higher activity than the dispersed catalysts from conventional precursors.

  1. Strain-Induced Segregation in Bimetallic Multiply Twinned Particles.

    PubMed

    Peng, Lingxuan; Van Duyne, Richard P; Marks, Laurence D

    2015-05-21

    We analyze the possibility of strain-induced segregation in bimetallic multiply twinned particles by an analytic first-order expansion within a continuum model. The results indicate that while the change in free energy may be small, there will be a noticeable segregation of larger atoms to the external surface and smaller ones to the core, which could have interesting effects when such nanoparticles are used as heterogeneous catalysts.

  2. Fracture evaluation of fusion line cracks in bimetallic welds

    SciTech Connect

    Scott, P.M.; Rudland, D.L.; Francini, R.B.; Marschall, C.; Wilkoswski, G.M.

    1996-12-01

    There are many locations in nuclear power plants piping systems where carbon steel pipe or components are jointed to stainless steel pipe or components with a bimetallic weld. The objective of the research described in this paper was to assess the accuracy of current fracture analyses for the case of a crack along a carbon steel to austenitic weld fusion line. To achieve th is objective, material property data and data from a large-diameter (i.e., 36-inch) pipe fracture experiment were developed to assess current analytical methods. The bimetallic welds evaluated in this program were bimetallic welds obtained from a canceled Combustion Engineering plant. The welds joined sections of the carbon steel cold-leg piping system to stainless steel safe ends that were to be welded to stainless steel pump housings. The weld procedure involved buttering the carbon steel pipe with Inconel 182 weld metal and then completing the bulk of the weld using a shielded-metal-arc weld (SMAW) process using Inconel 182 weld rod. The major conclusion drawn as a result of these efforts was that the fracture behavior of the bimetallic weld evaluated in this program could be evaluated with reasonable accuracy using the strength and toughness properties of the carbon steel pipe base metal in conjunction with conventional J-estimation schemes. As will be discussed in this paper, this conclusion is only valid for the case where the weld is made using an Inconel weld procedure. If the weld is made using a stainless steel weld procedure, then decarburization at the fusion line may affect the fusion line toughness.

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

    PubMed

    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.

  4. Synthesis and characterization of Ni-Au bimetallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Nik Roselina, N. R.; Azizan, A.; Hyie, Koay Mei; Murad, Mardziah Che; Abdullah, Abdul Hakim

    2015-04-01

    Bimetallic structure of nanoparticles is of great interest due to their extraordinary properties, especially in combining the specialty of the core and its shell. This work reports the effect of pH on the synthesis of Ni-Au (nickel-gold) bimetallic nanoparticles. The synthesis involves a two-step process where Ni nanoparticles were first synthesized using polyol method with hydrazine as the reducing agent. This was followed by the process of reducing AuCl4- to Au in the solution containing pre-prepared Ni to form Ni-Au bimetallic nanoparticles using sodium citrate as the reducing agent. The results obtained from Transmission Electron Microscopy (TEM) show that the process can possibly produce either core-shell structure, or mixture of Ni and Au nanoparticles. Magnetic property of core-shell structure investigated using Vibrating Sample Magnetometer (VSM) demonstrated typical characteristic of ferromagnetic with an increased magnetization as compared to Ni nanoparticles. The saturation magnetization (Ms) and coercivity (Hc) were obtained as 19.1 emu/g and 222.3 Oe, respectively.

  5. Antibacterial activity of graphene supported FeAg bimetallic nanocomposites.

    PubMed

    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. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    SciTech Connect

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

    2011-08-30

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

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

    EPA Science Inventory

    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

    EPA Science Inventory

    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. Bimetallic fluid displacement apparatus. [for stirring and heating stored gases and liquids

    NASA Technical Reports Server (NTRS)

    Canning, T. N. (Inventor)

    1974-01-01

    Stirring and heating stored gases and liquids is accomplished by using the deformation of a bimetallic structure which deforms significantly when heated. The deformation is used to effect gradual or impulsive motion of a piston, vane, wire, or diaphram for displacement of the fluid. The heated bimetallic is also employed for heating the stored fluid.

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

    EPA Science Inventory

    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...

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

    EPA Science Inventory

    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...

  12. Analyzing velocity map images to distinguish the primary methyl photofragments from those produced upon C-Cl bond photofission in chloroacetone at 193 nm

    SciTech Connect

    Alligood, Bridget W.; Straus, Daniel B.; Butler, Laurie J.

    2011-07-21

    We use a combination of crossed laser-molecular beam scattering experiments and velocity map imaging experiments to investigate the three primary photodissociation channels of chloroacetone at 193 nm: C-Cl bond photofission yielding CH{sub 3}C(O)CH{sub 2} radicals, C-C bond photofission yielding CH{sub 3}CO and CH{sub 2}Cl products, and C-CH{sub 3} bond photofission resulting in CH{sub 3} and C(O)CH{sub 2}Cl products. Improved analysis of data previously reported by our group quantitatively identifies the contribution of this latter photodissociation channel. We introduce a forward convolution procedure to identify the portion of the signal, derived from the methyl image, which results from a two-step process in which C-Cl bond photofission is followed by the dissociation of the vibrationally excited CH{sub 3}C(O)CH{sub 2} radicals to CH{sub 3}+ COCH{sub 2}. Subtracting this from the total methyl signal identifies the methyl photofragments that result from the CH{sub 3}+ C(O)CH{sub 2}Cl photofission channel. We find that about 89% of the chloroacetone molecules undergo C-Cl bond photofission to yield CH{sub 3}C(O)CH{sub 2} and Cl products; approximately 8% result in C-C bond photofission to yield CH{sub 3}CO and CH{sub 2}Cl products, and the remaining 2.6% undergo C-CH{sub 3} bond photofission to yield CH{sub 3} and C(O)CH{sub 2}Cl products.

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

    PubMed

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

    2016-12-01

    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 O(I)) 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.

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

    PubMed

    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.

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

    PubMed

    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.

  16. Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran.

    PubMed

    Mulvey, Robert E; Blair, Victoria L; Clegg, William; Kennedy, Alan R; Klett, Jan; Russo, Luca

    2010-07-01

    The cleavage of ethers is commonly encountered in organometallic chemistry, although rarely studied in the context of new, emerging bimetallic reagents. Recently, it was reported that a bimetallic sodium-zinc base can deprotonate cyclic tetrahydrofuran under mild conditions without opening its heterocyclic (OC(4)) ring. In marked contrast to this synergic sedation, herein we show that switching to the more reactive sodium-magnesium or sodium-manganese bases promotes cleavage of at least six bonds in tetrahydrofuran, but uniquely the ring fragments are captured in separate crystalline complexes. Oxide fragments occupy guest positions in bimetallic, inverse crown ethers and C(4) fragments ultimately appear in bimetallated butadiene molecules. These results demonstrate the special synergic reactivity that can be executed by bimetallic reagents, which include the ability to capture and control, and thereby study, reactive fragments from sensitive substrates.

  17. Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran

    NASA Astrophysics Data System (ADS)

    Mulvey, Robert E.; Blair, Victoria L.; Clegg, William; Kennedy, Alan R.; Klett, Jan; Russo, Luca

    2010-07-01

    The cleavage of ethers is commonly encountered in organometallic chemistry, although rarely studied in the context of new, emerging bimetallic reagents. Recently, it was reported that a bimetallic sodium-zinc base can deprotonate cyclic tetrahydrofuran under mild conditions without opening its heterocyclic (OC4) ring. In marked contrast to this synergic sedation, herein we show that switching to the more reactive sodium-magnesium or sodium-manganese bases promotes cleavage of at least six bonds in tetrahydrofuran, but uniquely the ring fragments are captured in separate crystalline complexes. Oxide fragments occupy guest positions in bimetallic, inverse crown ethers and C4 fragments ultimately appear in bimetallated butadiene molecules. These results demonstrate the special synergic reactivity that can be executed by bimetallic reagents, which include the ability to capture and control, and thereby study, reactive fragments from sensitive substrates.

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

    PubMed

    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.

  19. Spectroscopy at metal cluster surfaces. Final report, September 15, 1993--September 14, 1996

    SciTech Connect

    Duncan, M.A.

    1998-06-01

    The focus of this research program is the study of gas phase metal clusters to evaluate their potential as models for the fundamental interactions present in catalysis. To do this, the authors characterize the chemical bonding present between the component atoms in metal clusters as well as the bonding exhibited by {open_quotes}physisorption{close_quotes} on metal atom or metal cluster surfaces. Electronic spectra, vibrational frequencies and bond dissociation energies are measured for both neutral and ionized clusters with a variety of laser/mass spectrometry techniques. The authors are particularly interested in bimetallic cluster systems, and how their properties compare to those of corresponding pure metal clusters.

  20. Applications of extended X-ray absorption fine-structure spectroscopy to studies of bimetallic nanoparticle catalysts.

    PubMed

    Frenkel, Anatoly I

    2012-12-21

    Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to study short range order in heterometallic alloys for almost four decades. In this critical review, experimental, theoretical and data analytical approaches are revisited to examine their power, and limitations, in studies of bimetallic nanocatalysts. This article covers the basics of EXAFS experiments, data analysis, and modelling of nanoscale clusters. It demonstrates that, in the best case scenario, quantitative information about the nanocatalyst's size, shape, details of core-shell architecture, as well as static and dynamic disorder in metal-metal bond lengths can be obtained. The article also emphasizes the main challenge accompanying such insights: the need to account for the statistical nature of the EXAFS technique, and discusses corrective strategies.

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

    NASA Astrophysics Data System (ADS)

    Peña-Rodríguez, Ovidio; Pal, Umapada

    2011-12-01

    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. A lightweight bimetallic actuator for spacecraft thermal control

    NASA Technical Reports Server (NTRS)

    Schilling, K. L.

    1971-01-01

    The design, development, and construction of two types of active thermal-control systems are described. These designs are based on the controlled angular deflections of spiral-wound bimetallic actuators. The use of these actuators and lightweight louvers results in a frictionless system that is low in weight yet simple in design and low in cost. Both designs exhibit high reliability, good performance repeatability, and do not require power from the spacecraft. Design philosophy and implementation, design tradeoffs, and materials selection are reviewed. The test program is described, and results are presented.

  3. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, October--December 1993

    SciTech Connect

    Schmidt, E.; Kirby, S.; Song, Chunshan; Schobert, H.H.

    1994-04-01

    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 infinite contact between the catalyst and coal. The primary objective of this research is to explore the potential of bimetallic dispersed catalysts from heterometallic molecular precursors in their use in model compound liquefaction reactions. This quarterly report describes the use of three precursors in model compound reactions. The first catalyst is a heterometallic complex consisting of two transition metals, Mo and Ni, and sulfur in a single molecule. The second is a thiocubane type complex consisting of cobalt, molybdenum and sulfur. The third is a thiocubane type cluster consisting of iron and sulfur and the fourth, the pure inorganic salt ammonium tetrathiomolybdate (ATM). It was found that the structure and the ligands in the model complexes affect the activity of the resulting catalyst significantly. The optimum reaction at a pressure of 6.9 MPa hydrogen gas varied for different catalysts. The bimetallic catalysts generated in situ from the organometallic precursor are more active than monometallic catalysts like ATTM and the thiocubane type cluster Fe{sub 4}. Main products are hydrogenated phenanthrene derivatives, like DBP, THP, sym-OHP, cis- and trans-unsym-OHP with minor isomerization products such as sym-OHA. Our results indicate that other transition metal and ligand combinations in the organometallic precursors and the use of another model compound could result in substantially higher conversion activity.

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

    PubMed

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

    PubMed

    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.

  6. Investigation of the reaction of hydroxy and carbon monoxide to form hydrogen and carbon dioxide by Photoelectron-Photofragment Coincidence spectroscopy in a cryogenic ion beam trap

    NASA Astrophysics Data System (ADS)

    Johnson, Christopher Joseph

    2011-12-01

    The HOCO radical plays a crucial role in a wide variety of chemical processes, including atmospheric CO2 regulation and combustion chemistry, as an intermediate in the elementary reaction OH + CO → H + CO2 . However, scant information exists on this species due to the difficulties in studying it. Previous photoelectron-photofragment coincidence (PPC) studies performed in this laboratory have identified key processes occurring on the HOCO potential energy surface, but are complicated by the presence of internal excitation in the precursor anions, leading to uncertainties in product energies and dynamics. To address this, a new instrument has been constructed which incorporates a cryogenically cooled linear electrostatic storage device, providing a cold source of anions for dissociative photodetachment studies by PPC spectroscopy. The enhanced resolution and well-characterized energetics provided by this instrument have allowed the fundamental energetics and processes occurring on the HOCO potential energy surface to be studied in unprecedented detail. New data shows unambiguous confirmation of the presence of tunneling in the reaction HOCO → H + CO2. Careful study of this product channel has led to the generation a model one-dimensional potential barrier describing this process directly from experimental tunneling data, and tunneling lifetimes over a range of relevant internal energies to be predicted. High resolution photodetachment experiments provide a reassignment of the electron affinities of both cis- and trans-HOCO and the determination of several normal mode frequencies not previously measured in the gas phase, each with the support of high-level ab initio quantum chemical calculations. Further details on the previously-unknown isomer well depths and the process of isomerization have been extracted using this information. Finally, nonresonant two-photon photodetachment studies of NO2 -, a species with striking electronic structure similarities to HOCO

  7. From First Principles Design to Realization of Bimetallic Catalysts for Ultrahigh Selectivity - Final Project Report

    SciTech Connect

    Richard M. Crooks

    2007-04-11

    (A) Synthesis, Characterization, and Fundamental Properties of Bimetallic DENs. AuAg alloy and core/shell bimetallic DENs were synthesized and characterized. Selective extraction was used as a structural characterization tool for these bimetallic nanoparticles. This is significant because there are few easily accessible methods for structure elucidation of bimetallic nanoparticles in this size regime. As a first step towards the synthesis of catalytically active, bimetallic heterogeneous materials we reported the incorporation of Au and Pd monometallic DENs and AuPd bimetallic DENs into amorphous titania networks. The compositional fidelity of the original DENs, and to some extent their size, is retained following dendrimer removal. Gas-phase catalytic activity for CO oxidation is higher for the bimetallic catalysts than for the corresponding Pd-only and Au-only monometallics. (B) Electrocatalysts based on dendrimer-encapsulated nanoparticles. Platinum dendrimer-encapsulated nanoparticles (DENs) were prepared within fourth-generation, hydroxyl-terminated, poly(amidoamine) dendrimers and immobilized on glassy carbon electrodes using an electrochemical immobilization strategy. X-ray photoelectron spectroscopy, electron microscopy, and electrochemical experiments confirm that the Pt DENs are about 1.4 nm in diameter and that they remain within the dendrimer following surface immobilization. The resulting Pt DEN films were electrocatalytically active for the oxygen reduction reaction (ORR). The films are also robust, surviving up to 50 consecutive cyclic voltammograms and sonication. Monometallic Pd DENs were also prepared and found to have little catalytic activity for the ORR. However, PtPd bimetallic DENs had catalytic activity nearly identical to that found for Pt-only DENs. This indicates an overall catalytic enhancement for the bimetallic electrocatalysts.

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

    SciTech Connect

    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.

  9. Tuning the Composition of AuPt Bimetallic Nanoparticles for Antibacterial Application**

    PubMed Central

    Zhao, Yuyun; Ye, Chunjie; Liu, Wenwen; Chen, Rong; Jiang, Xingyu

    2014-01-01

    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. PMID:24828967

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

    PubMed

    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.

  11. Mechanical properties of bimetallic one-dimensional structures

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.).

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

    NASA Astrophysics Data System (ADS)

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

    PubMed

    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.

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

    PubMed

    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.

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

    PubMed

    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.

  17. SERS activity studies of Ag/Au bimetallic films prepared by galvanic replacement.

    PubMed

    Wang, Chaonan; Fang, Jinghuai; Jin, Yonglong

    2012-10-01

    Ag films on Si substrates were fabricated by immersion plating, which served as sacrificial materials for preparation of Ag/Au bimetallic films by galvanic replacement method. SEM images displayed that the sacrificial Ag films presenting island morphology experienced interesting structural evolution process during galvanic replacement reaction, and nano-scaled holes were formed in the resultant bimetallic films. SERS measurements using crystal violet as an analyte showed that SERS intensities of bimetallic films were enhanced significantly compared with that of pure Ag films and related mechanisms were discussed. Immersion plating experiment carried out on Ag films on PEN substrates fabricated by photoinduced reduction method further confirmed that galvanic replacement is an easy method to fabricate Ag/Au bimetallic and a potential approach to improve the SERS performance of Ag films.

  18. Chemistry of Bimetallic Linked Cyclopentadienyl Complexes: Progress Report, 1 December 1986 --30 November 1989

    DOE R&D Accomplishments Database

    Schrock, R. R.

    1989-01-01

    Research continued on the chemistry and preparation of bimetallic cyclopentadienyl complexes containing up to two tungsten or one tungsten and a cobalt, rhodium, or ruthenium. The general method for preparation and analysis of polyenes is also discussed. (CBS)

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

    PubMed

    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.

  20. Facile synthesis of Cu-Pd bimetallic multipods for application in cyclohexane oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Zhuo-Qun; Huang, Jianliu; Zhang, Lan; Sun, Mei; Wang, You-Cheng; Lin, Yue; Zeng, Jie

    2014-10-01

    The synergy between Cu and Pd makes Cu-Pd bimetallic nanocrystals interesting materials for investigation. The scarcity of shapes of Cu-Pd bimetallic nanocrystals motivated us to explore highly branched structures, which may promote a wide range of applications. In this communication, we report a facile synthesis of Cu-Pd bimetallic multipods (19.2 ± 1.2 nm), on branches of which some high-index facets were exposed. Modification of reaction parameters concerning capping agents and reductant led to the formation of other shapes, including sphere-like nanocrystals (SNCs). When loaded onto TiO2, the as-prepared Cu-Pd bimetallic multipods exhibited excellent catalytic activity for the oxidation of cyclohexane by hydrogen peroxide and higher selectivity towards cyclohexanone than monometallic catalysts and SNCs/TiO2.

  1. Fundamental investigations of supported monometallic and bimetallic catalysts by proton magnetic resonance spectroscopy

    SciTech Connect

    Wu, Xi.

    1990-09-21

    Proton magnetic resonance spectroscopy, or nuclear magnetic resonance (NMR) of hydrogen, has been applied to investigate silica-supported Group VIII monometallic and Group VIII-Group IB bimetallic catalysts and alumina- and silica-supported platinum-rhenium bimetallic catalysts. Two adsorbed states of hydrogen, i.e., irreversible and reversible hydrogen, on the surfaces of monometallic Ru, Pt, and Cu particles and bimetallic Ru-Group Ib, Pt-Group Ib, and Pt-Re particles were observed directly via proton NMR. The same amounts of the irreversible hydrogen adsorbed on pure Ru catalysts were measured by both proton NMR and the volumetric technique. The electronic environments on surfaces of monometallic catalysts are sensitive to changes in metal dispersion, state of adsorbed hydrogen, and residual chlorine. Surface compositions for the Ru--Cu and Pt--Cu bimetallic catalysts were determined by NMR of adsorbed hydrogen. 297 refs., 96 figs., 19 tabs.

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

    PubMed

    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 Nanoshells for Metal – Enhanced Fluorescence with Broad Band Fluorophores

    PubMed Central

    Zhang, Jian; Fu, Yi; Mahdavi, Farhad

    2012-01-01

    In this article, we reported the near-field interactions between the Ru(bpy)32+ complexes and plasmon resonances from the bimetallic nanoshells. The metallic nanoshells were fabricated on 20 nm silica spheres as cores by depositing 10 nm monometallic or bimetallic shells. There were approx. 15 Ru(bpy)32+ complexes in the silica core. The metal shells were constituted of silver or/and gold. The bimetallic shells could be generated in homogeneous or heterogeneous geometries. The homogeneous bimetallic shells contained 10 nm silver-gold alloys. The heterogeneous bimetallic shells contained successive 5 nm gold and 5 nm silver shells, or alternatively, 5 nm silver and 5 nm gold shells. Optical properties of metal nanoshells were studied on both the ensemble spectra and single nanoparticle imaging measurements. The heterogeneous bimetallic shells were found to have a large scale of metal-enhanced emission relative to the monometallic or homogeneous bimetallic shells. It is because the heterogeneous bimetallic shells may display split dual plasmon resonances which can interact with the excitation and emission bands of the Ru(bpy)32+ complexes in the silica cores leading to more efficient near-field interactions. The prediction can be demonstrated by the lifetimes. Therefore, it is suggested that both the compositions and geometries of the metal shells can influence the interactions with the fluorophores in the cores. This observation also offers us an opportunity for developing plasmon-based fluorescence metal nanoparticles as novel nanoparticle imaging agents which have high performances in fluorescence cell or tissue imaging. PMID:23230456

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    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.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

  5. Structural evolution of atomically precise thiolated bimetallic [Au(12+n)Cu₃₂(SR)(30+n)]⁴⁻ (n = 0, 2, 4, 6) nanoclusters.

    PubMed

    Yang, Huayan; Wang, Yu; Yan, Juanzhu; Chen, Xi; Zhang, Xin; Häkkinen, Hannu; Zheng, Nanfeng

    2014-05-21

    A series of all-thiol stabilized bimetallic Au-Cu nanoclusters, [Au(12+n)Cu32(SR)(30+n)](4-) (n = 0, 2, 4, 6 and SR = SPhCF3), are successfully synthesized and characterized by X-ray single-crystal analysis and density functional theory (DFT) calculations. Each cluster consists of a Keplerate two-shell Au12@Cu20 core protected by (6 - n) units of Cu2(SR)5 and n units of Cu2Au(SR)6 (n = 0, 2, 4, 6) motifs on its surface. The size and structural evolution of the clusters is atomically controlled by the Au precursors and countercations used in the syntheses. The clusters exhibit similar optical absorption properties that are not dependent on the number of surface Cu2Au(SR)6 units. Although DFT suggests an electronic structure with an 18-electron superatom shell closure, the clusters display different thermal stabilities. [Au(12+n)Cu32(SR)(30+n)](4-) clusters with n = 0 and 2 are more stable than those with n = 4 and 6. Moreover, an oxidation product of the clusters, [Au13Cu12(SR)20](4-), is structurally identified to gain insight into how the clusters are oxidized.

  6. Spectroscopy of Reactive Molecules and Clusters

    NASA Astrophysics Data System (ADS)

    Johnson, Matthew Stanley

    This thesis presents spectroscopic investigations of reactive molecules and clusters. The techniques of laser excited fluorescence, infrared predissociation spectroscopy, and photoelectron spectroscopy were employed to investigate systems relating to fundamental cluster chemistry, ion solvation, and atmospheric ozone depletion. An instrument was developed to investigate van der Waals complexes of refractory elements. A pulsed laser ablation cluster source harnessed the cooling power of a supersonic free jet to condense weakly bound neutral clusters. Laser excited fluorescence was used to characterize the products of the source, which included adducts of aluminum atoms with water molecules, hydrogen, and argon. The species Al(H_2O), AlAr and AlH were identified. The infrared predissociation spectra of positive and negative cluster ions were investigated using a tandem time-of-flight instrument. In this work the photofragment yield spectrum of mass-selected I^-(H _2O) and I^-(H _2O)_2 complexes was measured between 3170 and 3800 cm^{ -1}. The dominant features in the I ^-(H_2O) spectra were assigned as a hydrogen bonded OH stretch and a free OH stretch. Ab initio calculations were used to aid in spectral assignment and for geometrical information concerning I ^-(H_2O). Absorptions in the iodide water dimer cluster are attributed to a symmetric and an antisymmetric bonded OH stretch, and a free OH stretch. Chlorine nitrate is a key reservoir of stratospheric chlorine, and as such its photolysis branching ratio is crucial to partitioning of species involved with stratospheric ozone depletion. The He(I) photoelectron spectrum of chlorine nitrate was measured and assigned in order to understand the photodissociation behavior of chlorine nitrate. The results include the ionization potential of the molecule (10.86 eV), and the assignment of the first ionization peak to a nonbonding chlorine atomic orbital.

  7. Photoelectron imaging and photodissociation of ozonide in O{sub 3}{sup −} ⋅ (O{sub 2}){sub n} (n = 1-4) clusters

    SciTech Connect

    Mann, Jennifer E.; Troyer, Mary E.; Jarrold, Caroline Chick

    2015-03-28

    The photoelectron images of O{sub 3}{sup −} and O{sub 3}{sup −} ⋅ (O{sub 2}){sub n} (n = 1–4) have been measured using 3.49 eV photon energy. The spectra exhibit several processes, including direct photodetachment and photodissociation with photodetachment of O{sup −} photofragments. Several spectra also exhibit autodetachment of vibrationally excited O{sub 2}{sup −} photofragments. Comparison of the bare O{sub 3}{sup −} photoelectron spectra to that of the complexes shows that the O{sub 3}{sup −} core is preserved upon clustering with several O{sub 2} molecules, though subtle changes in the Franck-Condon profile of the ground state photodetachment transition suggest some charge transfer from O{sub 3}{sup −} to the O{sub 2} molecules. The electron affinities of the complexes increase by less than 0.1 eV with each additional O{sub 2} molecule, which is comparable to the corresponding binding energy [K. Hiraoka, Chem. Phys. 125, 439-444 (1988)]. The relative intensity of the photofragment O{sup −} detachment signal to the O{sub 3}{sup −} ⋅ (O{sub 2}){sub n} direct detachment signal increases with cluster size. O{sub 2}{sup −} autodetachment signal is only observed in the O{sub 3}{sup −}, O{sub 3}{sup −} ⋅ (O{sub 2}){sub 3}, and O{sub 3}{sup −} ⋅ (O{sub 2}){sub 4} spectra, suggesting that the energy of the dissociative state also varies with the number of O{sub 2} molecules present in the cluster.

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

    PubMed

    Slater, Thomas J A; Janssen, Arne; Camargo, Pedro H C; Burke, M Grace; Zaluzec, Nestor J; Haigh, Sarah J

    2016-03-01

    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.

  9. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    SciTech Connect

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

    In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

  10. Mapping thermal conductivity using bimetallic atomic force microscopy probes

    NASA Astrophysics Data System (ADS)

    Grover, Ranjan; McCarthy, Brendan; Sarid, Dror; Guven, Ibrahim

    2006-06-01

    We demonstrate a technique to measure local thermal conductivity of materials using an atomic force microscope equipped with a commercial silicon cantilever coated by a thin metal film. This bimaterial cantilever acts as a bimetallic strip that bends when heated by a focused laser beam. The bending is apparent as a topographic distortion, which varies with the amount of heat flowing from the cantilever's tip into the sample. By comparing the surface topographies of the sample, as measured with heated and unheated cantilevers, the local thermal conductivity of the tip-sample contact area can be determined. Experimental results with this system are presented and found to be in good agreement with a finite element model.

  11. A theory of adhesion at a bimetallic interface - Overlap effects.

    NASA Technical Reports Server (NTRS)

    Ferrante, J.; Smith, J. R.

    1973-01-01

    A preliminary calculation of the chemical bonding adhesive interaction between metal surfaces is provided. In this first theory the Hohenberg and Kohn formalism is used to give the bimetallic adhesive binding energy versus separation. The close-packed planes of Al, Mg, and Zn are considered. The effect of simple overlap of the metal-vacuum distributions is determined. The importance of registry between contact surfaces is ascertained. A minimum in the binding energy curve is exhibited for all combinations. The theoretical predictions agree with trends in bond strengths taken from available experimental data. An insight into the mechanisms involved in metallic transfer is given. The relationship between adhesive energies, cohesive energies, and surface energies is discussed.

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

    DOE PAGES

    Slater, Thomas J. A.; Janssen, Arne; Camargo, Pedro H. C.; ...

    2015-10-22

    This paper presents an investigation of the limitations and optimization 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 compensatemore » for variations in the intensity of spectrum images at each sample tilt. Lastly, 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« less

  13. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    PubMed Central

    Guo, Wei; Vlachos, Dionisios G.

    2015-01-01

    Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N−H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design. PMID:26443525

  14. Bulk-Forming Simulation of Bimetallic Watchcase Components

    NASA Astrophysics Data System (ADS)

    Kong, T. F.; Chan, L. C.

    2014-10-01

    This article presents a study of the effects of process parameters in bulk-forming bimetallic watchcase components using finite-element (FE) simulation. This study aimed to determine the suitable forming temperature T and ram speed S for attaining the complete die filling of bimetals. A complicated watchcase component made of 3-mm-thick AISI 316L stainless steel (SS316L) and 6-mm-thick 6063 aluminum alloy (AA6063) was used as the example. The processes were simulated with T of 400°C, 500°C, 600°C, 700°C, 800°C, and 900°C and S of 20 mm/s, 40 mm/s, and 60 mm/s. Although the AA6063 was not heated in the beginning, it flowed faster than the SS316L during the process, and hence, the incomplete die filling was found mainly in the SS316L region. To avoid the incomplete die filling and strengthen the intermetallic bond between two dissimilar metals, the T of 900°C was suggested. The S of 40 mm/s was recommended also because this could save much forming energy and prevent the damage of tools. The experimental verification was carried out under process conditions that were employed in the simulations. An infrared thermal imaging camera and a 300-ton mechanical press were used to monitor the T and testify the bulk-forming operation, respectively. The data acquired from the experiments, on average, agreed strongly with those predicted by the simulations. On the basis of the results in this study, engineers can gain a better understanding of bulk-forming bimetallic components and be able to determine the T and S efficiently for similar processes.

  15. The selective hydrogenation of crotonaldehyde over bimetallic catalysts

    SciTech Connect

    Schoeb, Ann M.

    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.

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    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.

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

    DOE PAGES

    Bedford, Nicholas M.; Showalter, Allison R.; Woehl, Taylor J.; ...

    2016-09-01

    Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when mixing two different metallic species 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 synthesizedmore » 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 were 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 solute tempering molecular dynamic 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. Finally, taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be

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

    SciTech Connect

    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.

    2016-09-01

    Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when mixing two different metallic species 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 were 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 solute tempering molecular dynamic 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. Finally, taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be leveraged

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

    SciTech Connect

    Ong, Yee Pin; Yoon, Tiem Leong; Lim, Thong Leng

    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.

  1. Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry

    SciTech Connect

    Durham, Jessica L.; Poyraz, Altug S.; Takeuchi, Esther S.; Marschilok, Amy C.; Takeuchi, Kenneth J.

    2016-08-26

    Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and mass of the final system. Material multi-functionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cation can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multi-mechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM’O) or phosphorous oxides (MM’PO) where M = Ag and M’ = V or Fe. One discharge process can be described as reduction-displacement where Ag+ is reduced to Ag0 and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in-situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional

  2. Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry

    DOE PAGES

    Durham, Jessica L.; Poyraz, Altug S.; Takeuchi, Esther S.; ...

    2016-08-26

    Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and massmore » of the final system. Material multi-functionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cation can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multi-mechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM’O) or phosphorous oxides (MM’PO) where M = Ag and M’ = V or Fe. One discharge process can be described as reduction-displacement where Ag+ is reduced to Ag0 and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in-situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity

  3. Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry.

    PubMed

    Durham, Jessica L; Poyraz, Altug S; Takeuchi, Esther S; Marschilok, Amy C; Takeuchi, Kenneth J

    2016-09-20

    Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and mass of the final system. Material multifunctionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cations can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multimechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM'O) or phosphorus oxides (MM'PO) where M = Ag and M' = V or Fe. One discharge process can be described as reduction-displacement where Ag(+) is reduced to Ag(0) and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity, determining the

  4. Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry

    SciTech Connect

    Durham, Jessica L.; Poyraz, Altug S.; Takeuchi, Esther S.; Marschilok, Amy C.; Takeuchi, Kenneth J.

    2016-08-26

    Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and mass of the final system. Material multi-functionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cation can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multi-mechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM’O) or phosphorous oxides (MM’PO) where M = Ag and M’ = V or Fe. One discharge process can be described as reduction-displacement where Ag+ is reduced to Ag0 and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in-situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional

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

    PubMed

    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.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Fracture evaluations of fusion line cracks in nuclear pipe bimetallic welds

    SciTech Connect

    Scott, P.; Francini, R.; Rahman, S.; Rosenfield, A.; Wilkowski, G.

    1995-04-01

    In both BWRs and PWRs there are many locations where carbon steel pipe or components are joined to stainless steel pipe or components with a bimetallic weld. The objective of the research described in this report was to assess the accuracy of current fracture analyses for the case of a crack along a carbon steel to austenitic weld fusion line. To achieve the program objective, material property data and data from a large-diameter pipe fracture experiment were developed to assess current analytical methods. The bimetallic welds evaluated in this program were bimetallic welds obtained from a cancelled Combustion Engineering plant. The welds joined sections of the carbon steel cold-leg piping system to stainless steel safe ends that were to be welded to stainless steel pump housings. The major conclusion drawn as a result of these efforts was that the fracture behavior of the bimetallic weld evaluated in this program could be evaluated with reasonable accuracy using the strength and toughness properties of the carbon steel pipe material in conjunction with conventional elastic-plastic fracture mechanics or limit-load analyses. This may not be generally true for all bimetallic welds, as discussed in this report.

  9. Reactivity of Pd/Fe Bimetallic Nanotubes in Dechlorination of Coplanar Polychlorinated Biphenyls

    PubMed Central

    Zahran, Elsayed M.; Bhattacharyya, Dibakar; Bachas, Leonidas G.

    2013-01-01

    A new class of bimetallic materials based on palladium-decorated iron nanotubes is described that demonstrates high reactivity in dechlorination reactions. This high dechlorination efficiency was attributed to the high surface area to volume ratio of the hollow nanotubes structure. Herein, we evaluated the effect of different conditions, such as the nanotube size, and the palladium loading on the efficiency of the dechlorination of PCB 77, a model coplanar polychlorinated biphenyl (PCB), by the Pd/Fe bimetallic nanotubes system. The efficiency of the dechlorination was lowered by decreasing the tube diameter from 200 to 100 nm. In addition, the interior surface as well as the exterior surface of the as-synthesized Pd/Fe bimetallic nanotubes was found to contribute to the high efficiency of the dechlorination of PCB 77. The dechlorination of PCB 77 by Pd/Fe bimetallic nanotubes demonstrated small activation energy indicating diffusion controlled reaction. The as-prepared Pd/Fe bimetallic nanotubes showed extended lifetime activity when used in multiple dechlorination cycles. PMID:23332879

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

    PubMed

    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.

  11. Hydrodechlorination of chlorobenzene over polymer-stabilized palladium-platinum bimetallic colloidal nanocatalysts.

    PubMed

    Liu, Manhong; Wang, Chao; Yu, William W

    2010-11-01

    Poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized Pd, Pt, Pd-Pt nanocatalysts were prepared and characterized by transmission electron microscopy (TEM). Hydrogenation of chlorobenzene was carried out over these colloidal nanocatalysts under ambient conditions. The catalytic properties for the hydrogenation of chlorobenzene depended on the composition of the bimetallic nanocatalysts. The conversion of chlorobenzene over PVP-Pd (83.64%) was higher than that of PVP-Pt (66.67%), which indicated that the activity of Pd was higher than that of Pt. In 10 hrs. the conversions of all the bimetallic nanocatalysts were higher than that of PVP-Pt (66.67%) monometallic nanocatalysts, and the maximum conversion of chlorobenzene (95.34%) was achieved using PVP-Pd/Pt = 1/1 catalytic system, which was much higher than that of the physical mixture of monometallic nanocatalysts (PVP-Pd and PVP-Pt) at the same Pd/Pt ratio as the PVP-Pd/Pt bimetallic nanocatalysts used. The selectivity to benzene and cyclohexane of the bimetallic nanocatalysts (with < or = 40 mol% Pt) was similar to that of PVP-Pd monometallic nanocatalysts, and nearly approximately 100% selectivity to benzene could be obtained, the selectivity to cyclohexane increased slowly with increasing of platinum content in bimetallic nanocatalysts.

  12. Effect of Synthesis Techniques on Crystallization and Optical Properties of Ag-Cu Bimetallic Nanoparticles

    NASA Astrophysics Data System (ADS)

    Xiong, Ziye; Qin, Fen; Huang, Po-Shun; Nettleship, Ian; Lee, Jung-Kun

    2016-04-01

    Silver (Ag)-copper (Cu) bimetallic nanoparticles (NPs) were synthesized by the reduction of silver nitrate and copper (II) acetate monohydrate using ethylene glycol in a microwave (MW) heating system with controlled reaction times ranging from 5 min to 30 min. The molar ratio Ag/Cu was varied from 1:1 to 1:3. The effect of reaction conditions on the bimetallic NPs structures and compositions were characterized by x-ray photoelectron spectroscopy, x-ray diffraction and transmission electron microscopy. The average particle size was approximately 150 nm. The surface plasmon resonance (SPR) of Ag-Cu bimetallic NPs was investigated by monitoring the SPR band peak behavior via UV/Vis spectrophotometry. The resonance peak positions and peak widths varied due to the different structures of the bimetallic NPs created under the synthesis conditions. In the MW heating method, the reduction of Cu was increased and Cu was inhomogeneously deposited over the Ag cores. As the composition of Cu becoming higher in the Ag-Cu bimetallic NPs, the absorption between 400 nm to 600 nm was greatly enhanced.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

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

    2011-12-31

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

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

    SciTech Connect

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

    2011-01-01

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

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

    PubMed

    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.

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

    PubMed

    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-nitrophenol

  18. Sulfentrazone dechlorination by iron-nickel bimetallic nanoparticles.

    PubMed

    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.

  19. Fundamental studies of supported bimetallic catalysts by NMR spectroscopy

    SciTech Connect

    Savargaonkar, Nilesh

    1996-10-17

    Various hydrogenation reactions on transition metals are important commercially whereas certain hydrogenolysis reactions are useful from fundamental point of view. Understanding the hydrogen mobility and kinetics of adsorption-desorption of hydrogen is important in understanding the mechanisms of such reactions involving hydrogen. The kinetics of hydrogen chemisorption was studied by means of selective excitation NMR on silica supported Pt, Rh and Pt-Rh catalysts. The activation energy of hydrogen desorption was found to be lower on silica supported Pt catalysts as compared to Rh and Pt-Rh catalysts. It was found that the rates of hydrogen adsorption and desorption on Pt-Rh catalyst were similar to those on Rh catalyst and much higher as compared to Pt catalyst. The Ru-Ag bimetallic system is much simpler to study than the Pt-Rh system and serves as a model system to characterize more complicated systems such as the K/Ru system. Ag was found to decrease the amounts of adsorbed hydrogen and the hydrogen-to-ruthenium stoichiometry. Ag reduced the populations of states with low and intermediate binding energies of hydrogen on silica supported Ru catalyst. The rates of hydrogen adsorption and desorption were also lower on silica supported Ru-Ag catalyst as compared to Ru catalyst. This report contains introductory information, the literature review, general conclusions, and four appendices. An additional four chapters and one appendix have been processed separately for inclusion on the data base.

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

    PubMed

    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.

  1. Salt flux synthesis of single and bimetallic carbide nanowires

    NASA Astrophysics Data System (ADS)

    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.

  2. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    DOE PAGES

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

    In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-Hmore » bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.« less

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    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-nitrophenol < k2-nitrophenol < k3-nitrophenol. Thermal conductivity is measured as a function of volume fraction and it is observed that the incorporation of the alloy nanoparticles 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.

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

    PubMed

    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.

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

    PubMed Central

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

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    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

    2016-01-01

    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. PMID:27471193

  9. An inorganic capping strategy for the seeded growth of versatile bimetallic nanostructures

    DOE PAGES

    Pei, Yuchen; Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; ...

    2015-09-11

    Metal nanostructures have attracted great attention in various fields due to their tunable properties through precisely tailored sizes, compositions and structures. Using mesoporous silica (mSiO2) as the inorganic capping agent and encapsulated Pt nanoparticles as the seeds, we developed a robust seeded growth method to prepare uniform bimetallic nanoparticles encapsulated in mesoporous silica shells (PtM@mSiO2, M = Pd, Rh, Ni and Cu). Unexpectedly, we found that the inorganic silica shell is able to accommodate an eight-fold volume increase in the metallic core by reducing its thickness. The bimetallic nanoparticles encapsulated in mesoporous silica shells showed enhanced catalytic properties and thermalmore » stabilities compared with those prepared with organic capping agents. As a result, this inorganic capping strategy could find a broad application in the synthesis of versatile bimetallic nanostructures with exceptional structural control and enhanced catalytic properties.« less

  10. An inorganic capping strategy for the seeded growth of versatile bimetallic nanostructures

    SciTech Connect

    Pei, Yuchen; Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; Goh, Tian -Wei; Brashler, Kyle; Gustafson, Jeffrey A.; Huang, Wenyu

    2015-09-11

    Metal nanostructures have attracted great attention in various fields due to their tunable properties through precisely tailored sizes, compositions and structures. Using mesoporous silica (mSiO2) as the inorganic capping agent and encapsulated Pt nanoparticles as the seeds, we developed a robust seeded growth method to prepare uniform bimetallic nanoparticles encapsulated in mesoporous silica shells (PtM@mSiO2, M = Pd, Rh, Ni and Cu). Unexpectedly, we found that the inorganic silica shell is able to accommodate an eight-fold volume increase in the metallic core by reducing its thickness. The bimetallic nanoparticles encapsulated in mesoporous silica shells showed enhanced catalytic properties and thermal stabilities compared with those prepared with organic capping agents. As a result, this inorganic capping strategy could find a broad application in the synthesis of versatile bimetallic nanostructures with exceptional structural control and enhanced catalytic properties.

  11. Scaling-Relation-Based Analysis of Bifunctional Catalysis: The Case for Homogeneous Bimetallic Alloys

    DOE PAGES

    Andersen, Mie; Medford, Andrew J.; Norskov, Jens K.; ...

    2017-04-14

    Here, we present a generic analysis of the implications of energetic scaling relations on the possibilities for bifunctional gains at homogeneous bimetallic alloy catalysts. Such catalysts exhibit a large number of interface sites, where second-order reaction steps can involve intermediates adsorbed at different active sites. Using different types of model reaction schemes, we show that such site-coupling reaction steps can provide bifunctional gains that allow for a bimetallic catalyst composed of two individually poor catalyst materials to approach the activity of the optimal monomaterial catalyst. However, bifunctional gains cannot result in activities higher than the activity peak of the monomaterialmore » volcano curve as long as both sites obey similar scaling relations, as is generally the case for bimetallic catalysts. These scaling-relation-imposed limitations could be overcome by combining different classes of materials such as metals and oxides.« less

  12. EXAFS and XANES structural characterization of bimetallic AuPd vapor derived catalysts

    NASA Astrophysics Data System (ADS)

    Balerna, A.; Evangelisti, C.; Schiavi, E.; Vitulli, G.; Bertinetti, L.; Martra, G.; Mobilio, S.

    2013-04-01

    Using an innovative procedure known as metal vapor synthesis (MVS) to prepare bimetallic catalysts, starting from Au and Pd vapors, [AuPd] co-evaporated and [Au][Pd] separately evaporated bimetallic catalysts were achieved. After being tested, the catalytic activity and selectivity of the [AuPd] catalyst turned out to be higher than the [Au][Pd] ones. Using EXAFS spectroscopy it was shown that, in the [AuPd] samples, small bimetallic AuPd nanoparticles were present, having an Au rich core surrounded by an AuPd alloyed shell while in the [Au][Pd] sample there was the presence of monometallic Au and Pd nanoparticles showing some alloying only in the boundary regions. The EXAFS results were also qualitatively confirmed by the XANES spectra.

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

    SciTech Connect

    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).

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Plasmonic emission enhancement of colloidal quantum dots in the presence of bimetallic nanoparticles

    SciTech Connect

    Sadeghi, S. M.; Hatef, A.; Meunier, M.; Nejat, A.; Campbell, Q.

    2014-04-07

    We studied plasmonic features of bimetallic nanostructures consisting of gold nanoisland cores semi-coated with a chromium layer and explored how they influence emission of CdSe/ZnS quantum dots. We showed that, compared with chromium-covered glass substrates without the gold cores, the bimetallic nanostructures could significantly enhance the emission of the quantum dots. We studied the impact of the excitation intensity and thickness of the chromium layer on this process and utilized numerical means to identify the mechanisms behind it. Our results suggest that when the chromium layer is thin, the enhancement process is the result of the bimetallic plasmonic features of the nanostructures. As the chromium layer becomes thick, the impact of the gold cores is screened and the enhancement mostly happens mostly via the field enhancement of chromium nanoparticles in the absence of significant energy transfer from the quantum dots to these nanoparticles.

  17. General trend for adsorbate-induced segregation of subsurface metal atoms in bimetallic surfaces

    NASA Astrophysics Data System (ADS)

    Menning, Carl A.; Chen, Jingguang G.

    2009-05-01

    It is well known that the unique chemical properties of transition metal alloys depend on the configuration of metal atoms of the bimetallic surfaces. Using density functional theory calculations, the thermodynamic potential for segregation of an admetal from the subsurface to surface configuration is shown to correlate linearly with the difference in occupied d-band center, Δɛd, between these two configurations for a wide range of bimetallic systems. The thermodynamic potential for segregation is also shown to increase with the Pauling electronegativity for several adsorbates, including atomic H, O, C, N, S, and Se. A generalized equation is provided to predict the stable surface configuration for the bimetallic systems with different adsorbates.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. Cancer Clusters

    MedlinePlus

    ... Genetics Services Directory Cancer Prevention Overview Research Cancer Clusters On This Page What is a cancer cluster? ... the number of cancer cases in the suspected cluster Many reported clusters include too few cancer cases ...

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Sonochemical preparation of bimetallic Co/Cu nanoparticles in aqueous solution

    SciTech Connect

    Jia Yaoshun; Niu Helin; Wu Mingzai; Ning Min; Zhu Hongfei; Chen Qianwang . E-mail: cqw@ustc.edu.cn

    2005-09-01

    Co/Cu bimetallic nanocrystallites, with average diameter of 50 nm, were prepared by a sonochemical method in the hydrazine solution of copper chloride and cobalt chloride. Cobalt was face-centered cubic phase when synthesized and remained fcc phase throughout the annealing process. X-ray diffractometer (XRD), transmission electron microscope (TEM), differential scanning calorimetry (DSC), vibrating sample magnetometry (VSM), inductively coupled plasma-atomic emission spectrometer (ICP-AES) measurements were carried out to investigate their structural and magnetic properties. It was found that the magnetic properties of bimetallic nanocrystallites were close to that of the sputtered alloys.

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

    SciTech Connect

    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.

  5. Synthesis and structural characterization of bimetallic iron-nickel carbido cluster complexes.

    PubMed

    Saha, Sumit; Zhu, Lei; Captain, Burjor

    2010-04-05

    In acetonitrile solvent, Fe(5)(CO)(15)(mu(5)-C), 1, reacts with Ni(COD)(2) at room temperature to afford the iron-nickel complex Fe(5)Ni(NCMe)(CO)(15)(mu(6)-C), 3. The acetonitrile ligand in 3 can be replaced by CO and NH(3) to yield Fe(5)Ni(CO)(16)(mu(6)-C), 4, and Fe(5)Ni(NH(3))(CO)(15)(mu(6)-C), 6, respectively. When refluxed in acetonitrile solvent, compound 3 loses a vertex to form the square pyramidal Fe(4)Ni complex Fe(4)Ni(NCMe)(2)(CO)(12)(mu(5)-C), 7. Compound 7 readily converts to Fe(4)Ni(NCMe)(CO)(13)(mu(5)-C), 8, by losing one of its acetonitrile ligands. Addition of acetonitrile to 8 gives compound 7. When heated to 110 degrees C under an atmosphere of CO, both compounds 7 and 8 furnish the octahedral Fe(4)Ni(2) complex Fe(4)Ni(2)(CO)(15)(mu(6)-C), 9. All six compounds were structurally characterized by single-crystal X-ray diffraction analyses.

  6. Development of clad boiler tubes extruded from bimetallic centrifugal castings

    NASA Astrophysics Data System (ADS)

    Sponseller, D. L.; Timmons, G. A.; Bakker, W. T.

    1998-04-01

    Wrought tubes of T-11 steel, externally clad with SS310, have been produced by a new method (U.S. Patent 5,558,150). The alloys were united directly from the molten state by centrifugal casting. In the optimum process, temperatures were controlled to prevent meltback of the SS310 outer layer by the higher melting T-11 stream. Hollow extrusion billets were prepared from the heavy-walled cast bimetallic tubes and successfully hot extruded (at a ratio of 13.4) to 84-mm (3.3 in.) OD X 64-mm (2.5-in.) ID tubes, and (at a ratio of 37.6) to 51-mm (2-in.) OD X 38-mm (1.5-in.) ID tubes. In all, 10 castings were produced, and 12 billets were extruded to tubes. For the most part, thicknesses of the cladding and of the tube wall are rather uniform around the circumference and from end to end of the tubes. Hardness and tensile properties of annealed 51-mm (2-in.) tubes are uniform from end to end of a tube, and between tubes, and readily conform to ASTM A 213; tubes satisfy the flattening and flaring requirements of ASTM A 450. The cladding is metallurgically bonded to the base metal, as revealed by metallography, and by two tests developed for this study: a bond shear strength test and a twist test. In the latter test, rings 3.1 mm (0.125 in.) in thickness are slotted and severely twisted with a special tool. In tubes made by the optimum process, minute fissures that form adjacent to some of the pressure points during twist testing occupy just 3 % of the bond-line length. Cost estimates for commercial production of 51-mm (2-in.) tubes via the centrifugal casting route suggest that such tubes should be considerably less expensive than conventionally clad tubes (extruded from composite billets assembled from heavy-walled wrought tubes).

  7. Development of clad boiler tubes extruded from bimetallic centrifugal castings

    SciTech Connect

    Sponseller, D.L.; Timmons, G.A.; Bakker, W.T.

    1995-12-31

    Wrought tubes of T-11 steel, externally clad with SS310, have been produced by a new method. The alloys were united directly from the molten state by centrifugal casting. In the optimum process, temperatures are controlled to prevent meltback of the SS310 outer layer by the higher-melting T-11 stream. Hollow extrusion billets were prepared from the heavy-walled cast bimetallic tubes and successfully hot extruded (at a ratio of 13.4) to 3.3-inch OD x 2.5-inch ID tubes, and (at a ratio of 37.6) to 2-inch OD x 1.5-inch ID tubes. In all, ten castings were produced, and 12 billets were extruded to tubes. For the most part, thicknesses of the cladding and tube wall are rather uniform around the circumference and from end to end of the tubes. Hardness and tensile Properties of annealed 2-inch tubes are uniform from end to 6nd of a tube, and between tubes, and readily conform to ASTM A 213; tubes satisfy the flattening and flaring requirements of ASTM A 450. The cladding is metallurgically bonded to the base metal, as revealed by metallography, and by two tests developed for this study: a bond hear-strength test and a twist test. In the latter test, rings 0.125 inch in thickness are slotted and severely twisted with a special tool. In tubes made by the optimum process, minute fissures that form adjacent to some of the pressure points during twist testing just 2.7 percent of the bond-line length. Cost estimates OCCUPY for commercial production of 2-inch tubes via the centrifugal casting route suggest that such tubes should be considerably less expensive than conventionally clad tubes (extruded from composite billets assembled from heavy-walled wrought tubes).

  8. Metastability and structural polymorphism in noble metals: the role of composition and metal atom coordination in mono- and bimetallic nanoclusters.

    PubMed

    Sanchez, Sergio I; Small, Matthew W; Bozin, Emil S; Wen, Jian-Guo; Zuo, Jian-Min; Nuzzo, Ralph G

    2013-02-26

    This study examines structural variations found in the atomic ordering of different transition metal nanoparticles synthesized via a common, kinetically controlled protocol: reduction of an aqueous solution of metal precursor salt(s) with NaBH₄ at 273 K in the presence of a capping polymer ligand. These noble metal nanoparticles were characterized at the atomic scale using spherical aberration-corrected scanning transmission electron microscopy (C(s)-STEM). It was found for monometallic samples that the third row, face-centered-cubic (fcc), transition metal [(3M)-Ir, Pt, and Au] particles exhibited more coherently ordered geometries than their second row, fcc, transition metal [(2M)-Rh, Pd, and Ag] analogues. The former exhibit growth habits favoring crystalline phases with specific facet structures while the latter samples are dominated by more disordered atomic arrangements that include complex systems of facets and twinning. Atomic pair distribution function (PDF) measurements further confirmed these observations, establishing that the 3M clusters exhibit longer ranged ordering than their 2M counterparts. The assembly of intracolumn bimetallic nanoparticles (Au-Ag, Pt-Pd, and Ir-Rh) using the same experimental conditions showed a strong tendency for the 3M atoms to template long-ranged, crystalline growth of 2M metal atoms extending up to over 8 nm beyond the 3M core.

  9. Ag-Au bimetallic nanoclusters formed from a homogeneous gas phase: a new thermodynamic expression confirmed by molecular dynamics simulation.

    PubMed

    Akbarzadeh, H; Shamkhali, A N; Mehrjouei, E

    2017-02-01

    In this work, two probabilistic and thermodynamic limits for formation of a bimetallic nanocluster from a homogeneous gas phase were obtained in order to investigate the related phenomena using molecular dynamics simulation. Therefore, by application of some simple assumptions from thermodynamics and statistical mechanics, a new expression for composition of the nanocluster was derived which depends only on the initial conditions of the system and one adjustable parameter. This expression can be easily fitted to the results of molecular dynamics and can be used as a measure of the thermodynamic contribution in the cluster formation process. Then, molecular dynamics simulations were performed for several systems containing the same total number of metallic atoms and different concentrations of Ag and Au atoms. The results of this study exhibited that depending on different initial compositions of Ag and Au types, fcc and icosahedral structures are formed. Moreover, increase of the initial Ag concentration leads to products whose compositions are more controlled by probability limits. However, longer simulation times indicated that creation of more thermodynamically favoured nanoclusters depends on the formation of more probable ones in the early stages of the simulation.

  10. Tetranuclear Zn/4f coordination clusters as highly efficient catalysts for Friedel-Crafts alkylation.

    PubMed

    Griffiths, Kieran; Kumar, Prashant; Akien, Geoffrey R; Chilton, Nicholas F; Abdul-Sada, Alaa; Tizzard, Graham J; Coles, Simon J; Kostakis, George E

    2016-06-14

    A series of custom-designed, high yield, isoskeletal tetranuclear Zn/4f coordination clusters showing high efficiency as catalysts with low catalytic loadings in Friedel-Crafts alkylation are described for the first time. The possibility of altering the 4f centers in these catalysts without altering the core topology allows us to further confirm their stability via EPR and NMR, as well to gain insights into the plausible reaction mechanism, showcasing the usefulness of these bimetallic systems as catalysts.

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

    SciTech Connect

    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].

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

    PubMed

    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.

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

    PubMed Central

    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

  14. Green synthesis of Fe0 and bimetallic Fe0 for oxidative catalysis and reduction applications

    EPA Science Inventory

    A single-step green approach to the synthesis of nanoscale zero valent iron (nZVI) and nanoscale bimetallic (Fe0/Pd) particles using tea (Camellia sinensis) polyphenols is described. The expedient reaction between polyphenols and ferric chloride (FeCl3) occurs within a minute at ...

  15. Density and Shape Effects in the Acoustic Propulsion of Bimetallic Nanorod Motors.

    PubMed

    Ahmed, Suzanne; Wang, Wei; Bai, Lanjun; Gentekos, Dillon T; Hoyos, Mauricio; Mallouk, Thomas E

    2016-04-26

    Bimetallic nanorods are propelled without chemical fuels in megahertz (MHz) acoustic fields, and exhibit similar behaviors to single-metal rods, including autonomous axial propulsion and organization into spinning chains. Shape asymmetry determines the direction of axial movement of bimetallic rods when there is a small difference in density between the two metals. Movement toward the concave end of these rods is inconsistent with a scattering mechanism that we proposed earlier for acoustic propulsion, but is consistent with an acoustic streaming model developed more recently by Nadal and Lauga ( Phys. Fluids 2014 , 26 , 082001 ). Longer rods were slower at constant power, and their speed was proportional to the square of the power density, in agreement with the acoustic streaming model. The streaming model was further supported by a correlation between the disassembly of spinning chains of rods and a sharp decrease in the axial speed of autonomously moving motors within the levitation plane of the cylindrical acoustic cell. However, with bimetallic rods containing metals of different densities, a consistent polarity of motion was observed with the lighter metal end leading. Speed comparisons between single-metal rods of different densities showed that those of lower density are propelled faster. So far, these density effects are not explained in the streaming model. The directionality of bimetallic rods in acoustic fields is intriguing and offers some new possibilities for designing motors in which shape, material, and chemical asymmetry might be combined for enhanced functionality.

  16. Plasmon-induced broadband fluorescence enhancement on Al-Ag bimetallic substrates

    NASA Astrophysics Data System (ADS)

    Hao, Qi; Du, Deyang; Wang, Chenxi; Li, Wan; Huang, Hao; Li, Jiaqi; Qiu, Teng; Chu, Paul K.

    2014-08-01

    Surface enhanced fluorescence (SEF) utilizes the local electromagnetic environment to enhance fluorescence from the analyte on the surface of a solid substrate with nanostructures. While the detection sensitivity of SEF is improved with the development of nano-techniques, detection of multiple analytes by SEF is still a challenge due to the compromise between the high enhancing efficiency and broad response bandwidth. In this article, a high-efficiency SEF substrate with broad response bandwidth is obtained by embedding silver in an aluminum film to produce additional bonding and anti-bonding hybridized states. The bimetallic film is fabricated by ion implantation and the ion energy and fluence are tailored to control subsurface location of the fabricated bimetallic nanostructures. The process circumvents the inherent limit of aluminum materials and extends the plasmon band of aluminum from deep UV to visible range. Fluorescence from different dyes excited by 310 nm to 555 nm is enhanced by up to 11 folds on the single bimetallic film and the result is theoretically confirmed by finite-difference time-domain simulations. This work demonstrates that bimetallic film can be used for optical detection of multiple analytes.

  17. Green synthesis of Fe0 and bimetallic Fe0 for oxidative catalysis and reduction applications

    EPA Science Inventory

    A single-step green approach to the synthesis of nanoscale zero valent iron (nZVI) and nanoscale bimetallic (Fe0/Pd) particles using tea (Camellia sinensis) polyphenols is described. The expedient reaction between polyphenols and ferric chloride (FeCl3) occurs within a minute at ...

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

    EPA Science Inventory

    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 ...

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

    PubMed

    Pozun, Zachary D; Rodenbusch, Stacia E; Keller, Emily; Tran, Kelly; Tang, Wenjie; Stevenson, Keith J; Henkelman, Graeme

    2013-04-18

    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.

  20. Non-precious bimetallic catalysts for selective dehydrogenation of an organic chemical hydride system.

    PubMed

    Al-ShaikhAli, Anaam H; Jedidi, Abdesslem; Cavallo, Luigi; Takanabe, Kazuhiro

    2015-08-21

    Methylcyclohexane (MCH)-toluene (TOL) chemical hydride cycles as hydrogen carrier systems are successful with the selective dehydrogenation 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.

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

    PubMed

    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. Borylation of propargylic substrates by bimetallic catalysis. Synthesis of allenyl, propargylic, and butadienyl Bpin derivatives.

    PubMed

    Zhao, Tony S N; Yang, Yuzhu; Lessing, Timo; Szabó, Kálmán J

    2014-05-28

    Bimetallic Pd/Cu and Pd/Ag catalytic systems were used for borylation of propargylic alcohol derivatives. The substrate scope includes even terminal alkynes. The reactions proceed stererospecifically with formal SN2' pathways to give allenyl boronates. Opening of propargyl epoxides leads to 1,2-diborylated butadienes probably via en allenylboronate intermediate.

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

    EPA Science Inventory

    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 ...

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

    NASA Astrophysics Data System (ADS)

    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.

  5. The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

    SciTech Connect

    Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; Stach, Eric A.; Senanayake, Sanjaya D.; Chen, Donna A.; Monnier, John R.; Weidner, John W.

    2016-02-23

    Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratio of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.

  6. The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

    DOE PAGES

    Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; ...

    2016-02-23

    Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratiomore » of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.« less

  7. Modeling of coalescence, agglomeration, and phase segregation in microgravity processing of bimetallic composite materials

    NASA Technical Reports Server (NTRS)

    Davis, Robert H.

    1992-01-01

    The overall objective of this research is to develop models to predict drop-size-distribution evolutions due to droplet collisions and coalescence during processing within the miscibility gap of bimetallic liquid-phase-miscibility-gap materials. The individual and collective action of gravitational and nongravitational mechanisms on the relative motion and coalescence of drops are considered.

  8. A tale of two forces: simultaneous chemical and acoustic propulsion of bimetallic micromotors.

    PubMed

    Wang, Wei; Duan, Wentao; Zhang, Zexin; Sun, Mei; Sen, Ayusman; Mallouk, Thomas E

    2015-01-21

    Bimetallic gold-ruthenium microrods are propelled in opposite directions in water by ultrasound and by catalytic decomposition of hydrogen peroxide. This property was used to effect reversible swarming, to stall and reverse autonomous axial propulsion, and to study the chemically powered movement of acoustically levitated microrods.

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

    PubMed

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

    2014-10-21

    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.

  10. Confinement effects on the shape and composition of bimetallic nano-objects in carbon nanotubes.

    PubMed

    Li, X; Hungria, T; Garcia Marcelot, C; Axet, M R; Fazzini, P-F; Tan, R P; Serp, P; Soulantica, K

    2016-02-07

    CoPt and FePt nanostructures have been efficiently confined in carbon nanotubes (CNTs). A marked confinement effect has been evidenced, both on bimetallic nano-object shape and composition. In large diameter CNTs small Co- and Fe-rich nanoparticles are formed, while in small diameter CNTs Pt-rich nanowires are selectively produced.

  11. Chemistry of bimetallic linked cyclopentadienyl complexes: Progress report, 1 December 1986--30 November 1989

    SciTech Connect

    Schrock, R.R.

    1986-12-01

    Research continued on the chemistry and preparation of bimetallic cyclopentadienyl complexes containing up to two tungsten or one tungsten and a cobalt, rhodium, or ruthenium. The general method for preparation and analysis of polyenes is also discussed. 7 figs., 2 tabs. (CBS)

  12. Effects of Metal Blending in Random Bimetallic Single-Chain Magnets: Synergetic, Antagonistic, or Innocent.

    PubMed

    Wang, Yan-Qin; Yue, Qi; Gao, En-Qing

    2017-01-18

    A family of isomorphous three-dimensional metal-organic frameworks based on bimetallic (FeCo, FeNi, and CoNi) chains with random metal sites have been prepared and magnetically characterized. The solid-solution-type bimetallic materials inherit intrachain ferromagnetic interactions and single-chain-magnet (SCM) behaviors from the homometallic parent materials. Interestingly, different composition dependence of magnetic behaviors has been found. The Fe(II)1-x Ni(II)x series (0≤x≤1) show an innocent composition dependence, where the blocking temperature of slow relaxation decreases monotonically as Fe(II) is replaced by less anisotropic Ni(II) . The Fe(II)1-x Co(II)x series show an unexpected antagonistic blending effect on slow relaxation: blending Fe(II) and Co(II) tends to depress the spin dynamics, and the bimetallic materials with intermediate composition show significantly lower blocking temperature than both Fe(II) and Co(II) materials. This is quite the opposite of what happens in the Co1-x Nix series, where Co(II) and Ni(II) seem to have a synergetic effect so that slow relaxation in bimetallic systems can be promoted to higher temperature than both Co(II) and Ni(II) materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Photoluminescent AuCu bimetallic nanoclusters as pH sensors and catalysts.

    PubMed

    Chen, Po-Cheng; Ma, Jia-Ying; Chen, Li-Yi; Lin, Guan-Lin; Shih, Chung-Chien; Lin, Tai-Yuan; Chang, Huan-Tsung

    2014-04-07

    A facile and one-pot approach to the preparation of gold (Au) and copper (Cu) bimetallic nanoclusters (NCs) is unveiled. AuCu NCs reveal features of orange photoluminescence (PL), reversible pH-dependent PL properties, and efficient catalytic activity for degradation of methylene blue (MB).

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

    SciTech Connect

    Bhatia, Sandeep

    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.

  15. Recent progress in the structure control of Pd–Ru bimetallic nanomaterials

    PubMed Central

    Wu, Dongshuang; Kusada, Kohei; Kitagawa, Hiroshi

    2016-01-01

    Abstract Pd and Ru are two key elements of the platinum-group metals that are invaluable to areas such as catalysis and energy storage/transfer. To maximize the potential of the Pd and Ru elements, significant effort has been devoted to synthesizing Pd–Ru bimetallic materials. However, most of the reports dealing with this subject describe phase-separated structures such as near-surface alloys and physical mixtures of monometallic nanoparticles (NPs). Pd–Ru alloys with homogenous structure and arbitrary metallic ratio are highly desired for basic scientific research and commercial material design. In the past several years, with the development of nanoscience, Pd–Ru bimetallic alloys with different architectures including heterostructure, core-shell structure and solid-solution alloy were successfully synthesized. In particular, we have now reached the stage of being able to obtain Pd–Ru solid-solution alloy NPs over the whole composition range. These Pd–Ru bimetallic alloys are better catalysts than their parent metal NPs in many catalytic reactions, because the electronic structures of Pd and Ru are modified by alloying. In this review, we describe the recent development in the structure control of Pd–Ru bimetallic nanomaterials. Aiming for a better understanding of the synthesis strategies, some fundamental details including fabrication methods and formation mechanisms are discussed. We stress that the modification of electronic structure, originating from different nanoscale geometry and chemical composition, profoundly affects material properties. Finally, we discuss open issues in this field. PMID:27877905

  16. Exceptional methanol electro-oxidation activity by bimetallic concave and dendritic Pt-Cu nanocrystals catalysts

    NASA Astrophysics Data System (ADS)

    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.

  17. ENHANCED CORRISION-BASED PD/MG BIMETALLIC SYSTEMS FOR DECHLORINATION OF PCBS

    EPA Science Inventory

    Polychlorinated biphenyls (PCBs) are toxic pollutants notorious for their aquatic and sedimentary prevalence and recalcitrant nature. Bimetallic systems like Pd/Fe have been widely studied for degrading them. Mg, with oxidation potential higher than Fe, has been reported to dechl...

  18. PD/MG BIMETALLIC CORROSION SYSTEMS FOR DECHLORINATION OF PCB CONTAMINATED MATRICES

    EPA Science Inventory

    Polychlorinated biphenyls (PCBs), a family of 209 compounds manufactured till mid70's, are toxic pollutants that persist in the environment. Enhanced corrosion of an active metal combined with catalytic hydrogenation properties of Pd in bimetallic cells can effectively reduce PCB...

  19. Velocity map imaging study of BrCl photodissociation at 467 nm: determination of all odd-rank (K = 1 and 3) anisotropy parameters for the Cl(2P(3/2)0) photofragments.

    PubMed

    Smolin, Andrey G; Vasyutinskii, Oleg S; Vieuxmaire, Olivier P J; Ashfold, Michael N R; Balint-Kurti, Gabriel G; Orr-Ewing, Andrew J

    2006-03-07

    Resonance-enhanced multiphoton ionization and velocity map imaging of the Cl(2P(3/2)0) fragments of BrCl photolysis at 467.16 nm have been used to obtain a complete set of orientation parameters (with ranks K = 1 and 3) describing the polarization of the electronic angular momentum. The experiments employ two geometries distinguished only by the circular or linear polarization of the photolysis laser beam. Normalized difference images constructed from the data accumulated using a right or left circularly polarized probe-laser beam, counterpropagating with the photolysis laser, were fitted to basis images corresponding to contributions from various odd-rank anisotropy parameters. Expressions are given for the difference images in terms of the K = 1 and 3 anisotropy parameters, which describe coherent and incoherent parallel and perpendicular excitation and dissociation mechanisms. The nonzero values of the anisotropy parameters are indicative of nonadiabatic dissociation dynamics, with likely contributions from flux on the A 3Pi1,B 3Pi(0+),C 1Pi1, and X 1sigma+(0+) states as well as one further omega = 1 state, all of which correlate adiabatically to Cl(2P(3/2)0) + Br(2P(3/2)0) photofragments. The magnitudes of the parameters depend both on the amplitudes of dissociative flux in these states, and also on the phases accumulated by the nuclear wave functions for different dissociation pathways.

  20. Real-time detection of S(1D2) photofragments produced from the 1B2(1Σu+) state of CS2 by vacuum ultraviolet photoelectron imaging using 133 nm probe pulses

    NASA Astrophysics Data System (ADS)

    Horio, Takuya; Spesyvtsev, Roman; Furumido, Yu; Suzuki, Toshinori

    2017-07-01

    Ultrafast photodissociation dynamics from the 1B2(1Σu+) state of CS2 are studied by time-resolved photoelectron imaging using the fourth (4ω, 198 nm) and sixth (6ω, 133 nm) harmonics of a femtosecond Ti:sapphire laser. The 1B2 state of CS2 was prepared with the 4ω pulses, and subsequent dynamics were probed using the 6ω vacuum ultraviolet (VUV) pulses. The VUV pulses enabled real-time detection of S(1D2) photofragments, produced via CS2*(1B2(1Σu+)) → CS(X 1Σ+) + S(1D2). The photoionization signal of dissociating CS2*(1B2(1Σu+)) molecules starts to decrease at about 100 fs, while the S(1D2) fragments appear with a finite (ca. 400 fs) delay time after the pump pulse. Also discussed is the configuration interaction of the 1B2(1Σu+) state based on relative photoionization cross-sections to different cationic states.

  1. Two-photon state selection and angular momentum polarization probed by velocity map imaging: Application to H atom photofragment angular distributions from the photodissociation of two-photon state selected HCl and HBr

    SciTech Connect

    Manzhos, Sergei; Romanescu, Constantin; Loock, Hans-Peter; Underwood, Jonathan G.

    2004-12-15

    A formalism for calculating the angular momentum polarization of an atom or a molecule following two-photon excitation of a J-selected state is presented. This formalism is used to interpret the H atom photofragment angular distributions from single-photon dissociation of two-photon rovibronically state selected HCl and HBr prepared via a Q-branch transition. By comparison of the angular distributions measured using the velocity map imaging technique with the theoretical model it is shown that single-photon dissociation of two-photon prepared states can be used for pathway identification, allowing for the identification of the virtual state symmetry in the two-photon absorption and/or the symmetry of the dissociative state. It is also shown that under conditions of excitation with circularly polarized light, or for excitation via non-Q-branch transitions with linearly polarized light the angular momentum polarization is independent of the dynamics of the two-photon transition and analytically computable.

  2. Two-photon state selection and angular momentum polarization probed by velocity map imaging: application to H atom photofragment angular distributions from the photodissociation of two-photon state selected HCl and HBr.

    PubMed

    Manzhos, Sergei; Romanescu, Constantin; Loock, Hans-Peter; Underwood, Jonathan G

    2004-12-15

    A formalism for calculating the angular momentum polarization of an atom or a molecule following two-photon excitation of a J-selected state is presented. This formalism is used to interpret the H atom photofragment angular distributions from single-photon dissociation of two-photon rovibronically state selected HCl and HBr prepared via a Q-branch transition. By comparison of the angular distributions measured using the velocity map imaging technique with the theoretical model it is shown that single-photon dissociation of two-photon prepared states can be used for pathway identification, allowing for the identification of the virtual state symmetry in the two-photon absorption and/or the symmetry of the dissociative state. It is also shown that under conditions of excitation with circularly polarized light, or for excitation via non-Q-branch transitions with linearly polarized light the angular momentum polarization is independent of the dynamics of the two-photon transition and analytically computable.

  3. 2012 MOLECULAR AND IONIC CLUSTERS GORDON RESEARCH CONFERENCE, JANUARY 29 - FEBRUARY 3, 2012

    SciTech Connect

    Anne McCoy

    2012-02-03

    The Gordon Research Conference on 'Molecular and Ionic Clusters' focuses on clusters, which are the initial molecular species found in gases when condensation begins to occur. Condensation can take place solely from molecules interacting with each other, mostly at low temperatures, or when molecules condense around charged particles (electrons, protons, metal cations, molecular ions), producing ion molecule clusters. These clusters provide models for solvation, allow a pristine look at geometric as well as electronic structures of molecular complexes or matter in general, their interaction with radiation, their reactivity, their thermodynamic properties and, in particular, the related dynamics. This conference focuses on new ways to make clusters composed of different kinds of molecules, new experimental techniques to investigate the properties of the clusters and new theoretical methods with which to calculate the structures, dynamical motions and energetics of the clusters. Some of the main experimental methods employed include molecular beams, mass spectrometry, laser spectroscopy (from infrared to XUV; in the frequency as well as the time domain) and photoelectron spectroscopy. Techniques include laser absorption spectroscopy, laser induced fluorescence, resonance enhanced photoionization, mass-selected photodissociation, photofragment imaging, ZEKE photoelectron spectroscopy, etc. From the theoretical side, this conference highlights work on potential surfaces and measurable properties of the clusters. The close ties between experiment, theory and computation have been a hallmark of the Gordon Research Conference on Molecular and Ionic Clusters. In the 2012 meeting, we plan to have sessions that will focus on topics including: (1) The use of cluster studies to probe fundamental phenomena; (2) Finite size effects on structure and thermodynamics; (3) Intermolecular forces and cooperative effects; (4) Molecular clusters as models for solvation; and (5) Studies of

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

    PubMed

    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.

  5. The adsorption and desorption of hydrogen and carbon monoxide on bimetallic RePt(111) surfaces

    NASA Astrophysics Data System (ADS)

    Godbey, David J.; Somorjai, G. A.

    1988-10-01

    Bimetallic surfaces of rhenium on Pt(111) were prepared by vapor depositing rhenium on Pt(111). The adsorption and desorption behavior of CO and H 2 on bimetallic PtRe surfaces were studied using temperature programmed desorption, and compared to the behavior of CO and H 2 on the monometallic Pt(111) and Re(0001) counterparts. Depositing rhenium on a Pt(111) surface decreased the activation energy of desorption of hydrogen, and a surface composed of 0.37 monolayers of rhenium on Pt(111) showed an activation energy of hydrogen desorption that was 2.5 {kcal}/{mol} less than the 19 {kcal}/{mol} displayed by the monometallic Pt(111) surface. In contrast, the activation energy of desorption of CO from bimetallic surfaces depended very little on the bimetallic surface composition, and a value of 27 {kcal}/{mol} was observed for low CO coverages. At saturation exposures of both H 2 and CO, maximum adsorption capacities were obtained for bimetallic surfaces. A surface composed of 0.2 monolayers of rhenium on Pt(111) adsorbed 20% more hydrogen than did Pt(111) alone, while a surface composed of 0.3 monolayers of rhenium on Pt(111) adsorbed 40% more CO than did Pt(111) alone. The results obtained show that surfaces exposing both rhenium and platinum atoms show adsorption/desorption behavior towards hydrogen and CO that is different than the behavior shown by either monometallic platinum or rhenium surfaces. Since the chemisorption behavior cannot be explained as a simple combination of the two metallic components of the surface, it is concluded that an electronic interaction between the two metals at the platinum-rhenium interface modifies the bonding of adsorbates at the mixed metal sites.

  6. Cluster headache

    MedlinePlus

    Histamine headache; Headache - histamine; Migrainous neuralgia; Headache - cluster; Horton's headache; Vascular headache - cluster ... Doctors do not know exactly what causes cluster headaches. They ... (chemical in the body released during an allergic response) or ...

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

    PubMed

    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.

  8. Effect of calcination temperature on Mg-Al bimetallic oxides as sorbents for the removal of F(-) in aqueous solutions.

    PubMed

    Moriyama, Sayo; Sasaki, Keiko; Hirajima, Tsuyoshi

    2014-01-01

    Bimetallic oxides were synthesized from hydrotalcite using increasing calcination temperatures (873, 1073, 1273 K). These bimetallic oxides were fully characterized and the sorption density of F(-) was investigated. X-ray diffraction patterns for the produced bimetallic oxides showed that MgO was the primary phase within the range of investigated calcination temperatures, but MgO crystallinity increased with calcination temperature and an additional MgAl2O4 phase was formed. In the process of F(-) sorption, the bimetallic oxides were primarily transformed into hydrotalcite with intercalation of F(-). The Higher calcination temperature increased the MgAl2O4 phase, which did not contribute to the immobilization of F(-). These findings show that optimizing the calcination temperature can be used to maximize the sorption density of this material for F(-) removal. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

    PubMed

    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 <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. 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

  10. Development of clad boiler tubes extruded from bimetallic centrifugal castings

    SciTech Connect

    Sponseller, D.L.; Bakker, W.T.; Timmons, G.A.

    1998-04-01

    Wrought tubes of T-11 steel, externally clad with SS310, have been produced by a new method. The alloys were united directly from the molten state by centrifugal casting. In the optimum process, temperatures were controlled to prevent meltback of the SS310 outer layer by the higher melting T-11 stream. Hollow extrusion billets were prepared from the heavy-walled cast bimetallic tubes and successfully hot extruded to 84-mm OD x 64-mm ID tubes, and to 51-mm OD x 38-mm ID tubes. For the most part, thicknesses of the cladding and of the tube wall are rather uniform around the circumference and from end to end of the tubes. Hardness and tensile properties of annealed 51-mm tubes are uniform from end to end of a tube, and between tubes, and readily conform to ASTM A 213; tubes satisfy the flattening and flaring requirements of ASTM A 450. The cladding is metallurgically bonded to be base metal, as revealed by metallography, and by two tests developed for this study: a bond shear strength test and a twist test. In the latter test, rings 3.1 mm in thickness are slotted and severely twisted with a special tool. In tubes made by the optimum process, minute fissures that form adjacent to some of the pressure points during twist testing occupy just 3% of the bond-line length. Cost estimates for commercial production of 51-mm tubes via the centrifugal casting route suggest that such tubes should be considerably less expensive than conventionally clad tubes (extruded from composite billets assembled from heavy-walled wrought tubes). Such tubes should be attractive for the following applications in utility boilers: high-corrosion areas of existing coal-fired boilers, in both steam-generating tubes and superheaters; water walls, screen tubes, and superheater tubes of municipal waste-incineration boilers; future ultra super-critical boilers operating a higher temperatures and pressures; and steam-generating tubes of Syngas coolers of integrated coal gasification power plants.

  11. Thermal decomposition of mono- and bimetallic magnesium amidoborane complexes.

    PubMed

    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

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

    PubMed Central

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

    2016-01-01

    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. 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. Conclusion 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

  13. CLUSTER CHEMISTRY

    SciTech Connect

    Muetterties, Earl L.

    1980-05-01

    Metal cluster chemistry is one of the most rapidly developing areas of inorganic and organometallic chemistry. Prior to 1960 only a few metal clusters were well characterized. However, shortly after the early development of boron cluster chemistry, the field of metal cluster chemistry began to grow at a very rapid rate and a structural and a qualitative theoretical understanding of clusters came quickly. Analyzed here is the chemistry and the general significance of clusters with particular emphasis on the cluster research within my group. The importance of coordinately unsaturated, very reactive metal clusters is the major subject of discussion.

  14. Ligand-protected gold clusters: the structure, synthesis and applications

    NASA Astrophysics Data System (ADS)

    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.

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

    DOE PAGES

    Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; ...

    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 scanningmore » 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. As a result, 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.« less

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

    SciTech Connect

    Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; Anjum, Dalaver H.; Kanoun, Mohammed B.; Scaranto, Jessica; Hedhili, Mohamed N.; Khalid, Syed; Laveille, Paco V.; D'Souza, Lawrence; Clo, Alain; Basset, Jean -Marie

    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. As a result, 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.

  17. The chemical properties of bimetallic surfaces: Importance of ensemble and electronic effects in the adsorption of sulfur and SO 2

    NASA Astrophysics Data System (ADS)

    Rodriguez, José A.

    The understanding of the interaction of sulfur with bimetallic surfaces is a critical issue for preventing the deactivation of hydrocarbon reforming catalysts and for the design of better hydrodesulfurization catalysts. The alloying or combination of two metals can lead to materials with special chemical properties due to an interplay of “ensemble” and “electronic” effects. In recent years, several new interesting phenomena have been discovered when studying the interaction of sulfur with bimetallic surfaces using the modern techniques of surface science. Very small amounts of sulfur are able to induce dramatic changes in the morphology of bimetallic surfaces that combine noble metals (Cu, Ag, Au) and transition metals. This phenomenon can lead to big modifications in the activity and selectivity of bimetallic catalysts used for hydrocarbon reforming. In many cases, bimetallic bonding produces a significant redistribution of charge around the bonded metals. The electronic perturbations associated with the formation of a heteronuclear metal-metal bond can affect the reactivity of the bonded metals toward sulfur. This can be a very important issue to consider when trying to minimize the negative effects of sulfur poisoning (Sn/Pt versus Ag/Pt and Cu/Pt catalysts) or when trying to improve the performance of desulfurization catalysts (Co/Mo and Ni/Mo systems). Clearly much more work is necessary in this area, but new concepts are emerging that can be useful for designing more efficient bimetallic catalysts.

  18. Bimetallic gold-silver nanoplate array as a highly active SERS substrate for detection of streptavidin/biotin assemblies.

    PubMed

    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. Copyright © 2013. Published by Elsevier B.V.

  19. Surface plasmon resonance sensing of a biomarker of Alzheimer disease in an intensity measurement mode with a bimetallic chip

    NASA Astrophysics Data System (ADS)

    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.

  20. Controlled Surface Segregation Leads to Efficient Coke-Resistant Nickel/Platinum Bimetallic Catalysts for the Dry Reforming of Methane

    SciTech Connect

    Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; Anjum, Dalaver H.; Kanoun, Mohammed B.; Scaranto, Jessica; Hedhili, Mohamed N.; Khalid, Syed; Laveille, Paco V.; Lawrence D'Souza; Clo, Alain; Basset, Jean-Marie

    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. Kinetics and mechanism of the liquid-phase oxidation of cyclohexene. V. Oxidation of cyclohexene in the presence of bimetallic catalysts

    SciTech Connect

    Baevskii, M.Yu.; Litvintsev, I.Yu.; Sapunov, V.N.

    1988-11-01

    The kinetics of the liquid-phase oxidation of cyclohexene in the presence of homogeneous bimetallic catalysts Co-V, Pb-V, Pb-Mo was investigated. It was shown that the activity of the bimetallic catalyst found is determined to a large degree by the nature of the epoxiding metal. A general model is proposed for the oxidation of cyclohexene in the presence of bimetallic catalysts.

  2. Understanding the atomic-level process of CO-adsorption-driven surface segregation of Pd in (AuPd)147 bimetallic nanoparticles.

    PubMed

    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.

  3. Density functional study of hydrogen binding on gold and silver-gold clusters.

    PubMed

    Zhao, Shuang; Ren, YunLi; Ren, YunLai; Wang, JianJi; Yin, WeiPing

    2010-04-15

    A theoretical study was carried out on the binding of hydrogen on small bimetallic Ag(m)Au(n) (m + n < or = 5) and pure Au(n) (n < or = 5) clusters with neutral, negative, and positive charge state. It is found that the composition and charge state of clusters have strong influence on the most favorable binding site. The adiabatic ionization potentials, electron affinities, and hydrogen binding energies of cluster hydrides increase with the Au content increasing for the given cluster size. The cationic silver-gold cluster hydrides prefer ejection of Au-containing products whereas the anionic silver-gold cluster hydrides prefer ejection of Ag-containing products. The magnitude of metal-H frequency in combination with the metal-H bond length indicates that, with the same type of the binding site, the Au-H interaction is stronger than the Ag-H interaction.

  4. Growth of Three-Shell Onionlike Bimetallic Nanoparticles

    NASA Astrophysics Data System (ADS)

    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.

  5. Growth of three-shell onionlike bimetallic nanoparticles.

    PubMed

    Baletto, F; Mottet, C; Ferrando, R

    2003-04-04

    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.

  6. Rotationally resolved spectroscopy of the A~ 2A1<--X~ 2B1 transition of H2S+ above the barrier to linearity using the mass-analyzed threshold ionization photofragment excitation technique

    NASA Astrophysics Data System (ADS)

    Han, Songhee; Kang, Tae Yeon; Kim, Sang Kyu

    2010-03-01

    The à A21←X˜ B21 transitions of H2S+ above the barrier to linearity have been investigated with the energy resolution high enough to identify individual rotational transition lines for the first time. The rotational cooling of the cation is achieved either by the direct ionization or mass-analyzed threshold ionization (MATI) technique employed in the vacuum-ultraviolet laser excitation of the jet-cooled H2S. Subsequent photoexcitation leads to the H2S+→H2+S+ dissociation and the S+ product yield taken as a function of the excitation energy gives the photofragment excitation (PHOFEX) spectra. The combined use of MATI and PHOFEX techniques greatly simplifies the spectrum allowing the accurate identification of the rotationally resolved bands which is otherwise a formidable task due to the intrinsic complexity of the à A21←X˜ B21 transition. Highly excited states of Ã(0,7,0), Ã(0,8,0), and Ã(0,9,0) vibronic levels with different K quantum numbers which are located above the barrier to linearity are thoroughly investigated. The bent-to-quasilinear transition of H2S+ above the barrier to linearity shows the characteristics of the Renner-Teller effect, showing the large A rotational constant and strong intensity borrowing of the highly vibrationally excited ground levels such as X˜(0,23,0) or X˜(0,24,0) in the dipole-allowed excitation. Spectroscopic parameters of term values, rotational, and spin-orbit coupling constants are precisely determined in this work, providing the most quantitative spectroscopic structure of the H2S+ to date. Quantum-state dependent photodissociation dynamics are also discussed from spectral features of PHOFEX.

  7. Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks.

    PubMed

    Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng; Lu, Weigang; Wang, Xuan; Zhang, Qiang; Bosch, Mathieu; Liu, Tian-Fu; Lian, Xizhen; Zhou, Hong-Cai

    2015-12-01

    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 M(2+) 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. In(3+) 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Kinetic Study on the Formation of Bimetallic Core-Shell Nanoparticles via Microemulsions

    PubMed Central

    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

  9. Core–Shell Bimetallic Nanoparticles Robustly Fixed on the Outermost Surface of Magnetic Silica Microspheres

    PubMed Central

    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

  10. Template-Directed Approach Towards the Realization of Ordered Heterogeneity in Bimetallic Metal-Organic Frameworks.

    PubMed

    Kim, Daeok; Coskun, Ali

    2017-03-29

    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.

  11. Theoretical analysis of D-type optical fiber sensor with a bimetallic layer

    NASA Astrophysics Data System (ADS)

    Liu, Yaobo; Liu, Yueming; Hu, Liaolin

    2008-12-01

    In this paper, we consider a SPR sensor based on D-type optical fiber with bimetallic combination. In pursuit of both higher sensitivity and larger operating range, firstly, we separately analyze the influence of parameters such as the length of coating L, the incident angle θ and the thickness of Au-coating layer d. when the optimum parameters of sensor are determined, we analyze the performance of the sensor with different bimetallic combination consist of Au, Ag, Cu and Al. Lastly, we can get a conclusion that the sensor with L=5mm,d=25nm, θ=88° and Au-Ag at x=0.8 can provide the best performance in terms of the sensitivity and operating range.

  12. Synthesis, characterization, and growth simulations of Cu-Pt bimetallic nanoclusters.

    PubMed

    Khanal, Subarna; Spitale, Ana; Bhattarai, Nabraj; Bahena, Daniel; Velazquez-Salazar, J Jesus; Mejía-Rosales, Sergio; M Mariscal, Marcelo; José-Yacaman, Miguel

    2014-01-01

    Highly monodispersed Cu-Pt bimetallic nanoclusters were synthesized by a facile synthesis approach. Analysis of transmission electron microscopy (TEM) and spherical aberration (C s)-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.

  13. Uncovering the Stabilization Mechanism in Bimetallic Ruthenium-Iridium Anodes for Proton Exchange Membrane Electrolyzers.

    PubMed

    Saveleva, Viktoriia A; Wang, Li; Luo, Wen; Zafeiratos, Spyridon; Ulhaq-Bouillet, Corinne; Gago, Aldo S; Friedrich, K Andreas; Savinova, Elena R

    2016-08-18

    Proton exchange membrane (PEM) electrolyzers are attracting an increasing attention as a promising technology for the renewable electricity storage. In this work, near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) is applied for in situ monitoring of the surface state of membrane electrode assemblies with RuO2 and bimetallic Ir0.7Ru0.3O2 anodes during water splitting. We demonstrate that Ir protects Ru from the formation of an unstable hydrous Ru(IV) oxide thereby rendering bimetallic Ru-Ir oxide electrodes with higher corrosion resistance. We further show that the water splitting occurs through a surface Ru(VIII) intermediate, and, contrary to common opinion, the presence of Ir does not hinder its formation.

  14. Nanosized Pd-Au bimetallic phases on carbon nanotubes for selective phenylacetylene hydrogenation.

    PubMed

    Wang, Shenghua; Xin, Zhiling; Huang, Xing; Yu, Weizhen; Niu, Shuo; Shao, Lidong

    2017-02-22

    Palladium (Pd)-catalyzed selective hydrogenation of alkynes has been one of the most studied hydrogenation reactions in the last century. However, kinetic studies conducted to reveal the catalyst's active centers have been hindered because of dynamic surface changes on Pd during the reaction. In the present study, bimetallic Pd-Au nanoparticles supported on carbon nanotubes have been synthesized at room temperature as catalysts for selective hydrogenation of phenylacetylene, which show effectively enhanced selectivity compared to their monometallic counterparts. Structural and surface analyses of fresh and reacted catalysts reveal that selective hydrogenation of phenylacetylene is favored over nanosized Pd-Au bimetallic phases due to modifications in the Pd surface in terms of neighboring site isolation and electron density reduction.

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

    NASA Astrophysics Data System (ADS)

    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. Decomposition kinetics of ammonia in gaseous stream by a nanoscale copper-cerium bimetallic catalyst.

    PubMed

    Hung, Chang-Mao

    2008-01-15

    This study performance is to examine the kinetics over nanoscale copper-cerium bimetallic catalyst under selective catalytic oxidation (SCO) of ammonia to N(2) in a tubular fixed-bed reactor (TFBR) at temperatures from 150 to 400 degrees C in the presence of oxygen. The nanoscale copper-cerium bimetallic catalyst was prepared by co-precipitation with Cu(NO(3))(2) and Ce(NO(3))(3) at molar ratio of 6:4. Experimental results showed that the catalyst with transmission electron microscopy (TEM) revealed that copper and cerium are well dispersed and catalyst in the form of nanometer-sized particles. Moreover, the kinetic behavior of NH(3) oxidation with catalysis can be accounted by using the rate expression of the Langmuir-Hinshelwood type kinetic model. Kinetic parameters are also developed on the basis of the differential reactor data. Also, experimental results are compared with those of the model predicted.

  17. Synthesis of a discrete-action thermo-bimetallic actuator with a tongue

    NASA Astrophysics Data System (ADS)

    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.

  18. Photochemistry and Redox Chemistry of an Unsymmetrical Bimetallic Copper(I) Complex.

    PubMed

    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.

  19. Photoluminescent AuCu bimetallic nanoclusters as pH sensors and catalysts

    NASA Astrophysics Data System (ADS)

    Chen, Po-Cheng; Ma, Jia-Ying; Chen, Li-Yi; Lin, Guan-Lin; Shih, Chung-Chien; Lin, Tai-Yuan; Chang, Huan-Tsung

    2014-03-01

    A facile and one-pot approach to the preparation of gold (Au) and copper (Cu) bimetallic nanoclusters (NCs) is unveiled. AuCu NCs reveal features of orange photoluminescence (PL), reversible pH-dependent PL properties, and efficient catalytic activity for degradation of methylene blue (MB).A facile and one-pot approach to the preparation of gold (Au) and copper (Cu) bimetallic nanoclusters (NCs) is unveiled. AuCu NCs reveal features of orange photoluminescence (PL), reversible pH-dependent PL properties, and efficient catalytic activity for degradation of methylene blue (MB). Electronic supplementary information (ESI) available: Experimental section and Fig. S1-S16. See DOI: 10.1039/c3nr06123j

  20. Phase diagram and structural evolution of Ag-Au bimetallic nanoparticles: molecular dynamics simulations.

    PubMed

    Yeo, Sang Chul; Kim, Da Hye; Shin, Kihyun; Lee, Hyuck Mo

    2012-02-28

    We studied the structural evolution of a 270-atom Ag-Au bimetallic nanoparticle (2 nm in size) with varying composition and temperature. The liquid to solid transition region and the solid-state structure were investigated using molecular dynamics simulations. To determine the exact transition temperature region, we applied the mean square displacement and structure deviation methods, as well as the generally used caloric curve of potential energy versus temperature. The results showed that a complete solid-solution phase diagram of the binary Ag-Au system was obtained. Irrespective of the composition, the freezing temperature of a Ag-Au bimetallic nanoparticle was lower than that of the bulk state by a margin of several hundred degrees, and three different solid-state structures are proposed in relation to the Au composition. Our phase diagram offers guidance for the application of Ag-Au nanoparticles.

  1. Synthesis, characterization, and growth simulations of Cu–Pt bimetallic nanoclusters

    PubMed Central

    Khanal, Subarna; Spitale, Ana; Bhattarai, Nabraj; Bahena, Daniel; Velazquez-Salazar, J Jesus; Mejía-Rosales, Sergio

    2014-01-01

    Summary Highly monodispersed Cu–Pt bimetallic nanoclusters were synthesized by a facile synthesis approach. Analysis of transmission electron microscopy (TEM) and spherical aberration (C s)-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. PMID:25247120

  2. Design and synthesis of bimetallic electrocatalyst with multilayered Pt-skin surfaces.

    SciTech Connect

    Wang, C.; Chi, M.; Li, D.; Strmcnik, D.; van der Vliet, D.; Wang, G.; Komanicky, V.; Chang, K.-C.; Paulikas, A. P.; Tripkovic, D.; Pearson, J.; More, K. L.; Markovic, N. M.; Stamenkovic, V. R.

    2011-01-01

    Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

  3. Design and Synthesis of Bimetallic Electrocatalyst with Multilayered Pt-Skin Surfaces

    SciTech Connect

    Wang, Chao; Chi, Miaofang; Li, Dongguo; Strmcnik, Dusan; Van der Vliet, Dennis; Wang, Guofeng; Komanicky, Vladimir; Chang, Kee-Chul; Paulikas, Arvydas; Tripkovic, Dusan; Pearson, John; More, Karren Leslie; Markovic, Nenad; Stamenkovic, Vojislav

    2011-01-01

    Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

  4. Validation of Two Hydrocodes with a Bi-Metallic Shaped Charge Experiment

    SciTech Connect

    Ingraham, Daniel J.

    2012-08-16

    Staggered grid (SGH) and cell-centered (CCH) Lagrangian Hydro are two approaches to modeling high explosives (HE) experiments. HE experiments involve complex flows. For example, the discontinuity in the tangential velocity across a frictionless contact surface. In this work, the SGH and CCH schemes with a contact surface algorithm are used to simulate a bimetallic shaped charge experiment using FLAG. Experiment will be performed at LANL in the coming year and used to validate the SGH and CCH schemes results.

  5. Calibrating bimetallic grayscale photomasks to photoresist response for precise micro-optics fabrication

    NASA Astrophysics Data System (ADS)

    Chapman, Glenn H.; Qarehbaghi, Reza; Roche, Santiago

    2014-03-01

    Microfabricating high resolution micro-optics structures requires shape control to <1/8th wavelength (~60nm) in both vertical and horizontal surface precision. Grayscale bimetallic photomasks are bi-layer thermal resists consisting of two thin layers of Bi-on-Indium or Tin-on-Indium. A focused laser spot creates a thermal metal oxide with a controllably transparency set by the beam power of optical density from ~3OD (unexposed) to <0.22OD (fully exposed). A directwrite raster-scan photomask laser system with a CW Argon-ion laser at 514nm for the bimetallic writing and 457nm line for measuring the OD change used a feedback-controlled Gaussian beam to achieve 256-level grayscale masks. Setting the graylevels required to achieve uniform vertical steps in the photoresist requires adjustment in transparency based on the exact response curves of a given resist/development process. An initial model is developed using the classic resist threshold dose exposure D0 and dose to clear Dc creating a power law relation between the required exposure dose for each thickness step and the mask transparency. However real resists behave differently than the simple model near the threshold requiring careful calibrating of mask graylevel transparencies with the photoresist response curve for a given resist/development process. Test structures ranging from steps to ramps and complex patterns were examined via both SEM and profilometry from the resulting bimetallic grayscale masks. Secondary corrections modify the needed bimetallic OD due to the exposure source spectrum differences from the 457nm measurement. This enhances the patterning of micro-optic and 3D MEMS structures.

  6. Manufacturing Systems Demonstration: Bimetallic Friction STIR Joining of AA6061 and High Hardness Steel

    DTIC Science & Technology

    2013-05-31

    processes. Another secondary benefit of heated stir joining processes is their capability of joining dissimilar metals which cannot be welded using...later at the TARDEC metals lab, has confirmed that the dissimilar metals were metallurgically bonded at the joint surface with a thin (2-5 μm) Al...Fe intermetallic present. Mechanical load testing determined that the bimetallic FSP joint was stronger than similar AA6061-to-AA6061 fusion- welded and

  7. pH-Triggered SERS via Modulated Plasmonic Coupling in Individual Bimetallic Nanocobs

    DTIC Science & Technology

    2011-01-01

    dry states. In contrast with previous examples of such bimetallic nano- cobs, we utilize here a responsive polyacrylic acid (PAA) nanocoating that...acts as a linker between the nanoparticles and nanowire. [ 37 ] The pH-responsive nature of the PAA nanocoating , which is sensitive to the...indicating that pH-induced changes in the wet PAA nanocoating are robust enough to maintain changes in the optical properties and morphology even in

  8. Controlling Bimetallic Nanostructures by the Microemulsion Method with Subnanometer Resolution Using a Prediction Model.

    PubMed

    Buceta, David; Tojo, Concha; Vukmirovic, Miomir B; Deepak, Francis Leonard; López-Quintela, M Arturo

    2015-07-14

    We present a theoretical model to predict the atomic structure of Au/Pt nanoparticles synthesized in microemulsions. Excellent concordance with the experimental results shows that the structure of the nanoparticles can be controlled at subnanometer resolution simply by changing the reactant concentration. The results of this study not only offer a better understanding of the complex mechanisms governing reactions in microemulsions, but open up a simple new way to synthesize bimetallic nanoparticles with ad hoc controlled nanostructures.

  9. Tailoring the carbon nanostructures grown on the surface of Ni-Al bimetallic nanoparticles in the gas phase.

    PubMed

    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 consumption of the melting Al matrix sites; sea urchin-like carbon nanotubes (SU-CNTs) of small diameter (∼10±4 nm) can be grown on the 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 presence of Al matrix in the bimetallic nanoparticles; SU-CNTs of large diameter (∼60±13 nm) can also 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.

  10. Study of supported PtCu and PdAu bimetallic nanoparticles using in-situ x-ray tools.

    SciTech Connect

    Oxford, S. M.; Lee, P. L.; Chupas, P. J.; Chapman, K. W.; Kung, M. C.; Kung, H. H.; Northwestern Univ.

    2010-01-01

    A combination of two synchrotron X-ray techniques, X-ray absorption spectroscopy (XAS), and pair distribution function analysis (PDF) with complementary Fourier transform infrared (FTIR) spectroscopy measurement, was used to characterize the composition distributions of PdAu and PtCu bimetallic particles after treatment in H{sub 2} or CO and in the presence of these gases. This is the first reported application of PDF to the study of supported bimetallic nanoparticles. We found that XAS was informative in determining the component distribution of an initial sample, but PDF was better suited to following changes in the distribution upon changing the gas environment. Thus, the surface of a PtCu bimetallic particle of about 2.5 nm after treatment in H{sub 2} was found to be enriched in Cu, while the core was bimetallic. There was no evidence of a component-segregated core?shell structure. Treatment in CO caused enrichment of Pt to the surface layer, with a concomitant migration of Cu to the core. The average particle size remained the same. For the PdAu bimetallic particles, the surface and core compositions were similar after H{sub 2} treatment, and Pd was enriched in the surface after CO treatment. The X-ray results compared favorably to infrared spectroscopy results. The results demonstrated that the two X-ray techniques in combination can generate new information not available with either technique alone or other techniques, about the elemental distribution of bimetallic particles under conditions relevant to catalysis. They could provide new insight into structure-function relationships and time-on-stream behavior of bimetallic catalysts.

  11. Air stable magnetic bimetallic Fe-Ag nanoparticles for advanced antimicrobial treatment and phosphorus removal.

    PubMed

    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.

  12. DNA-Mediated Morphological Control of Pd-Au Bimetallic Nanoparticles.

    PubMed

    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.

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

    PubMed

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

    2014-03-10

    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.

  14. Tuning the composition of AuPt bimetallic nanoparticles for antibacterial application.

    PubMed

    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.

  15. Laser synthesis of ligand-free bimetallic nanoparticles for plasmonic applications.

    PubMed

    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.

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

    PubMed

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

    2014-12-24

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

  17. Effects of bimetallic nanoparticles on seed germination frequency and biochemical characterisation of Eruca sativa.

    PubMed

    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.

  18. Reductive degradation of tetrabromobisphenol A over iron-silver bimetallic nanoparticles under ultrasound radiation.

    PubMed

    Luo, Si; Yang, Shaogui; Wang, Xiaodong; Sun, Cheng

    2010-04-01

    The present study described the degradation behavior of tetrabromobisphenol A (TBBPA) in Fe-Ag suspension solutions under ultrasonic radiation (US). The Fe-Ag bimetallic nanoparticles with core-shell structure were successfully synthesized by reduction and deposition of Ag on nanoscale Fe surface, and were further characterized by BET, XRD, TEM, SEM, X-ray fluorescence and X-ray photo-electron spectroscopy. The results revealed that the displacement plating produced a non-uniform overlayer of Ag additive on iron; the as-synthesized bimetallic nanoparticles were spherical with diameters of 20-100 nm aggregated in the form of chains. Batch studies demonstrated that the TBBPA (2 mg L(-1)) was completely degraded in 20 min over Fe-Ag nanoparticles, which has higher degradation efficiency than Fe(0) nanoparticles under US. The effects of Fe-Ag bimetallic nanoparticles loading, initial TBBPA concentration, pH of the solution, Ag loading and temperature on the reduction efficiency of TBBPA under US were investigated. The complete reduction of TBBPA in 20 min was determined selectively under the conditions of pH (pH=6.0+/-0.5), Ag loading(1 wt.%) at 30 degrees C over the fabricated Fe-Ag nanoparticles. Additionally, the major intermediates identified by LC-MS technique were tri-BBPA, di-BBPA, mono-BBPA and BPA and the degradation mechanism was also proposed.

  19. Fabrication of bimetallic microfluidic surface-enhanced Raman scattering sensors on paper by screen printing.

    PubMed

    Qu, Lu-Lu; Song, Qi-Xia; Li, Yuan-Ting; Peng, Mao-Pan; Li, Da-Wei; Chen, Li-Xia; Fossey, John S; Long, Yi-Tao

    2013-08-20

    Au-Ag bimetallic microfluidic, dumbbell-shaped, surface enhanced Raman scattering (SERS) sensors were fabricated on cellulose paper by screen printing. These printed sensors rely on a sample droplet injection zone, and a SERS detection zone at either end of the dumbbell motif, fabricated by printing silver nanoparticles (Ag NPs) and gold nanoparticles (Au NPs) successively with microscale precision. The microfluidic channel was patterned using an insulating ink to connect these two zones and form a hydrophobic circuit. Owing to capillary action of paper in the millimeter-sized channels, the sensor could enable self-filtering of fluids to remove suspended particles within wastewater without pumping. This sensor also allows sensitive SERS detection, due to advantageous combination of the strong surface enhancement of Ag NPs and excellent chemical stability of Au NPs. The SERS performance of the sensors was investigated by employing the probe rhodamine 6G, a limit of detection (LOD) of 1.1×10(-13)M and an enhancement factor of 8.6×10(6) could be achieved. Moreover, the dumbbell-shaped bimetallic sensors exhibited good stability with SERS performance being maintained over 14 weeks in air, and high reproducibility with less than 15% variation in spot-to-spot SERS intensity. Using these dumbbell-shaped bimetallic sensors, substituted aromatic pollutants in wastewater samples could be quantitatively analyzed, which demonstrated their excellent capability for rapid trace pollutant detection in wastewater samples in the field without pre-separation.

  20. Kinetically controlled autocatalytic chemical process for bulk production of bimetallic core-shell structured nanoparticles.

    PubMed

    Taufany, Fadlilatul; Pan, Chun-Jern; Rick, John; Chou, Hung-Lung; Tsai, Mon-Che; Hwang, Bing-Joe; Liu, Din-Goa; Lee, Jyh-Fu; Tang, Mau-Tsu; Lee, Yao-Chang; Chen, Ching-Iue

    2011-12-27

    Although bimetallic core@shell structured nanoparticles (NPs) are achieving prominence due to their multifunctionalities and exceptional catalytic, magnetic, thermal, and optical properties, the rationale underlying their design remains unclear. Here we report a kinetically controlled autocatalytic chemical process, adaptable for use as a general protocol for the fabrication of bimetallic core@shell structured NPs, in which a sacrificial Cu ultrathin layer is autocatalytically deposited on a dimensionally stable noble-metal core under kinetically controlled conditions, which is then displaced to form an active ultrathin metal-layered shell by redox-transmetalation. Unlike thermodynamically controlled under-potential deposition processes, this general strategy allows for the scaling-up of production of high-quality core-shell structured NPs, without the need for any additional reducing agents and/or electrochemical treatments, some examples being Pd@Pt, Pt@Pd, Ir@Pt, and Ir@Pd. Having immediate and obvious commercial potential, Pd@Pt NPs have been systematically characterized by in situ X-ray absorption, electrochemical-FTIR, transmission electron microscopy, and electrochemical techniques, both during synthesis and subsequently during testing in one particularly important catalytic reaction, namely, the oxygen reduction reaction, which is pivotal in fuel cell operation. It was found that the bimetallic Pd@Pt NPs exhibited a significantly enhanced electrocatalytic activity, with respect to this reaction, in comparison with their monometallic counterparts.

  1. Synthesis and characterization of immobilized Ni-Co bimetallic using Tapanuli clay for catalyst application

    SciTech Connect

    Nuryanti,; Juwono, Ariadne L.; Krisnandi, Yuni K.

    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.

  2. A Review on Bimetallic Nickel-Based Catalysts for CO2 Reforming of Methane.

    PubMed

    Bian, Zhoufeng; Das, Sonali; Wai, Ming Hui; Hongmanorom, Plaifa; Kawi, Sibudjing

    2017-07-15

    In recent years, CO2 reforming of methane (dry reforming of methane, DRM) has become an attractive research area because it converts two major greenhouse gasses into syngas (CO and H2 ), which can be directly used as fuel or feedstock for the chemical industry. Ni-based catalysts have been extensively used for DRM because of its low cost and good activity. A major concern with Ni-based catalysts in DRM is severe carbon deposition leading to catalyst deactivation, and a lot of effort has been put into the design and synthesis of stable Ni catalysts with high carbon resistance. One effective and practical strategy is to introduce a second metal to obtain bimetallic Ni-based catalysts. The synergistic effect between Ni and the second metal has been shown to increase the carbon resistance of the catalyst significantly. In this review, a detailed discussion on the development of bimetallic Ni-based catalysts for DRM including nickel alloyed with noble metals (Pt, Ru, Ir etc.) and transition metals (Co, Fe, Cu) is presented. Special emphasis has been provided on the underlying principles that lead to synergistic effects and enhance catalyst performance. Finally, an outlook is presented for the future development of Ni-based bimetallic catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

    NASA Astrophysics Data System (ADS)

    Ji, Jianlong; Li, Pengwei; Sang, Shengbo; Zhang, Wendong; Zhou, Zhaoying; Yang, Xing; Dong, Hualai; Li, Gang; Hu, Jie

    2014-03-01

    Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and UV-vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA) models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electric field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO) flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS) activity, using 4-mercaptopyridine (4-MP) as model molecules.

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

    PubMed Central

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

    2014-01-01

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

  5. Prediction of atomic structure of Pt-based bimetallic nanoalloys by using genetic algorithm

    NASA Astrophysics Data System (ADS)

    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.

  6. Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

    SciTech Connect

    Ji, Jianlong; Li, Pengwei; Sang, Shengbo Zhang, Wendong Li, Gang; Hu, Jie; Zhou, Zhaoying Yang, Xing; Dong, Hualai

    2014-03-15

    Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and UV–vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA) models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electric field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO) flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS) activity, using 4-mercaptopyridine (4-MP) as model molecules.

  7. The effect of intermolecular hydrogen bonding on the fluorescence of a bimetallic platinum complex.

    PubMed

    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.

  8. Ionic liquid assisted synthesis of Au-Pd bimetallic particles with enhanced electrocatalytic activity.

    PubMed

    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.

  9. Nanocomposite of bimetallic nanodendrite and reduced graphene oxide as a novel platform for molecular imprinting technology.

    PubMed

    Patra, Santanu; Roy, Ekta; Madhuri, Rashmi; Sharma, Prashant K

    2016-04-28

    In this present work, for the first time, we are reporting a green synthesis approach for the preparation of vinyl modified reduced graphene oxide-based magnetic and bimetallic (Fe/Ag) nanodendrite (RGO@BMNDs). Herein, the RGO@BMNDs acts as a platform for the synthesis of the pyrazinamide (PZA)-imprinted polymer matrix and used for designing of the electrochemical sensor. We have demonstrated how the change in morphology could affect the electrochemical and magnetic property of nanomaterials and for this the reduced graphene oxide-based bimetallic nanoparticle (Fe/Ag) was also prepared It was found that the combination of graphene and bimetallic nanodendrites shows improvement as well as enhancement in the electrocatalytic activity and adsorption capacity, in comparison to their respective nanoparticles. The application of imprinted-RGO@BMNDs sensor was explored for trace level detection of PZA (Limit of detection = 6.65 pg L(-1), S/N = 3), which is a drug used for the cure of Tuberculosis. This is lowest detection limit reported so far for the detection of PZA. The sensor is highly selective, cost-effective, simple and free from any interfering effect. The real time application of the sensor was explored by successful detection of PZA in pharmaceutical and human blood serum, plasma and urine samples.

  10. Fabrication of ultra-thin nanostructured bimetallic foils by Accumulative Roll Bonding and Asymmetric Rolling

    PubMed Central

    Yu, Hailiang; Lu, Cheng; Tieu, A. Kiet; Godbole, Ajit; Su, Lihong; Sun, Yong; Liu, Mao; Tang, Delin; Kong, Charlie

    2013-01-01

    This paper reports a new technique that combines the features of Accumulative Roll Bonding (ARB) and Asymmetric Rolling (AR). This technique has been developed to enable production of ultra-thin bimetallic foils. Initially, 1.5 mm thick AA1050 and AA6061 foils were roll-bonded using ARB at 200°C, with 50% reduction. The resulting 1.5 mm bimetallic foil was subsequently thinned to 0.04 mm through four AR passes at room temperature. The speed ratio between the upper and lower AR rolls was 1:1.3. The tensile strength of the bimetallic foil was seen to increase with reduction in thickness. The ductility of the foil was seen to reduce upon decreasing the foil thickness from 1.5 mm to 0.14 mm, but increase upon further reduction in thickness from 0.14 mm to 0.04 mm. The grain size was about 140 nm for the AA6061 layer and 235 nm for the AA1050 layer, after the third AR pass. PMID:23918002

  11. Reaction of 1,1,1-trichloroethane with zero-valent metals and bimetallic reductants

    SciTech Connect

    Fennelly, J.P.; Roberts, A.L.

    1998-07-01

    Information concerning the pathways and products of reaction of 1,1,1-trichloroethane (1,1,1-TCA) with zero-valent metals may be critical to the success of in situ treatment techniques. Many researchers assume that alkyl polyhalides undergo reduction via stepwise hydrogenolysis (replacement of halogen by hydrogen). Accordingly, 1,1,1-TCA should react to 1,1-dichloroethane (1,1-DCA), to chloroethane, and finally to ethane. Experiments conducted in laboratory-scale batch reactors indicate, however, that with zinc, iron, and two bimetallic reductants (nickel-plated iron and copper-plated iron) this simplistic stepwise scheme cannot explain observed results. 1,1,1-TCA was found to react rapidly with zinc to form ethane and 1,1-DCA. Independent experiments confirmed that 1,1-DCA reacts too slowly to represent an intermediate in the formation of ethane. In reactions with iron, nickel/iron, and copper/iron, cis-2-butene, ethylene, and 2-butyne were also observed as minor products. Product ratios were dependent on the identity of the metal or bimetallic reductant, with zinc resulting in the lowest yield of chlorinated product. For reactions with iron and bimetallic reductants, a scheme involving successive one-electron reduction steps to form radicals and carbenoids can be invoked to explain the absence of observable intermediates, as well as the formation of products originating from radical or possibly from carbenoid coupling.

  12. Efficient method for the conversion of agricultural waste into sugar alcohols over supported bimetallic catalysts.

    PubMed

    Tathod, Anup P; Dhepe, Paresh L

    2015-02-01

    Promoter effect of Sn in the PtSn/γ-Al2O3 (AL) and PtSn/C bimetallic catalysts is studied for the conversion of variety of substrates such as, C5 sugars (xylose, arabinose), C6 sugars (glucose, fructose, galactose), hemicelluloses (xylan, arabinogalactan), inulin and agricultural wastes (bagasse, rice husk, wheat straw) into sugar alcohols (sorbitol, mannitol, xylitol, arabitol, galactitol). In all the reactions, PtSn/AL showed enhanced yields of sugar alcohols by 1.5-3 times than Pt/AL. Compared to C, AL supported bimetallic catalysts showed prominent enhancement in the yields of sugar alcohols. Bimetallic catalysts characterized by X-ray diffraction study revealed the stability of catalyst and absence of alloy formation thereby indicating that Pt and Sn are present as individual particles in PtSn/AL. The TEM analysis also confirmed stability of the catalysts and XPS study disclosed formation of electron deficient Sn species which helps in polarizing carbonyl bond to achieve enhanced hydrogenation activity.

  13. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Final report

    SciTech Connect

    Chunshan Song; Schobert, H.H.; Parfitt, D.P.

    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.

  14. Chemical reduction kinetics of nitrate in aqueous solution by Mg/Cu bimetallic particles.

    PubMed

    Mortazavi, S B; Ramavandi, B; Moussavi, G

    2011-01-01

    Synthesized magnesium/copper (Mg/Cu) bimetallic particles have shown good potential for use in the reduction of nitrate from aqueous solutions. This study was conducted to investigate the main factors affecting the kinetics of nitrate reduction by Mg/Cu particles (<100 microm) in uncontrolled reaction conditions. The Mg/Cu bimetallic particles removed the majority of the various nitrate concentrations tested (50, 100, 150, 200 and 300 mg L(-1)) within a short period. The time required for the removal of 90.6% of the NO3(-) from a 100 mg L(-1) solution was about 20 min using 2 gL(-1) bimetallic Mg/Cu at an initial solution pH of 6. The activation energy (Ea) for nitrate reduction by Mg/Cu over the temperature range of 5 to 60 degrees C was 14.21 kJ mol(-1). The experimental results of the kinetic analysis from batch studies indicated that a higher initial nitrate concentration yielded a greater reaction-rate constant and the denitrification rate increased with increase Mg/Cu dosage.

  15. Bimetallic non-alloyed NPs for improving the broadband optical absorption of thin amorphous silicon substrates

    PubMed Central

    2014-01-01

    We propose the use of bimetallic non-alloyed nanoparticles (BNNPs) to improve the broadband optical absorption of thin amorphous silicon substrates. Isolated bimetallic NPs with uniform size distribution on glass and silicon are obtained by depositing a 10-nm Au film and annealing it at 600°C; this is followed by an 8-nm Ag film annealed at 400°C. We experimentally demonstrate that the deposition of gold (Au)-silver (Ag) bimetallic non-alloyed NPs (BNNPs) on a thin amorphous silicon (a-Si) film increases the film's average absorption and forward scattering over a broad spectrum, thus significantly reducing its total reflection performance. Experimental results show that Au-Ag BNNPs fabricated on a glass substrate exhibit resonant peaks at 437 and 540 nm and a 14-fold increase in average forward scattering over the wavelength range of 300 to 1,100 nm in comparison with bare glass. When deposited on a 100-nm-thin a-Si film, Au-Ag BNNPs increase the average absorption and forward scattering by 19.6% and 95.9% compared to those values for Au NPs on thin a-Si and plain a-Si without MNPs, respectively, over the 300- to 1,100-nm range. PMID:24725390

  16. Experimental and computational investigations of sulfur-resistant bimetallic catalysts for reforming of biomass gasification products

    SciTech Connect

    Rangan, Meghana; Yung, Matthew M.; Medlin, J. William

    2011-11-17

    A combination of density functional theory (DFT) calculations and experimental studies of supported catalysts was used to identify H{sub 2}S-resistant biomass gasification product reforming catalysts. DFT calculations were used to search for bimetallic, nickel-based (1 1 1) surfaces with lower sulfur adsorption energies and enhanced ethylene adsorption energies. These metrics were used as predictors for H{sub 2}S resistance and activity toward steam reforming of ethylene, respectively. Relative to Ni, DFT studies found that the Ni/Sn surface alloy exhibited enhanced sulfur resistance and the Ni/Ru system exhibited an improved ethylene binding energy with a small increase in sulfur binding energy. A series of supported bimetallic nickel catalysts was prepared and screened under model ethylene reforming conditions and simulated biomass tar reforming conditions. The observed experimental trends in activity were consistent with theoretical predictions, with observed reforming activities in the order Ni/Ru > Ni > Ni/Sn. Interestingly, Ni/Ru showed a high level of resistance to sulfur poisoning compared with Ni. This sulfur resistance can be partly explained by trends in sulfur versus ethylene binding energy at different types of sites across the bimetallic surface.

  17. Ferrocenyl-cymantrenyl hetero-bimetallic chalcones: Synthesis, structure and biological properties

    NASA Astrophysics Data System (ADS)

    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.

  18. Cation exchange resin immobilized bimetallic nickel-iron nanoparticles to facilitate their application in pollutants degradation.

    PubMed

    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.

  19. Trends in methanol decomposition on transition metal alloy clusters from scaling and Brønsted–Evans–Polanyi relationships

    SciTech Connect

    Mehmood, Faisal; Rankin, Rees B.; Greeley, Jeffrey; Curtiss, Larry A.

    2012-05-15

    A combination of first principles Density Functional Theory calculations and thermochemical scaling relationships are employed to estimate the thermochemistry and kinetics of methanol decomposition on unsupported subnanometer metal clusters. The approach uses binding energies of various atomic and molecular species, determined on the pure metal clusters, to develop scaling relationships that are then further used to estimate the methanol decomposition thermodynamics for a series of pure and bimetallic clusters with four atoms per cluster. Additionally, activation energy barriers are estimated from Brønsted–Evans–Polanyi plots relating transition and final state energies on these clusters. The energetic results are combined with a simple, microkinetically-inspired rate expression to estimate reaction rates as a function of important catalytic descriptors, including the carbon and atomic oxygen binding energies to the clusters. Finally, based on these analyses, several alloy clusters are identified as promising candidates for the methanol decomposition reaction.

  20. Vegard's law-like behavior for Mn(m)Tc(n) alloy clusters: a first-principles prediction.

    PubMed

    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.

  1. Bimetallic Nanocatalysts in Mesoporous Silica for Hydrogen Production from Coal-Derived Fuels

    SciTech Connect

    Kuila, Debasish; Ilias, Shamsuddin

    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

  2. Plasmonic Properties of Bimetallic Nanostructures and Their Applications in Hydrogen Sensing and Chemical Reactions

    NASA Astrophysics Data System (ADS)

    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

  3. Meaningful Clusters

    SciTech Connect

    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.

  4. Selective Hydrogenation of Phenylacetylene on Bimetallic Cu-Pd and Cu-Pt Catalysts

    NASA Astrophysics Data System (ADS)

    Cladaras, George

    The development of selective catalysts has become a key concept in improving the efficiency of processes. Controlling the product distribution of a reaction can result in fewer by-products and reduce energy requirements for process equipment downstream. The selective hydrogenation of alkynes to alkenes is of major importance to industrial polymerization processes where alkyne/diene impurities can poison the polymerization catalyst and have an unwanted inhibiting effect on the growth of the polymer chain. In many circumstances, bimetallic catalysts have proved to have superior catalytic properties such as greater activity, selectivity or stability compared to their monometallic analogs. A study by the Sykes group (Chemistry, Tufts) in collaboration with our group has shown that in ultra-high vacuum (UHV), the addition of Pd minority species (0.01 ML) onto an otherwise inert Cu(111) single crystal surface can activate the Cu surface for selective hydrogenation reactions. This thesis work is an extension of the surface science study to the preparation of bimetallic catalysts at the nanoscale and their testing in hydrogenation reactions at ambient reaction conditions. The overall aim of this work was to develop single atom alloy Pd-Cu and Pt-Cu catalysts which are highly active and selective for the selective hydrogenation reaction of phenylacetylene to styrene. The bimetallic catalysts were prepared by a colloidal synthesis of Cu nanoparticles immobilized on gamma-alumina support and the precious metals as a minority species were deposited by galvanic replacement. The prepared materials and synthesis technique were characterized with electron microscopy (TEM), UV-Vis spectroscopy, X-Ray diffraction (XRD), temperature programmed reduction (TPR), BET surface area measurements, chemisorption experiments and X-ray photoelectron spectroscopy (XPS). The resulting catalysts can be described as gamma-Al2O3 supported Cu nanoparticles with a narrow size distribution. The Pt

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

    PubMed

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

    2010-10-01

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

  6. Reverse Micelle Synthesis and Characterization of Supported Pt/Ni Bimetallic Catalysts on gamma-Al2O3

    SciTech Connect

    B Cheney; J Lauterbach; J Chen

    2011-12-31

    Reverse micelle synthesis was used to improve the nanoparticle size uniformity of bimetallic Pt/Ni nanoparticles supported on {gamma}-Al{sub 2}O{sub 3}. Two impregnation methods were investigated to optimize the use of the micelle method: (1) step-impregnation, where Ni nanoparticles were chemically reduced in microemulsion and then supported, followed by Pt deposition using incipient wetness impregnation, and (2) co-impregnation, where Ni and Pt were chemically reduced simultaneously in microemulsion and then supported. Transmission electron microscopy (TEM) was used to characterize the particle size distribution. Atomic absorption spectroscopy (AAS) was used to perform elemental analysis of bimetallic catalysts. Extended X-ray absorption fine structure (EXAFS) measurements were utilized to confirm the formation of the Pt-Ni bimetallic bond in the step-impregnated catalyst. CO pulse chemisorption and Fourier transform infrared spectroscopy (FTIR) studies of 1,3-butadiene hydrogenation in a batch reactor were performed to determine the catalytic activity. Step-impregnated Pt/Ni catalyst demonstrated enhanced hydrogenation activity over the parent monometallic Pt and Ni catalysts due to bimetallic bond formation. The catalyst synthesized using co-impregnation showed no enhanced activity, behaving similarly to monometallic Ni. Overall, our results indicate that reverse micelle synthesis combined with incipient wetness impregnation produced small, uniform nanoparticles with bimetallic bonds that enhanced hydrogenation activity.

  7. Synergistic effect in the oxidation of benzyl alcohol using citrate-stabilized gold bimetallic nanoparticles supported on alumina

    NASA Astrophysics Data System (ADS)

    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.

  8. A new ligand system based on a bipyridine-functionalized calix[4]arene backbone leading to mono- and bimetallic complexes.

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

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

  10. Utilization of greenhouse gases through dry reforming: screening of nickel-based bimetallic catalysts and kinetic studies.

    PubMed

    Fan, Mun-Sing; Abdullah, Ahmad Zuhairi; Bhatia, Subhash

    2011-11-18

    A series of bimetallic catalysts containing nickel supported over MgO-ZrO2 were tested for activity in the dry reforming of carbon dioxide. A nickel-cobalt bimetallic catalyst gave the best performance in terms of conversion and coke resistance from a range of Ni-X bimetallic catalysts, X=Ca, K, Ba, La, and Ce. The nitrogen-adsorption and hydrogen-chemisorption studies showed the Ni-Co bimetallic supported catalyst to have good surface area with high metal dispersion. This contributed to the high catalytic activity, in terms of conversion activity and stability of the catalyst, at an equimolar methane/carbon dioxide feed ratio. The kinetics of methane dry reforming are studied in a fixed-bed reactor over an Ni-Co bimetallic catalyst in the temperature range 700-800 °C by varying the partial pressures of CH4 and CO2. The experimental data were analyzed based on the proposed reaction mechanism using the Langmuir-Hinshelwood kinetic model. The activation energies for methane and carbon dioxide consumption were estimated at 52.9 and 48.1 kJ mol(-1), respectively. The lower value of CO2 activation energy compared to the activation energy of CH4 indicated a higher reaction rate of CO2, which owes to the strong basicity of nanocrystalline support, MgO-ZrO2.

  11. Three-dimensional defocused orientation sensing of single bimetallic core-shell gold nanorods as multifunctional optical probes.

    PubMed

    Kim, Geun Wan; Lee, So Young; Ha, Ji Won

    2017-03-13

    Bimetallic core-shell gold nanorods (AuNRs) are promising multifunctional orientation probes that can be employed in biological and physical studies. This paper presents the optical properties of single AuNRs coated with palladium (Pd) and platinum (Pt) under scattering-based dark-field (DF) microscopy. Strong longitudinal plasmon damping was observed for the bimetallic AuNRs due to Pd and Pt metals on the AuNR surface. Despite the strong plasmon damping, the bimetallic AuNRs yielded characteristic doughnut-shaped scattering patterns under defocused DF microscopy. Interestingly, a solid bright spot appeared at the center of the defocused scattering patterns due to strong damping in the longitudinal plasmon and the increased contribution from the transverse dipoles to the image patterns, which was verified further by a simulation study. Furthermore, the defocused scattering field distributions enabled a determination of the three-dimensional (3D) orientations of single bimetallic AuNRs through a pattern-match analysis technique without angular degeneracy. Therefore, deeper insight into the optical properties and defocused scattering patterns of single bimetallic AuNRs is provided, which can be used to develop multifunctional optical probes that are capable of sensing of the 3D orientation of a probe, biomolecules based on LSPR shift, gas and humidity, etc.

  12. Adsorption of a single gold or silver atom on vanadium oxide clusters.

    PubMed

    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.

  13. Synthesis and electron microscopy characterization of bimetallic nanoparticles and atomically controlled Au nanoclusters

    NASA Astrophysics Data System (ADS)

    Bhattarai, Nabraj

    The properties of metal nanoparticles are controlled by their composition, shape, size and crystalline structure. Nanoparticles and nanoclusters with controlled shape and size were synthesized and investigated using atomic resolution images from aberration corrected scanning/transmission electron microscopy (STEM) and mass spectrometry (MS). Gold-palladium (Au-Pd) core-shell nanocube and triangular nanoparticles were prepared by a seed-mediated growth process and the growth mechanism was studied by varying the volume of Pd precursors added to the Au seed solution. The atomic resolution STEM images revealed that the nanocube is formed from a single-crystal Au seed with rapid growth along <111> directions while the triangular nanoparticles were obtained with growth preferentially along <110> directions rather than <111> direction. The strain generated by the lattice mismatch between fcc-Au and fcc-Pd, is released by Shockley partial dislocations (SPD), combined with stacking faults (SF) that appear at the final (outer) Pd layer. Then, as the shell grows the SPDs and SFs appear at the interface and combine with misfit dislocations, which finally diffuse to the free surfaces due to the alloying of Au into the Pd shell. In related work, magneto-plasmonic gold-cobalt (Au-Co) nanoparticles of diameter 4-nm were generated by a phase-transfer process and investigated by STEM, where the Z-contrast imaging and energy dispersive x-ray spectroscopy (EDS) showed inhomogeneous alloying between Au and Co at the nanoscale. The observed ferromagnetic behavior carries significance in biomedical applications. In addition, selected metallic (Au144(SR)60) and bimetallic (CuAu144) nanoclusters were obtained with thiolate-ligand protection and characterized using optical, MS, and STEM techniques. The optical spectrum and MS results established the monodispersity and purity of the nanoclusters. Another important aspect is that the emergence of broad strong plasmonic band centered near 520

  14. Bismuth-doped tin clusters: experimental and theoretical studies of neutral Zintl analogues.

    PubMed

    Heiles, Sven; Johnston, Roy L; Schäfer, Rolf

    2012-07-26

    The electron count of gas-phase clusters is increased gradually by element substitution in order to mimic the total number of electrons of known stable closo-clusters. A combination of elements from the fourth and fifth group of the periodic table such as Sn and Bi is well-suited for this approach. Hence, these small Sn-Bi clusters are investigated by employing the electric field deflection method. For clusters in the series Sn(M-N)Bi(N) (M = 5-13, N = 1-2), the beam profiles obtained in cryogenic experiments are dominated by beam broadening, indicating the presence of a permanent electric dipole moment that is sensitive to the (rigid) cluster structure. An intensive search for the global minimum structure employing a density functional theory/genetic algorithm method is performed. Dielectric properties for the identified low-energy isomers are computed. The structural and dielectric properties are used in beam profile simulations in order to discuss the experimental data. Comparison of theoretical and experimental results enables identification of the growing pattern of these small bimetallic clusters. For multiply doped clusters, it is concluded that the dopant atoms do not form direct Bi-Bi bonds, but more interestingly, a rearrangement of the cluster skeleton becomes apparent. The structural motifs are different from pure tin clusters but rather are rationalized using the corresponding structures of tin anions or are based on the Wade-Mingos concept. Further evidence for this idea is deduced from nuclear independent chemical shift calculations, which show nearly identical behavior for negatively charged pure and neutral bimetallic clusters. All of these findings are consistent with the idea of neutral Zintl analogues in the gas phase.

  15. Insertion of a single-molecule magnet inside a ferromagnetic lattice based on a 3D bimetallic oxalate network: towards molecular analogues of permanent magnets.

    PubMed

    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.

  16. About the Clusters Program

    EPA Pesticide Factsheets

    The Environmental Technology Innovation Clusters Program advises cluster organizations, encourages collaboration between clusters, tracks U.S. environmental technology clusters, and connects EPA programs to cluster needs.

  17. Catalytic dechlorination of monochlorobenzene with a new type of nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant.

    PubMed

    Han, Yi; Li, Wei; Zhang, Minghui; Tao, Keyi

    2008-05-01

    A unique type of nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant was prepared and used for dechlorination of monochlorobenzene (MCB). The sample Ni(B)/Fe(B) was synthesized by an electroless plating method, in which nanoscale Ni(B) was deposited on the surface of nanoscale Fe(B) synthesized by chemical reduction. The results suggest that the nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant has higher dechlorination efficiency than Ni/Fe(B) catalytic reductant prepared by replacing Fe(B) with Ni(2+) in aqueous solution. The Ni content was found to be an important factor in catalytic dechlorination, with the dechlorination rate increasing with Ni content. The electroless plating method improve the efficiency of the Ni(2+) in the solution. Dechlorination takes place with the existence of nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant via a pseudo-first-order reaction.

  18. X-ray Absorption Spectroscopy of Bimetallic Pt-Re Catalysts for Hydrogenolysis of Glycerol to Propanediols

    SciTech Connect

    O Daniel; A DeLaRiva; E Kunkes; A Datye; J Dumesic; R Davis

    2011-12-31

    Bimetallic Pt-Re nanoparticles supported on Norit carbon were effective at converting aqueous glycerol to 1,3 (34 %) and 1,2 (33 %) propanediol at 443 K under 4 MPa of H{sub 2}. Results from X-ray absorption spectroscopy and analytical transmission electron microscopy confirmed that the nanoparticles were indeed bimetallic, with a particle size less than 2 nm in diameter. The Pt L{sub III} near edge spectra indicated that the Pt was reduced to the metallic state by treatment in H{sub 2} at 473 K, but that a partial positive charge remained on the Re. These oxidized Re species could be associated with charged Re atoms dispersed on the carbon support because spillover of H atoms from Pt was required to reduce Re in the bimetallic particles.

  19. Facile Fabrication of Composition-Tuned Ru-Ni Bimetallics in Ordered Mesoporous Carbon for Levulinic Acid Hydrogenation

    SciTech Connect

    Yang, Ying; Gao, Guang; Zhang, Xin; Li, Fuwei

    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.

  20. Bimetallic and Trimetallic Nanoparticles for Fuel Cell Electrocatalysis

    SciTech Connect

    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.

  1. Data Clustering

    NASA Astrophysics Data System (ADS)

    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

  2. Synthesis and behavior of (Pd + Cu)/Al{sub 2}O{sub 3} catalysts prepared from bimetallic precursors

    SciTech Connect

    Nosova, L.V.; Zaikovskii, V.I.; Kalinkin, A.V.

    1995-05-01

    In hydrogenolysis of ethanol the specific activities of (Pd + Cu)/Al{sub 2}O{sub 3} catalysts are extremely lower than that of Pd/Al{sub 2}O{sub 3} This catalytic nonadditivity suggests that bimetallic particles are formed whose resistance to sintering is lower than that of monometallic ones. Analysis of the reduced (Pd + Cu)/Al{sub 2}O{sub 3} catalyst using electron microscopy, IR spectroscopy, and X-ray photoelectron spectroscopy reveals the presence of compositionally uniform bimetallic particles with a size of 30-40 {angstrom}, the surface of which is enriched in copper.

  3. The synergistic effect in the Fe-Co bimetallic catalyst system for the growth of carbon nanotube forests

    SciTech Connect

    Hardeman, D.; Esconjauregui, S. Cartwright, R.; D'Arsié, L.; Robertson, J.; Bhardwaj, S.; Cepek, C.; Oakes, D.; Clark, J.; Ducati, C.

    2015-01-28

    We report the growth of multi-walled carbon nanotube forests employing an active-active bimetallic Fe-Co catalyst. Using this catalyst system, we observe a synergistic effect by which—in comparison to pure Fe or Co—the height of the forests increases significantly. The homogeneity in the as-grown nanotubes is also improved. By both energy dispersive spectroscopy and in-situ x-ray photoelectron spectroscopy, we show that the catalyst particles consist of Fe and Co, and this dramatically increases the growth rate of the tubes. Bimetallic catalysts are thus potentially useful for synthesising nanotube forests more efficiently.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  5. Synthesis of Highly Dispersed and Highly Stable Supported Au– Pt Bimetallic Catalysts by a Two-Step Method

    SciTech Connect

    Wang, Xiaofeng; Zhao, Haiyan; Wu, Tianpin; Liu, Yuzi; Liang, Xinhua

    2016-12-12

    Highly dispersed and highly stable supported bimetallic catalysts were prepared using a two-step process. Pt nanoparticles (NPs) were first deposited on porous γ-Al2O3 particles by atomic layer deposition (ALD). Au NPs were synthesized by using gold(III) chloride as the Au precursor, and then immobilized on ALD Pt/γ-Al2O3 particles. The Au–Pt bimetallic catalysts were highly active and highly stable in a vigorously stirred liquid phase reaction of glucose oxidation.

  6. Comparative toxicity study of Ag, Au, and Ag-Au bimetallic nanoparticles on Daphnia magna.

    PubMed

    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

  7. Ultrafast excited-state dynamics in shape- and composition-controlled gold–silver bimetallic nanostructures

    DOE PAGES

    Zarick, Holly F.; Boulesbaa, Abdelaziz; Talbert, Eric M.; ...

    2017-02-01

    In this paper, we have examined the ultrafast dynamics of shape- and composition-controlled bimetallic Au/Ag core/shell nanostructures with transient absorption spectroscopy (TAS) as a function of Ag layer thickness (0–15 nm) and pump excitation fluence (50–500 nJ/pulse). Our synthesis approach generated both bimetallic nanocubes and nanopyramids with distinct dipolar plasmon resonances and plasmon dephasing behavior at the resonance. Lifetimes obtained from TAS at low powers (50 nJ/pulse) demonstrated minimal dependence on the Ag layer thickness, whereas at high power (500 nJ/pulse) a rise in electron–phonon coupling lifetime (τ1) was observed with increasing Ag shell thickness for both nanocubes and nanopyramids.more » This is attributable to the stronger absorption of the 400 nm pump pulse with higher Ag content, which induced higher electron temperatures. The phonon–phonon scattering lifetime (τ2) also rises with increasing Ag layer, contributed both by the increasing size of the Au/Ag nanostructures as well as by surface chemistry effects. Further, we observed that even the thinnest, 2 nm, Ag shell strongly impacts both τ1 and τ2 at high power despite minimal change in overall size, indicating that the nanostructure composition also strongly impacts the thermalization temperature following absorption of 400 nm light. We also observed a shape-dependent trend at high power, where τ2 increased for the nanopyramids with increasing Ag shell thickness and nanostructure size, but bimetallic nanocubes demonstrated an unexpected decrease in τ2 for the thickest, 15 nm, Ag shell. This was attributed to the larger number of corners and edges in the nanocubes relative to the nanopyramids.« less

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

    PubMed

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

    2014-09-10

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

  9. Growth of large aspect ratio AuAg bimetallic nanowires on Si(110) substrate

    NASA Astrophysics Data System (ADS)

    Bhukta, Anjan; Guha, Puspendu; Satpati, Biswarup; Maiti, Paramita; Satyam, Parlapalli V.

    2017-06-01

    Large aspect ratio bimetallic nanowire structures comprise potential applications in areas such as higher catalytic activity and surface Raman enhancement spectroscopy (SERS) substrates. By using the highly anisotropic ultra-clean Si(110) surface and with initial growth of sub monolayer (ML) Ag on such surface, a high aspect ratio AuAg bimetallic nanostructures can be formed. We report on the formation of large aspect ratio (>7.2 ± 0.8) AuAg nanowires on ultra-clean Si(110) surfaces using 0.5 ML Ag followed by 3.0 ML Au using molecular beam epitaxy (MBE) at a growth temperature of 300 °C. Under similar growth conditions without pre-deposition of Ag and only with deposition of 3.0 ML of Au consequences smaller aspect ratio (2.1 ± 0.1) monometallic Au nanostructures. The enhancement in aspect ratio of the nanostructures is attributed to the formation of one dimensional Ag layer (prior to Au growth) and Au-Ag bimetallic intermixing at elevated temperature. Considering deposition of 3.0 ML Au, a regime of substrate temperature ≈ 270-330 °C is found to be optimum to growth some of high aspect ratio (>25.0) AuAg nanowires as well. Exterior of this regime, at lower temperature due to low mobility of the ad-atoms and at higher temperature due to probable inter-diffusion of Ag, such extremely high aspect ratio AuAg nanowires found to be infrequent to grow. For growth at substrate temperature 300 °C, mean aspect ratio of the AuAg nanostructures is gradually increased in accordance with Au thickness up to 3.0 ML due to preferential accumulation of ad-atoms (Au, Ag) along Si < 1 1 bar 0 > and thereafter reduces for adequate accumulation along Si < 001 > .

  10. Surface plasmon polariton assisted optical switching in noble bimetallic nanoparticle system

    SciTech Connect

    Dhara, Sandip E-mail: chenkh@pub.iams.sinica.edu.tw; Lu, C.-Y.; Tu, W.-S.; Magudapathy, P.; Huang, Y.-F.; Chen, K.-H. E-mail: chenkh@pub.iams.sinica.edu.tw

    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.

  11. Surface plasmon polariton assisted optical switching in noble bimetallic nanoparticle system

    NASA Astrophysics Data System (ADS)

    Dhara, Sandip; Lu, C.-Y.; Magudapathy, P.; Huang, Y.-F.; Tu, W.-S.; Chen, K.-H.

    2015-01-01

    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+ is introduced first in the soda glass matrix by ion exchange technique. Subsequently, 400 keV Au+ is implanted in the sample for different fluences, which is followed by an ion beam annealing process using 1 MeV Si+ at a fixed fluence of 2 × 1016 ions.cm-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.

  12. Synthesis and ECL performance of highly efficient bimetallic ruthenium tris-bipyridyl complexes.

    PubMed

    Sun, Shiguo; Li, Fusheng; Liu, Fengyu; Yang, Xue; Fan, Jiangli; Song, Fengling; Sun, Licheng; Peng, Xiaojun

    2012-10-28

    In order to find the ideal carbon chain linkage number n for achieving the highest ECL in bimetallic ruthenium tris-bipyridyl complexes, a series of novel complexes [(bpy)(2)Ru(bpy')(CH(2))(n)(bpy')Ru(bpy)(2)](4+) (, where bpy is 2,2'-bipyridyl, n = 10, 12, 14) for a coreactant electrochemiluminescence (ECL) system have been synthesized. Their ECL properties at a Au electrode have been studied in 0.1 M phosphate buffer by using tripropylamine (TPrA), 2-(dibutylamino)ethanol (DBAE) and melamine as the coreactant, to compare with that of the previously reported bimetallic ruthenium analogous complex [(bpy)(2)Ru(bpy')(CH(2))(8)(bpy')Ru(bpy)(2)](4+). The results demonstrate that the ECL intensity depends largely on the length of the saturated carbon chain linkage number n. The highest ECL is reached when n = 10, suggesting that a synergistic effect on ECL enhancement co-exists between the two intramolecular linked ruthenium activating centers. Density functional theory (DFT) calculation demonstrated that the optimized bond distances between Ru and N(bpy') are the longest both in the ground and the excited triplet states in the case of n = 10, while those for Ru and N(bpy) are the shortest in the excited triplet states. All these factors may be responsible for the above mentioned results. This study provided a methodology to further improve and tune ECL efficiency by using bimetallic ruthenium complexes linked by a flexible saturated carbon chain.

  13. A molecular metal ferromagnet from the organic donor bis(ethylenedithio)tetraselenafulvalene and bimetallic oxalate complexes.

    PubMed

    Alberola, Antonio; Coronado, Eugenio; Galán-Mascarós, José R; Giménez-Saiz, Carlos; Gómez-García, Carlos J

    2003-09-10

    A new dual-function hybrid molecular material has been obtained from the organic donor bis(ethylenedithio)tetraselenafulvalene and the honeycomb oxalate-based bimetallic network [MnCr(ox)3]-. This multilayer material consists of layers of the inorganic anionic 2D network, responsible for the appearance of ferromagnetic ordering below 5.3 K, alternating with segregated layers of the organic cation radical responsible for the transport properties: metal-like conductivity is observed from room temperature down to 150 K.

  14. Bimetallic platinum-iron electrocatalyst supported on carbon fibers for coal electrolysis

    NASA Astrophysics Data System (ADS)

    Yu, Ping; Botte, Gerardine G.

    2015-01-01

    A novel bimetallic Pt-Fe electrode supported on carbon fibers (CFs) was prepared by chemical impregnation/reduction and evaluated for the electrolysis of coal to produce hydrogen. Characterization of the electrocatalyst was performed using X-ray Diffraction, Scanning Electron Microscopy, and Energy Dispersive Spectroscopy. The synthesized Pt-Fe particles were well dispersed on the surface of the CFs. The addition of Fe to the catalyst enhanced the electrooxidation of coal when compared to Pt alone. PtFe (1:1) supported on carbon fibers exhibited superior catalytic activity towards the conversion of coal than PtFe (7:3) and PtFe (3:7).

  15. Development of ruthenium-based bimetallic electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, Lingyun; Lee, Jong-Won; Popov, Branko N.

    Ruthenium-based bimetallic electrocatalysts with non-noble metals such as Ti, Cr, Fe, Co and Pb were synthesized on a porous carbon support using a chelation process. Rotating ring disk electrode measurements indicated that RuFeN x/C showed the catalytic activity and selectivity toward the four-electron reduction of oxygen to water comparable to those of the conventional Pt/C catalysts. The performance of the membrane-electrode assembly prepared with the RuFeN x/C cathode catalyst was evaluated for 150 h of continuous operation.

  16. Enhanced antibacterial activity of bimetallic gold-silver core-shell nanoparticles at low silver concentration

    NASA Astrophysics Data System (ADS)

    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. Unprecedented Carbonato Intermediates in Cyclic Carbonate Synthesis Catalysed by Bimetallic Aluminium(Salen) Complexes.

    PubMed

    Castro-Osma, José A; North, Michael; Offermans, Willem K; Leitner, Walter; Müller, Thomas E

    2016-04-21

    The mechanism by which [Al(salen)]2 O complexes catalyse the synthesis of cyclic carbonates from epoxides and carbon dioxide in the absence of a halide cocatalyst has been investigated. Density functional theory (DFT) studies, mass spectrometry and (1) H NMR, (13) C NMR and infrared spectroscopies provide evidence for the formation of an unprecedented carbonato bridged bimetallic aluminium complex which is shown to be a key intermediate for the halide-free synthesis of cyclic carbonates from epoxides and carbon dioxide. Deuterated and enantiomerically-pure epoxides were used to study the reaction pathway. Based on the experimental and theoretical results, a catalytic cycle is proposed.

  18. Bimetallic PtxCoy nanoparticles with curved faces for highly efficient hydrogenation of cinnamaldehyde

    NASA Astrophysics Data System (ADS)

    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

  19. Controlling bimetallic nanostructures by the microemulsion method with subnanometer resolution using a prediction model

    SciTech Connect

    Buceta, David; Tojo, Concha; Vukmirovic, Miomir B.; Deepak, F. Leonard; Lopez-Quintela, M. Arturo

    2015-06-02

    In this study, we present a theoretical model to predict the atomic structure of Au/Pt nanoparticles synthesized in microemulsions. Excellent concordance with the experimental results shows that the structure of the nanoparticles can be controlled at sub-nanometer resolution simply by changing the reactants concentration. The results of this study not only offer a better understanding of the complex mechanisms governing reactions in microemulsions, but open up a simple new way to synthesize bimetallic nanoparticles with ad-hoc controlled nanostructures.

  20. Fractal bimetallic plasmonic structures obtained by laser deposition of colloidal nanoparticles

    NASA Astrophysics Data System (ADS)

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

    2017-09-01

    We produce bimetallic Au:Ag thin films by laser irradiation of the mixed solutions. After several laser scans, granular nanometric films are found to grow with a well-controlled composition, thickness and morphology. By changing laser scanning parameters, the film morphology can be varied from island structures to quasi-periodic arrays. The optical properties of the deposited structures are found to depend on the film composition, thickness and spacing between the particles. The transmittance spectra of the deposited films are shown to be governed by their morphology.

  1. Electrical performances of pyroelectric bimetallic strip heat engines describing a Stirling cycle

    NASA Astrophysics Data System (ADS)

    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.

  2. A hydride-induced-reduction strategy for fabricating palladium-based core-shell bimetallic nanocrystals

    NASA Astrophysics Data System (ADS)

    Wang, Xingli; Wu, Binghui; Chen, Guangxu; Zhao, Yun; Liu, Pengxin; Dai, Yan; Zheng, Nanfeng

    2014-05-01

    One key challenge in making high-quality bimetallic nanocrystals is to prevent self-nucleation of individual metal components. We report in this work an effective seeded growth strategy that uses activated hydrogen atoms as the reducing agent to prepare core-shell bimetallic nanocrystals. In the developed method, Pd nanocrystals serve as the seed and catalyst as well to activate H2 for the reductive deposition of Ag. The unique feature of the developed method is that the activated hydrogen atoms are confined on the surface of the Pd seeds. Consequently, the self-nucleation of Ag is effectively inhibited so that the deposition of Ag occurs only on Pd. The mechanism studies reveal that reductive growth of Ag on Pd seeds proceeds until the Pd surface is fully covered by Ag. The Ag/Pd ratio in the prepared Pd@Ag nanocrystals is readily fine-tuned by the amount of AgNO3 or H2. The method is effective for depositing Ag on Pd nanocrystal seeds with different morphologies such as nanosheets, nanocubes, tetrahedra and nanowires. More importantly, the deposition of Ag on Pd nanowires allows preparation of flexible transparent electrode material with sheet electronic conductivity of 271 S sq-1 at a transmittance of over 90%.One key challenge in making high-quality bimetallic nanocrystals is to prevent self-nucleation of individual metal components. We report in this work an effective seeded growth strategy that uses activated hydrogen atoms as the reducing agent to prepare core-shell bimetallic nanocrystals. In the developed method, Pd nanocrystals serve as the seed and catalyst as well to activate H2 for the reductive deposition of Ag. The unique feature of the developed method is that the activated hydrogen atoms are confined on the surface of the Pd seeds. Consequently, the self-nucleation of Ag is effectively inhibited so that the deposition of Ag occurs only on Pd. The mechanism studies reveal that reductive growth of Ag on Pd seeds proceeds until the Pd surface is fully

  3. Synthesis of bimetallic gold/silver nanoparticles via in situ seeding

    NASA Astrophysics Data System (ADS)

    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.

  4. The Golden Crown: A Single Au Atom that Boosts the CO Oxidation Catalyzed by a Palladium Cluster on Titania Surfaces

    SciTech Connect

    Zhang, Jin; Alexandrova, Anastassia N.

    2013-07-18

    We show that at the subnano scale, the catalytic properties of surface-supported clusters can be majorly impacted by strategic doping and the choice for the supporting surface. This is a first-principles investigation of CO oxidation catalyzed by two subnanoclusters, Pd4Au and Pd5, deposited on rutile TiO2(110) surfaces. The titania surface was found to participate in the reaction directly via providing additional reaction pathways. The bimetallic cluster Pd4Au shows enhanced catalytic activity, whereas the monometallic Pd5 is poisoned and deactivated in the presence of CO and oxygen, and this trend is reversed from that in the gas phase.

  5. Thermal Dihydrogen Activation by a Closed-Shell AuCeO2(+) Cluster.

    PubMed

    Meng, Jing-Heng; He, Sheng-Gui

    2014-11-06

    Laser-ablation-generated AuCeO2(+) and CeO2(+) oxide clusters were mass-selected using a quadrupole mass filter and reacted with H2 in an ion trap reactor at ambient conditions. The reactions were characterized by mass spectrometry and density functional theory calculations. The gold-cerium bimetallic oxide cluster AuCeO2(+) is more reactive in H2 activation than the pure cerium oxide cluster CeO2(+). The gold atom is the active adsorption site and facilitates the heterolytic cleavage of H2 in collaboration with the separated O(2-) ion of the CeO2 support. To the best of our knowledge, this is the first example of thermal H2 activation by a closed-shell atomic cluster, which provides molecular-level insights into the single gold atom catalysis over metal oxide supports.

  6. Melting behaviour of gold-platinum nanoalloy clusters by molecular dynamics simulations

    SciTech Connect

    Ong, Yee Pin; Yoon, Tiem Leong; Lim, Thong Leng

    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.

  7. Acid clusters

    SciTech Connect

    Keesee, R.G.; Castleman, A.W. Jr.

    1986-04-01

    Molecular clusters can be considered to be the smallest size range of an aerosol particle size distribution. Nucleation from the gas phase to particles or droplets involves the formation of clusters in the initial stages. Consequently, knowledge of the properties and formation of clusters containing acids contribute to an understanding of acid rain. This paper presents an overview of results obtained in the laboratory on the formation and stability of both neutral and ionized acid clusters. With free jet expansion techniques, the authors have produced clusters of aqueous nitric acid, aqueous hydrochloric acid, aqueous sulfuric acid, acetic acid and aqueous sulfur dioxide. For analogy to buffering, the formation of clusters containing ammonia have also been examined. These have included ammonia with aqueous nitric acid, hydrogen sulfide and sulfur dioxide. The basic experiment involves expansion of vapor through a nozzle, collimation of the jet with a skimmer to form a well-directed molecular beam, and detection of clusters via electron impact ionization and mass spectrometry. Some variations include the introduction of a reactive gas into vacuum near the expansion as described elsewhere and the implementation of an electrostatic quadrupolar field to examine the polarity of the neutral clusters.

  8. SERRS and Absorption Spectra of Pyridine on AumAgn (m+n=6) Bimetallic Nanoclusters: Substrate Composition and Applied Electric Field Effects.

    PubMed

    Li, Quanjiang; Chen, Maodu

    2017-09-08

    Surface-enhanced Raman scattering (SERS) and absorption spectra of the pyridine molecule adsorbed on AumAgn (m+n=6) bimetallic cluster are theoretically investigated by time-dependent density functional theory (TD-DFT). The contributions of static chemical enhancement to the ground-state system are analyzed, and the static Raman intensity of Py-AumAgn complexes are enhanced on the order of 10. A method of visualization on charge transfer is used to distinguish the contributions of charge-transfer (CT) enhancement and electromagnetic enhancement (EM). The intensity of surface-enhanced resonance Raman scattering (SERRS) spectroscopy of Py-AumAgn are strongly enhanced on the order of 103-105, compared with the static Raman intensity of pyridine. The influence of static external electric field on SERS is investigated by calculating the optical properties of Py-Au3Ag3 complex. The intensity of SERRS spectra and normal Raman spectra can be significantly enhanced by the positive electric fields, and the intensities of specific Raman vibrational modes could be selectively enhanced or weakened by tuning the direction and strength of the static electric field applied on Py-Au3Ag3. © 2017 IOP Publishing Ltd.

  9. Mechanical properties of bimetallic crystalline and nanostructured nanowires.

    PubMed

    Hou, Marc; Melikhova, Oksana; Pisov, Stoyan

    2008-01-01

    Nanowires are basic components of interconnects at the nanoscale level in electronic as well as in electromechanical devices. Presently, there is a fast growing interest in their synthesis as well as in their mechanical testing. Focused ion beams now allow machining pillars with diameters as small as a few tens of nanometres and nanoindenter systems allow measuring strains at the atomic scale and compressive stresses up to the 10 GPa range. Such pillars typically contain less than millions of atoms, which makes their modelling and the modelling of their mechanical properties at the atomic scale realistic. A few Molecular Dynamics studies are presently available, discussing deformation mechanisms in thin narrow crystalline nanowires, but the literature about nanoalloy wires and nanostructured wires, as they can be synthesized from clusters, is almost non-existent. In the latter, the dislocation activity may be inhibited, leading to specific mechanical properties. By means of large scale computations, we use Ni3A1 to discuss the mechanical properties of crystalline and nanostructured nanowires. We also compare wires to their bulk counterparts. Both isothermal and isoenergetic whereby mechanical work converts into heat in the system-deformation mechanisms are considered. The comparison between pair correlation functions, stress distributions, configuration analysis and strain stress relations capture most of the stress-induced evolution mechanisms of nanowires with different diameters and structures, including elastic properties, dislocation activity, grain rotation and boundary motion, local melting, superplasticity and fracture. A structural transition which may be martensitic is predicted for the first time at the nanoscale level, suggesting possible shape memory properties of nanoalloy nanowires.

  10. Homogeneity and elemental distribution in self-assembled bimetallic Pd-Pt aerogels prepared by a spontaneous one-step gelation process.

    PubMed

    Oezaslan, M; Liu, W; Nachtegaal, M; Frenkel, A I; Rutkowski, B; Werheid, M; Herrmann, A-K; Laugier-Bonnaud, C; Yilmaz, H-C; Gaponik, N; Czyrska-Filemonowicz, A; Eychmüller, A; Schmidt, T J

    2016-07-27

    Multi-metallic aerogels have recently emerged as a novel and promising class of unsupported electrocatalyst materials due to their high catalytic activity and improved durability for various electrochemical reactions. Aerogels can be prepared by a spontaneous one-step gelation process, where the chemical co-reduction of metal precursors and the prompt formation of nanochain-containing hydrogels, as a preliminary stage for the preparation of aerogels, take place. However, detailed knowledge about the homogeneity and chemical distribution of these three-dimensional Pd-Pt aerogels at the nano-scale as well as at the macro-scale is still unclear. Therefore, we used a combination of spectroscopic and microscopic techniques to obtain a better insight into the structure and elemental distribution of the various Pd-rich Pd-Pt aerogels prepared by the spontaneous one-step gelation process. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) in combination with energy-dispersive X-ray spectroscopy (EDX) were employed in this work to uncover the structural architecture and chemical composition of the various Pd-rich Pd-Pt aerogels over a broad length range. The Pd80Pt20, Pd60Pt40 and Pd50Pt50 aerogels showed heterogeneity in the chemical distribution of the Pt and Pd atoms inside the macroscopic nanochain-network. The features of mono-metallic clusters were not detected by EXAFS or STEM-EDX, indicating alloyed nanoparticles. However, the local chemical composition of the Pd-Pt alloys strongly varied along the nanochains and thus within a single aerogel. To determine the electrochemically active surface area (ECSA) of the Pd-Pt aerogels for application in electrocatalysis, we used the electrochemical CO stripping method. Due to their high porosity and extended network structure, the resulting values of the ECSA for the Pd-Pt aerogels were higher than that for

  11. Removal of trichloroethylene DNAPL trapped in porous media using nanoscale zerovalent iron and bimetallic nanoparticles: direct observation and quantification.

    PubMed

    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.

  12. Fe-Co bimetallic alloy nanoparticles as a highly active peroxidase mimetic and its application in biosensing.

    PubMed

    Chen, Yujin; Cao, Haiyan; Shi, Wenbing; Liu, Hong; Huang, Yuming

    2013-06-04

    This article presents a new enzyme-mimic activity of non-noble metal-based bimetallic Fe-Co NPs. This type of enzyme-mimic exhibits much higher affinity to H2O2 over other NPs-based peroxidase mimetics by at least one order of magnitude due to the synergistic effects between the two metals.

  13. Final Technical Report: First Principles Investigations for the Ensemble Effects of PdAu and PtAu Bimetallic Nanocatalysts

    SciTech Connect

    Ruqian Wu

    2012-05-18

    Bimetallic surfaces with tunable chemical properties have attracted broad attention in recent years due to their ample potential for heterogeneous catalysis applications. The local chemical properties of constituents are strongly altered from their parent metals by 'ligand effect', a term encompassing the influences of charge transfer, orbital rehybridization and lattice strain. In comparison to the aforementioned, the 'ensemble effect' associated with particular arrangements of the active constituents have received much less attention, despite their notable importance towards the determination of reactivity and selectivity of bimetallic catalysts. We performed theoretical studies for understanding the ensemble effects on bimetallic catalysis: (i) simulations for the formation of different ensembles on PdAu and PtAu nanoclusters; (ii) studies of the size, shape, and substrate dependence of their electronic properties; and (iii) simulations for model reactions such as CO oxidation, methanol, ethylene and water dehydrogenation on PdAu and PtAu nanoclusters. In close collaboration with leading experimental groups, our theoretical research elucidated the fundamentals of Au based bimetallic nanocatalysts.

  14. Core-shell Rh-Pt nanocubes: A model for studying compressive strain effects in bimetallic nanocatalysts

    NASA Astrophysics Data System (ADS)

    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. Action of bimetallic nanocatalysts under reaction conditions and during catalysis: evolution of chemistry from high vacuum conditions to reaction conditions.

    PubMed

    Tao, Franklin Feng; Zhang, Shiran; Nguyen, Luan; Zhang, Xueqiang

    2012-12-21

    Bimetallic catalysts are one of the main categories of metal catalysts due to the tunability of electronic and geometric structures through alloying a second metal. The integration of a second metal creates a vast number of possibilities for varying the surface structure and composition of metal catalysts toward designing new catalysts. It is well acknowledged that the surface composition, atomic arrangement, and electronic state of bimetallic catalysts could be different from those before a chemical reaction or catalysis based on ex situ studies. Thanks to advances in electron-based surface analytical techniques, the surface chemistry and structure of bimetallic nanoparticles can be characterized under reaction conditions and during catalysis using ambient pressure analytical techniques including ambient pressure XPS, ambient pressure STM, X-ray absorption spectroscopy and others. These ambient pressure studies revealed various restructurings in the composition and arrangement of atoms in the surface region of catalysts under reaction conditions or during catalysis compared to that before reaction. These restructurings are driven by thermodynamic and kinetic factors. The surface energy of the constituent metals and adsorption energy of reactant molecules or dissociated species on a metal component are two main factors from the point of view of thermodynamics. Correlations between the authentic surface structure and chemistry of catalysts during catalysis and simultaneous catalytic performance were built for understanding catalytic mechanisms of bimetallic catalysts toward designing new catalysts with high activity, selectivity, and durability.

  16. Effect of mono- and bimetallic nanoparticles Fe, Ni, & Fe/Ni based on carbon nanocomposites on electrocatalytic properties of anodes

    NASA Astrophysics Data System (ADS)

    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.

  17. Kinetically controlled overgrowth of Ag or Au on Pd nanocrystal seeds: from hybrid dimers to nonconcentric and concentric bimetallic nanocrystals.

    PubMed

    Zhu, Cun; Zeng, Jie; Tao, Jing; Johnson, Matthew C; Schmidt-Krey, Ingeborg; Blubaugh, Lynn; Zhu, Yimei; Gu, Zhongze; Xia, Younan

    2012-09-26

    This article describes a systematic study of the nucleation and growth of Ag (and Au) on Pd nanocrystal seeds. By carefully controlling the reaction kinetics, the newly formed Ag atoms could be directed to selectively nucleate and then epitaxially grow on a specific number (ranging from one to six) of the six faces on a cubic Pd seed, leading to the formation of bimetallic nanocrystals with a variety of different structures. In addition to changing the injection rate of precursor, we also systematically investigated other reaction parameters including the capping agent, reductant, and reaction temperature. Our results suggest that the site-selective growth of Ag on cubic Pd seeds could be readily realized by optimizing these reaction parameters. On the basis of the positions of Pd seeds inside the bimetallic nanocrystals as revealed by TEM imaging and elemental mapping, we could identify the exact growth pathways and achieve a clear and thorough understanding of the mechanisms. We have successfully applied the same strategy based on kinetic control to cubic Pd seeds with different sizes and octahedral Pd seeds of one size to generate an array of novel bimetallic nanocrystals with well-controlled structures. With cubic Pd seeds as an example, we have also extended this strategy to the Pd-Au system. We believe this work will provide a promising route to the fabrication of bimetallic nanocrystals with novel structures and properties for applications in plasmonics, catalysis, and other areas.

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

    SciTech Connect

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

    2008-01-01

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

  19. Hydroxylation of Benzene via C-H Activation Using Bimetallic CuAg@g-C3N4

    EPA Science Inventory

    A photoactive bimetallic CuAg@g-C3N4 catalyst system has been designed and synthesized by impregnating copper and silver nanoparticles over the graphitic carbon nitride surface. Its application has been demonstrated in the hydroxylation of benzene under visible light.

  20. Asymmetric Synthesis of Ramariolides A and C through Bimetallic Cascade Cyclization and Z-E Isomerization Reaction.

    PubMed

    Pal, Pratik; Nanda, Samik

    2017-03-03

    A short and flexible asymmetric synthesis of ramariolides A and C was accomplished. A bimetallic catalytic system consisting of Pd-Cu-mediated cascade cyclization, unprecedented Z-E isomerization by a Ru-based metathesis catalyst, and late-stage stereoselective epoxidation are the key steps involved in the synthesis.

  1. Dry Reforming of Ethane and Butane with CO2 over PtNi/CeO2 Bimetallic Catalysts

    DOE PAGES

    Yan, Binhang; Yang, Xiaofang; Yao, Siyu; ...

    2016-09-21

    Dry reforming is a potential process to convert CO2 and light alkanes into syngas (H2 and CO), which can be subsequently transformed to chemicals and fuels. Here in this work, PtNi bimetallic catalysts have been investigated for dry reforming of ethane and butane using both model surfaces and supported powder catalysts. The PtNi bimetallic catalyst shows an improvement in both activity and stability as compared to the corresponding monometallic catalysts. The formation of PtNi alloy and the partial reduction of Ce4+ to Ce3+ under reaction conditions are demonstrated by in-situ Ambient Pressure X-ray Photoemission Spectroscopy (AP-XPS), X-ray Diffraction (XRD) andmore » X-ray Absorption Fine Structure (XAFS) measurements. A Pt-rich bimetallic surface is revealed by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) following CO adsorption. Combined in-situ experimental results and Density Functional Theory (DFT) calculations suggest that the Pt-rich PtNi bimetallic surface structure would weaken the binding of surface oxygenates/carbon species and reduce the activation energy for C-C bond scission, leading to an enhanced dry reforming activity.« less

  2. Bimetallic PtxCoy nanoparticles with curved faces for highly efficient hydrogenation of cinnamaldehyde.

    PubMed

    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.

  3. Seed germination and biochemical profile of Silybum marianum exposed to monometallic and bimetallic alloy nanoparticles.

    PubMed

    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.

  4. Catalytically Active Bimetallic Nanoparticles Supported on Porous Carbon Capsules Derived From Metal-Organic Framework Composites.

    PubMed

    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.

  5. Electrospun carbon nanofibers decorated with Ag-Pt bimetallic nanoparticles for selective detection of dopamine.

    PubMed

    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.

  6. Oxidizing capacity of periodate activated with iron-based bimetallic nanoparticles.

    PubMed

    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.

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

    PubMed

    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.

  8. Performance of vertically oriented graphene supported platinum-ruthenium bimetallic catalyst for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Bo, Zheng; Hu, Dan; Kong, Jing; Yan, Jianhua; Cen, Kefa

    2015-01-01

    This work reports the electrocatalytic performance of vertically oriented graphene (VG) supported Pt-Ru bimetallic catalysts toward methanol oxidation reaction (MOR). Dense networks of VG are directly synthesized on carbon paper (CP) via a microwave plamsa-enhanced chemical vapor deposition (PECVD) method. A repeated pulse potentials approach is applied in a conventional three-electrode electrochemical system for the co-electrodeposition of Pt-Ru bimetallic nanoparticles. It is found that, the decoration of VG can simultaneously lead to a ∼3.5 times higher catalyst mass loading and a ∼50% smaller nanoparticle size than the pristine CP counterparts. An optimum Pt molar ratio of 83.4% in the deposits, achieved with a [H2PtCl6]:[RuCl3] of 1:1 in the electrolyte, is clarified with synthetically considering the mass specific activity, CO tolerance, and catalytic stability. According to Tafel analysis and cyclic voltammetry (CV) tests, the Pt-Ru/VG catalyst with the optimized Pt molar ratio can realize a faster methanol dehydrogenation than Pt/VG, and present a significantly enhanced catalytic activity (maximum current density of 339.2 mA mg-1) than those using pristine CP and Vulcan XC-72 as the supports.

  9. Selective growth of Ag nanodewdrops on Au nanostructures: a new type of bimetallic heterostructure.

    PubMed

    Gao, Li; Fan, Louzhen; Zhang, Jian

    2009-10-06

    A new type of bimetallic Au-Ag heterostructured material was prepared by a selective growing strategy of a Ag nanodewdrop on the petal tip of a Au flower using an electrochemical method. The whole process was strictly controlled by forming the reactive tip of the flower petal and passivating the facet along the body of the metal petal using poly(vinyl pyrrolidone) (PVP) coating film. The formed Au-Ag heterostructured flowers (HSFs) were observed to be about 2 microm in diameter and have the Ag particles of about 50 nm settled on the tips of Au petals. The Au-Ag HSFs were found to display the superior properties on the surface-enhanced Raman scattering (SERS). The presence of Ag nanodewdrops could also facilitate the oxidation of Ru(bpy)3(2+) complex in electrogenerated chemiluminescence (ECL) measurements and dramatically enhance the emission intensity. The features of Au-Ag HSFs can promise a new type of heterogeneous bimetallic alloy material for the potential applications in chemical and biological sensors.

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

    PubMed Central

    Gao, Li

    2009-01-01

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

  11. Improving Light Harvesting in Dye-Sensitized Solar Cells Using Hybrid Bimetallic Nanostructures

    SciTech Connect

    Zarick, Holly F.; Erwin, William R.; Boulesbaa, Abdelaziz; Hurd, Olivia K.; Webb, Joseph A.; Puretzky, Alexander A.; Geohegan, David B.; Bardhan, Rizia

    2016-01-25

    In this paper, we demonstrate improved light trapping in dye-sensitized solar cells (DSSCs) with hybrid bimetallic gold core/silver shell nanostructures. Silica-coated bimetallic nanostructures (Au/Ag/SiO2 NSs) integrated in the active layer of DSSCs resulted in 7.51% power conversion efficiency relative to 5.97% for reference DSSCs, giving rise to 26% enhancement in device performance. DSSC efficiencies were governed by the particle density of Au/Ag/SiO2 NSs with best performing devices utilizing only 0.44 wt % of nanostructures. We performed transient absorption spectroscopy of DSSCs with variable concentrations of Au/Ag/SiO2 NSs and observed an increase in amplitude and decrease in lifetime with increasing particle density relative to reference. Finally, we attributed this trend to plasmon resonant energy transfer and population of the singlet excited states of the sensitizer molecules at the optimum concentration of NSs promoting enhanced exciton generation and rapid charge transfer into TiO2.

  12. Noble-metal-free bimetallic alloy nanoparticle-catalytic gasification of phenol in supercritical water

    DOE PAGES

    Jia, Lijuan; Yu, Jiangdong; Chen, Yuan; ...

    2017-02-27

    The exploration of non-noble-metal catalysts for high efficiency gasification of biomass in supercritical water (SCW) is of great significance for the sustainable development. A series of Ni–M (M = Co or Zn) bimetallic nanoparticles supported on graphitized carbon black were synthesized and examined as catalysts for gasification of phenol in SCW. We found that a nearly complete gasification of phenol can be achieved even at a low temperature of 450 °C with the bimetallic nanoparticles catalysts. Kinetic study indicated the activation energy for phenol gasification were 20.4 ± 2.6 and 43.6 ± 2.6 kJ/mol for Ni20Zn15 and Ni20Co15 catalyst, respectively.more » Furthermore, XRD, XPS and TEM were performed to characterize the catalysts and the results showed the formation of NiCo and NiZn alloy phase. Catalyst recycling experiments were also conducted to evaluate the stability of the catalysts. The characterization of used catalysts suggest that the severe agglomeration of nanoparticles leads to the decrease in catalytic activity.« less

  13. Bimetallic PtSn/C catalysts obtained via SOMC/M for glycerol steam reforming.

    PubMed

    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.

  14. Superhydrophobic surface with hierarchical architecture and bimetallic composition for enhanced antibacterial activity.

    PubMed

    Zhang, Mei; Wang, Ping; Sun, Hongyan; Wang, Zuankai

    2014-12-24

    Developing robust antibacterial materials is of importance for a wide range of applications such as in biomedical engineering, environment, and water treatment. Herein we report the development of a novel superhydrophobic surface featured with hierarchical architecture and bimetallic composition that exhibits enhanced antibacterial activity. The surface is created using a facile galvanic replacement reaction followed by a simple thermal oxidation process. Interestingly, we show that the surface's superhydrophobic property naturally allows for a minimal bacterial adhesion in the dry environment, and also can be deactivated in the wet solution to enable the release of biocidal agents. In particular, we demonstrate that the higher solubility nature of the thermal oxides created in the thermal oxidation process, together with the synergistic cooperation of bimetallic composition and hierarchical architecture, allows for the release of metal ions in a sustained and accelerated manner, leading to enhanced antibacterial performance in the wet condition as well. We envision that the ease of fabrication, the versatile functionalities, and the robustness of our surface will make it appealing for broad applications.

  15. Rheotaxis of Bimetallic Micromotors Driven by Chemical-Acoustic Hybrid Power.

    PubMed

    Ren, Liqiang; Zhou, Dekai; Mao, Zhangming; Xu, Pengtao; Huang, Tony Jun; Mallouk, Thomas E

    2017-09-18

    Rheotaxis is a common phenomenon in nature that refers to the directed movement of micro-organisms as a result of shear flow. The ability to mimic natural rheotaxis using synthetic micro/nanomotors adds functionality to enable their applications in biomedicine and chemistry. Here, we present a hybrid strategy that can achieve both positive and negative rheotaxis of synthetic bimetallic micromotors by employing a combination of chemical fuel and acoustic force. An acoustofluidic device is developed for the integration of the two propulsion mechanisms. Using acoustic force alone, bimetallic microrods are propelled along the bottom surface in the center of a fluid channel. The leading end of the microrod is always the less dense end, as established in earlier experiments. With chemical fuel (H2O2) alone, the microrods orient themselves with their anode end against the flow when shear flow is present. Numerical simulations confirm that this orientation results from tilting of the microrods relative to the bottom surface of the channel, which is caused by catalytically driven electro-osmotic flow. By combining this catalytic orientation effect with more powerful, density-dependent acoustic propulsion, both positive and negative rheotaxis can be achieved. The ability to respond to flow stimuli and collectively propel synthetic microswimmers in a directed manner indicates an important step toward practical applications.

  16. Improving Light Harvesting in Dye-Sensitized Solar Cells Using Hybrid Bimetallic Nanostructures

    DOE PAGES

    Zarick, Holly F.; Erwin, William R.; Boulesbaa, Abdelaziz; ...

    2016-01-25

    In this paper, we demonstrate improved light trapping in dye-sensitized solar cells (DSSCs) with hybrid bimetallic gold core/silver shell nanostructures. Silica-coated bimetallic nanostructures (Au/Ag/SiO2 NSs) integrated in the active layer of DSSCs resulted in 7.51% power conversion efficiency relative to 5.97% for reference DSSCs, giving rise to 26% enhancement in device performance. DSSC efficiencies were governed by the particle density of Au/Ag/SiO2 NSs with best performing devices utilizing only 0.44 wt % of nanostructures. We performed transient absorption spectroscopy of DSSCs with variable concentrations of Au/Ag/SiO2 NSs and observed an increase in amplitude and decrease in lifetime with increasing particlemore » density relative to reference. Finally, we attributed this trend to plasmon resonant energy transfer and population of the singlet excited states of the sensitizer molecules at the optimum concentration of NSs promoting enhanced exciton generation and rapid charge transfer into TiO2.« less

  17. Structural, electronic and adsorption properties of Rh(111)/Mo(110) bimetallic catalyst: A DFT study

    NASA Astrophysics Data System (ADS)

    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.

  18. Modification of TiO2 by Bimetallic Au-Cu Nanoparticles for Wastewater Treatment

    PubMed Central

    Hai, Zibin; Kolli, Nadia EL; Uribe, Daniel Bahena; Beaunier, Patricia; José-Yacaman, Miguel; Vigneron, Jackie; Etcheberry, Arnaud; Sorgues, Sébastien; Colbeau-Justin, Christophe; Chen, Jiafu; Remita, Hynd

    2016-01-01

    Au, Cu and bimetallic Au-Cu nanoparticles were synthesized on the surface of commercial TiO2 compounds (P25) by reduction of the metal precursors with tetrakis (hydroxymethyl) phosphonium chloride (THPC) (0.5 % in weight). The alloyed structure of Au-Cu NPs was confirmed by HAADF-STEM, EDS, HRTEM and XPS techniques. The photocatalytic properties of the modified TiO2 have been studied for phenol photodegradation in aqueous suspensions under UV-visible irradiation. The modification by the metal nanoparticles induces an increase in the photocatalytic activity. The highest photocatalytic activity is obtained with Au-Cu/TiO2 (Au/Cu 1:3). Their electronic properties have been studied by time resolved microwave conductivity (TRMC) to follow the charge-carrier dynamics. TRMC measurements show that the TiO2 modification with Au, Cu and Au-Cu nanoparticles plays a role in charge-carrier separations increasing the activity under UV-light. Indeed, the metal nanoparticles act as a sink for electron, decreasing the charge carrier recombination. The TRMC measurements show also that the bimetallic Au-Cu nanoparticles are more efficient in electron scavenging than the monometallic Au and Cu ones. PMID:27274844

  19. Modification of TiO2 by Bimetallic Au-Cu Nanoparticles for Wastewater Treatment.

    PubMed

    Hai, Zibin; Kolli, Nadia El; Uribe, Daniel Bahena; Beaunier, Patricia; José-Yacaman, Miguel; Vigneron, Jackie; Etcheberry, Arnaud; Sorgues, Sébastien; Colbeau-Justin, Christophe; Chen, Jiafu; Remita, Hynd

    2013-09-28

    Au, Cu and bimetallic Au-Cu nanoparticles were synthesized on the surface of commercial TiO2 compounds (P25) by reduction of the metal precursors with tetrakis (hydroxymethyl) phosphonium chloride (THPC) (0.5 % in weight). The alloyed structure of Au-Cu NPs was confirmed by HAADF-STEM, EDS, HRTEM and XPS techniques. The photocatalytic properties of the modified TiO2 have been studied for phenol photodegradation in aqueous suspensions under UV-visible irradiation. The modification by the metal nanoparticles induces an increase in the photocatalytic activity. The highest photocatalytic activity is obtained with Au-Cu/TiO2 (Au/Cu 1:3). Their electronic properties have been studied by time resolved microwave conductivity (TRMC) to follow the charge-carrier dynamics. TRMC measurements show that the TiO2 modification with Au, Cu and Au-Cu nanoparticles plays a role in charge-carrier separations increasing the activity under UV-light. Indeed, the metal nanoparticles act as a sink for electron, decreasing the charge carrier recombination. The TRMC measurements show also that the bimetallic Au-Cu nanoparticles are more efficient in electron scavenging than the monometallic Au and Cu ones.

  20. Characterization of Magnetic NiFe Nanoparticles with Controlled Bimetallic Composition

    SciTech Connect

    Liu, Yan; Chi, Yanxiu; Shan, Shiyao; Yin, Jun; Luo, Jin; Zhong, Chuan-Jian

    2014-02-25

    The exploration of the magnetic properties of bimetallic alloy nanoparticles for various technological applications requires the ability to control the morphology, composition, and surface properties. In this report, we describe new findings of an investigation of the morphology and composition of NiFe alloy nanoparticles synthesized under controlled conditions. The controllability over the bimetallic composition has been demonstrated by the observation of an approximate linear relationship between the composition in the nanoparticles and in the synthetic feeding. The morphology of the NiFe nanoparticles is consistent with an fcc-type alloy, with the lattice strain increasing linearly with the iron content in the nanoparticles. The alloy nanoparticles exhibit remarkable resistance to air oxidation in comparison with Ni or Fe particles. The thermal stability and the magnetic properties of the as-synthesized alloy nanoparticles are shown to depend on the composition. The alloy nanoparticles have also be sown to display low saturation magnetization and coercivity values in comparison with the Ni nanoparticles, in line with the superparamagnetic characteristic. These findings have important implications for the design of stable and controllable magnetic nanoparticles for various technological applications.