Evolution of three-shell onion-like and core-shell structures in （AgCo）201 bimetallic clusters

<正>This paper studies the structural evolution of（AgCo）₂₀₁ clusters with different Co concentrations under various temperature conditions by using molecular dynamics with the embedded atom method.The most stable position for Co atoms in the cluster is the subsurface layer at low temperature(lower than 200 K for the Ag₂₀₀Co₁ cluster).The position changes to the core layer with the increase of temperature,but there is an energy barrier in the middle layer. This makes the Ag-Co cluster form an Ag-Co-Ag three-shell onion-like configuration.When the temperature is high enough[higher than 800 K for（AgCo）₂₀₁ clusters with 50%Co],Co atoms can obtain enough energy to overcome the energy barrier and the cluster forms an Ag-Co core-shell configuration.Amorphization for the onion-like and core-shell clusters is induced by the large lattice misfit at Ag-Co interfaces.The structural evolution in the Ag-Co cluster is related to the release of excess energy.     

HAADF study of Au-Pt core-shell bimetallic nanoparticles

Bimetallic Pt/Au nanoparticles have been synthesized by the polyol method, stabilized by poly (vinylpyrrolidone) (PVP). The structure of the particles has been determined using transmission electron microscopy and a HAADF (High Angle Annular Dark Field) technique. Some particles present a core-shell structure, with a contrast not predicted by simple atomic number contrast (Z²). Strain fields present in the core-shell interface are thought to be the cause of this contrast, which depends on the orientation of the particle with respect to the electron beam. We propose HAADF as a useful technique to identified core-shell structures in nanoparticle systems. PACS 81.07.-b; 61.46+w; 68.37.Lp     

Surface reconstruction and decahedral structure of bimetallic nanoparticles

We report on energetic surface reconstruction phenomena observed on bimetallic nanoparticle systems of AuPd and AuCu, similar to a resolidification effect observed during the cooling process in lead clusters. These binary alloy nanoparticles show the fivefold edges truncated, resulting in [100] facets on decahedral structures, an effect largely envisioned and reported theoretically, with no experimental evidence so far. We demonstrate experimentally as well as by computational simulations that this new eutectic structure is favored in such nanoalloy systems.     

Synthesis and characterization of cobalt/gold bimetallic nanoparticles

Cobalt/gold (Co/Au) bimetallic nanoparticles are prepared by chemically reducing gold (III) chloride to gold in the presence of pre-synthesized Co nanoparticles. Transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption spectrometry, and a superconducting quantum interference device (SQUID) magnetometer have been used to characterize as-prepared bimetallic nanoparticles. Our findings demonstrate Au not only grows onto Co nanoparticles, forming a surface coating, but also diffuses into Co nanoparticles. The introduction of Au alters the crystalline structure of Co nanoparticles and changes their magnetic properties. Dodecanethiols induce a reorganization of as-prepared Co/Au bimetallic nanoparticles.     

Optical characterization of the polymer embedded alloyed bimetallic nanoparticles

A theoretical approach for the calculation of the bimetallic nanoparticles absorption spectra has been developed as an extension of the Mie theory in which nanoparticle dielectric function is found by the weighted linear combination of the dielectric functions for particles made of the corresponding pure metals. In the frame work of the theoretical model an expression for the resonance light absorption frequency were derived taking into account the interband transitions in the dielectric functions. We propose a simple method for the on-line monitoring of the bimetallic nanoparticles composition based on the measurement of the absorption peak position. Elaborated theoretical approach was used to investigate the polymer embedded Ag/Au nanoparticles which were prepared by reducing gold and silver salts (HAuCl4 and AgNO3, respectively) by ethylene glycol in presence of poly(vinyl pyrrolidone) (PVP) at room temperature. Calculated absorption spectra for the Ag/Au nanoscopic systems showed good agreement with the experimental data. Temporal evolution of the Ag/Au nanoparticles has also been investigated by this approach.     

Continuum model of bimetallic nanoparticles for calculating partial coordination numbers

A way of calculating partial coordination numbers is proposed for bimetallic nanoparticles with different radial distributions of atoms relative to a selected center. It is based on a continuum approximation for the atomic density distribution in the volume of nanoparticles (continuum model) and does not require the use of cluster-based models of nanoparticles to obtain information on the distribution of components in nanoparticles. The results obtained in this manner are compared to those from directly calculating the partial coordination numbers in atomic clusters.     

Synthesis and structure determination of bimetallic Au/Cu nanoparticles

The synthesis of bimetallic nanoparticles has become so important in recent times due to its multi-faceted applications. The structure of the synthesised particles influences directly their properties. In this paper, we report the synthesis of Au/Cu nanoparticles by a simultaneous reduction method, considering three different molar concentrations (AuCu, AuCu₃ and Au₃Cu) of the components. In order to determine the size and structure of the obtained clusters, the particles were examined by optical spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. One of the major factors, the minimum bimetal formation energy, was calculated by an embedded-atom method. The relation between the Au/Cu proportions has been demonstrated to affect the size of the particles and the corresponding structures. From the basic structural analysis it is found that the particles were fcc-like, multiple twin or multiple defect particles for the different Au/Cu concentrations. The smallest particles were identified for the Au/Cu sample with 50% of each, and the most crystalline structures were also obtained in the same sample. PACS 61.46.+w; 61.16.-d; 31.15.Qg     

GPU-based DPSO algorithm for structural optimization of Pt-Co bimetallic nanoparticles

Alloy nanoparticles (NPs) are potential candidates for catalysts in fuel cells applications, and their physical properties are associated with the corresponding stable structures. In this work, a GPU-based discrete particle swarm optimization (DPSO) method is designed to investigate the stable structure of Pt-Co alloy NPs. Register and an optimal block design are used to further increase the acceleration ratio. Comparative experiments on CPU and GPU show that the GPU-based DPSO algorithm possesses superior computational performance, and Register has a great influence on the acceleration ratio. Analyses on the stable structures of Pt-Co NPs demonstrate that Co atoms preferentially locate at vertex and edges of surface, yet Pt atoms exhibit a strong surface and sub-surface segregation only for their composition over 65%.     

Preparation and characterization of Co–Pt bimetallic magnetic nanoparticles

CoPt₃ nanoparticles are synthesized by a two-stage route using NaBH₄ as a reductant. The nanoparticles are characterized by thermogravimetry (TG) and differential thermal analysis (DTA), Fourier transform infrared (FT-IR), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Structural and spectroscopic studies show that the nanoparticles adopt a face-centered-cubic (FCC) crystalline structure with an average particle size of 2.6 nm. SQUID studies reveal that as-synthesized nanoparticles are superparamagnetic at room temperature and ferromagnetic at 1.85 K with coercivity of 980 Oe. Annealing of the samples at 500 °C causes an increase of particle size and a decrease of coercivity.     

Depth-profiling the composition of bimetallic nanoparticles using medium energy ion scattering

The near monolayer depth resolution of medium energy ion scattering is utilized to develop a probe of the depth dependent composition of bimetallic nanoparticles supported on planar oxide supports. The approach fits spectra of scattered ion intensity versus ion energy at well-defined scattering angles taking into account the asymmetric line shape in such spectra and also the depth dependent loss processes encountered by incident ions as they pass through the bimetallic particles.     

Particle swarm optimization of the stable structure of tetrahexahedral Pt-based bimetallic nanoparticles

Bimetallic nanoparticles, enclosed by high-index facets, have great catalytic activity and selectivity owing to the synergy effects of high-index facets and the electronic structures of alloy. In this paper, a discrete particle swarm optimization algorithm was employed to systematically investigate the structural stability and features of tetrahexahedral Pt-based bimetallic nanoparticles with high-index facets. Different Pt/Ag, Pt/Cu, Pt/Pd atom ratios and particle sizes were considered in this work. The simulation results reveal that these alloy nanoparticles exhibit considerably different structural characteristics. Pt–Ag nanoparticles tend to form Pt–Ag core–shell structure. Pt–Cu nanoparticles are preferred to take multi-shell structure with Cu on the outer surface while Pt–Pd nanoparticles present a mixing structure in the interior and Pd-dominated surface. Atomic distribution and bonding characteristics were applied to further characterize the structural features of Pt-based nanoparticles. This study provides an important insight into the structural stability and features of Pt-based nanoparticles with different alloys.     

Size effect on alloying ability and phase stability of immiscible bimetallic nanoparticles

In the present paper, the surface and size effects on the alloying ability and phase stability of immiscible alloy nanoparticles have been studied with calculating the heats of formation of Au-Pt alloy nanoparticles from the single element nanoparticles of their constituents (Au and Pt) with a simple thermodynamic model and an analytic embedded atom method. The results indicated that, besides the similar compositional dependence of heat of formation as in bulk alloys, the heat of formation of alloy nanoparticles exhibits notable size-dependence, and there exists a competition between size effect and compositional effect on the heat of formation of immiscible system. Contrary to the positive heat of formation for bulk-immiscible alloys, a negative heat of formation may be obtained for the alloy nanoparticles with a small size or dilute solute component, which implies a promotion of the alloying ability and phase stability of immiscible system on a nanoscale. The surface segregation results in an extension of the size range of particles with a negative heat of formation. The molecular dynamics simulations have indicated that the structurally and compositionally homogeneous AuPt nanoparticles tend to form a core-shell structure with temperature increasing.     

Structural optimization of Au–Pd bimetallic nanoparticles with improved particle swarm optimization method

Due to the dependence of the chemical and physical properties of the bimetallic nanoparticles(NPs) on their structures,a fundamental understanding of their structural characteristics is crucial for their syntheses and wide applications. In this article, a systematical atomic-level investigation of Au–Pd bimetallic NPs is conducted by using the improved particle swarm optimization(IPSO) with quantum correction Sutton–Chen potentials(Q-SC) at different Au/Pd ratios and different sizes. In the IPSO, the simulated annealing is introduced into the classical particle swarm optimization(PSO) to improve the effectiveness and reliability. In addition, the influences of initial structure, particle size and composition on structural stability and structural features are also studied. The simulation results reveal that the initial structures have little effects on the stable structures, but influence the converging rate greatly, and the convergence rate of the mixing initial structure is clearly faster than those of the core-shell and phase structures. We find that the Au–Pd NPs prefer the structures with Au-rich in the outer layers while Pd-rich in the inner ones. Especially, when the Au/Pd ratio is 6:4, the structure of the nanoparticle(NP) presents a standardized Pd_(core) Au_(shell) structure.     

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

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.     

Synthesis of graphene-supported monodisperse Au Pd bimetallic nanoparticles for electrochemical oxidation of methanol

Monodisperse Au Pd bimetallic nanoparticles(NPs) with different compositions are synthesized by using oleylamine(OAm) as reducing reagent, stabilizer, and solvent. To obtain Au Pd solid solution NPs, Pd–OAm and Au–OAm precursors are firstly prepared by mixing OAm with Palladium(II) acetylacetonate(Pd(acac)2) and HAu Cl4, respectively. Then Pd–OAm and Au–OAm precursor solutions are injected into a hot oleylamine solution to form Au Pd NPs. The size of these NPs ranges from 6.0 to 8.0 nm and the composition is controlled by varying the precursor ratio. The Au Pd NPs are loaded onto reduced graphene oxide(RGO) sheets to make catalysts. Alloy NPs show high electrocatalytic activity and stability toward methanol oxidation in the alkaline media. Their catalytic activity for methanol oxidation is found to be dependent on the NP composition. As the Pd component increases, the peak current densities during the forward scan gradually increase and reach the maximum at Au Pd2. The enhancement of alloy NPs for methanol oxidation can be attributed to a synergistic effect of Au and Pd on the surface of alloy NPs.     

Theoretical study of the chemisorption of CO on bimetallic RhCu surfaces and nanoparticles

The CO interaction with bimetallic RhCu surface models representing several compositions has been studied by first principles density functional theory calculations. The analysis of the bare bimetallic clusters Rh(4s) and Cu(3s) core-level binding energies indicates that is not possible to extract information about the oxidation state of the alloy components. The present calculations predict that CO does always sit on top sites, the influence of the alloy composition on the equilibrium geometry and vibrational frequency of CO chemisorbed at a given Rh or Cu site being very small. However, there is a large difference in the structural properties corresponding to CO chemisorption above either Rh or Cu. Therefore, the absolute value of the vibrational frequency of chemisorbed CO does not permit to extract any information about the alloy composition but afford to assign the chemisorption site. Finally, the CO adsorption energy does not follow a monotonic trend with composition. The use of the Constrained Space Orbital Variation analysis permits one to firmly establish that the difference in adsorption energy for different compositions cannot be explained through differences in the σ-donation and π-backdonation mechanisms.     

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

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.     

Reversible surface structural changes in Pt-based bimetallic nanoparticles during oxidation and reduction cycles

The surface states of supported PtNi nanoparticles treated at alternating O₂ and H₂ atmosphere were studied by X-ray photoelectron spectroscopy. Reversible structural changes at the surfaces of the supported PtNi nanoparticles in response to reaction gases were observed, showing NiO-rich surface in oxidizing gases and Pt-rich surface in reducing gases. The dynamic behaviors can be attributed to two opposite gas-driven mass transport processes at bimetallic particle surfaces, including surface segregation of Pt at the bimetallic particles in H₂ and encapsulation of the particles by NiO in O₂. The similar surface structural changes can be observed in other bimetallic catalyst systems, as exemplified in supported PtCu and PtCo nanoparticles.     

Exploration of bimetallic Pt-Pd/C nanoparticles as an electrocatalyst for oxygen reduction reaction

In this study, carbon supported Pt and Pt-Pd were synthesized as oxygen reduction reaction electrocatalysts for polymer electrolyte membrane fuel cells (PEMFCs). Pt and Pt-Pd nanoparticles have been synthesized by reduction of metal precursors in presence of NaBH₄. Various techniques such as X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX) and scanning electron microscopy (SEM) were utilized to study the prepared samples. Furthermore, electrochemical properties of the prepared samples were evaluated from cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The results showed, the crystallite size of electrocatalysts (Pt and Pt-Pd) is below 10 nm. The higher catalytic activity was detected for Pt-Pd/C electrocatalyst for oxygen reduction reaction (ORR). In addition, it is believed that the better performance of electrocatalyst is related to the synergic effect between Pt and Pd nanoparticles, weakening of the OO bond on Pd-modified Pt nanoparticles in ORR, uniform dispersion of Pd and Pt on the carbon support and higher electrochemical active surface area (EAS) of Pt-Pd/C electrocatalyst.     

Mono and bimetallic nanoparticles of gold,silver and palladium-catalyzed NADH oxidation-coupled reduction of Eosin-Y

Abstract  

Mono metallic (Au, Ag, Pd) and bimetallic (Au–Ag, Ag–Pd, Au–Pd) with 1:1 mol stoichiometry, nanoparticles are synthesized using one-pot, temperature controlled chemical method using cetyltrimethylammonium bromide (CTAB) as the capping agent. The particle sizes (Au = 5.6, Ag = 5.0, Pd = 6.0, Au–Ag = 9.2, Ag–Pd = 9.6, Au–Pd = 9.4 nm) are characterized by UV–Vis, HRTEM, and XRD measurements, respectively. CTAB bindings onto mono and bimetallic nanoparticles are analyzed by FTIR spectra. The catalytic activities of mono and bimetallic nanoparticles are tested on the reaction between NADH oxidation and Eosin-Y reduction. The effects of base, pH, ionic strength, nature of mono and bimetallic catalysts are studied and the reaction conditions are optimized. Bimetallic nanoparticles exhibited better catalysis than the mono metallic nanoparticles, which may be due to the electronic effects of the core to shell metal atoms.