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

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.     

Palladium-coated nickel nanoclusters: new Hiyama cross-coupling catalysts

The advantages of bimetallic nanoparticles as C-C coupling catalysts are discussed, and a simple, bottom-up synthesis method of core-shell Ni-Pd clusters is presented. This method combines electrochemical and 'wet chemical' techniques, and enables the preparation of highly monodispersed structured bimetallic nanoclusters. The double-anode electrochemical cell is described in detail. The core-shell Ni-Pd clusters were then applied as catalysts in the Hiyama cross-coupling reaction between phenyltrimethoxysilane and various haloaryls. Good product yields were obtained with a variety of iodo- and bromoaryls. We found that, for a fixed amount of Pd atoms, the core-shell clusters outperform both the monometallic Pd clusters and the alloy bimetallic Ni-Pd ones. THF is an excellent solvent for this process, with less than 2% homocoupling by-product. The roles of the stabiliser and the solvent are discussed.     

Facile fabrication of Ag-Pd bimetallic nanoparticles in ultrathin TiO(2)-gel films: nanoparticle morphology and catalytic activity

Ag-Pd bimetallic nanoparticles were prepared directly in ultrathin TiO(2)-gel films by a stepwise ion-exchange/reduction approach. Ion-exchange sites were created in ultrathin films using Mg(2+) ions as template. Ag(+) ion was then incorporated by ion exchange, and converted into metallic nanoparticles by low-temperature H(2) plasma, regenerating ion-exchange sites. The same procedure was then carried out for Pd(2+) ion, producing Pd-on-Ag bimetallic nanoparticles, as TEM observation and plasmon resonance absorption indicate. By contrast, reversed metal incorporation procedure appeared to give a mixture of individual Ag and Pd nanoparticles, as confirmed by TEM, absorption spectroscopy and X-ray photoelectron spectroscopy. For hydrogenation of methyl acrylate, the catalytic activity of the Pd-on-Ag nanoparticle is 367 times as large as that of commercial Pd black and 1.6 times as large as that of Pd monometallic nanoparticle. The outstanding catalytic activity was explicable by the large fraction of the surface-exposed Pd atoms. The formation process of the bimetallic nanoparticle and their general morphological feature are discussed.     

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

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.     

Structural characterization of catalytically active metal clusters in polymer membranes

Metal clusters were generated and stabilized in pore free, mechanically stable poly(amide imide) (PAI) polymer membranes in high dispersion and high concentration of typically 15wt-%. These membranes have been successfully tested for catalytic applications. Pure Pd-loaded and bimetallic Pd/Ag, Pd/Cu, Pd/Co, Pd/Pb PAI films were investigated by means of x-ray absorption spectroscopy, small and wide angle x-ray scattering and transmission electron microscopy to characterize the structure of the metal clusters in the protective polymer. The measurements consistently show a homogeneous distribution of metallic nanoclusters of 10–30 Å size within the membranes. Also, a smaller amount of larger aggregates up to 300 Å is observed in most of the films. The precise cluster size distribution critically depends on the solvents used as well as on other preparation parameters such as the stirring time of the metal precursor/polymer solution. In case of Pd/Ag and Pd/Pb bimetallic films no clear evidence for the formation of bimetallic clusters in the membrane, i.e. alloying of both metal components, is found. In Pd/Cu and Pd/Co membranes, chlorine from CuCl₂ and CoCl₂ precursors reacts with Pd which may influence the Pd catalytic behavior. Reduction and oxidation of the metal nanoclusters is quantitatively studied by means of x-ray absorption spectroscopy. Membrane properties are discussed with respect to catalytic applications.     

Melting phenomena: effect of composition for 55-atom Ag-Pd bimetallic clusters

Understanding the composition effect on the melting processes of bimetallic clusters is important for their applications. Here, we report the relationship between the melting point and the metal composition for the 55-atom icosahedral Ag-Pd bimetallic clusters by canonical Monte Carlo simulations, using the second-moment approximation of the tight-binding potentials (TB-SMA) for the metal-metal interactions. Abnormal melting phenomena for the systems of interest are found. Our simulation results reveal that the dependence of the melting point on the composition is not a monotonic change, but experiences three different stages. The melting temperatures of the Ag-Pd bimetallic clusters increase monotonically with the concentration of the Ag atoms first. Then, they reach a plateau presenting almost a constant value. Finally, they decrease sharply at a specific composition. The main reason for this change can be explained in terms of the relative stability of the Ag-Pd bimetallic clusters at different compositions. The results suggest that the more stable the cluster, the higher the melting point for the 55-atom icosahedral Ag-Pd bimetallic clusters at different compositions.     

Short-peptide-based hydrogel: a template for the in situ synthesis of fluorescent silver nanoclusters by using sunlight

N-terminally Fmoc-protected dipeptide, Fmoc-Val-Asp-OH, forms a transparent, stable hydrogel with a minimum gelation concentration of 0.2% w/v. The gelation property of the hydrogel was investigated by using methods such as transmission electron microscopy, field-emission scanning electron microscopy, atomic force microscopy and Fourier transform infrared spectroscopy. The silver-ion-encapsulating hydrogel can efficiently and spontaneously produce fluorescent silver nanoclusters under sunlight at physiological pH (7.46) by using a green chemistry approach. Interestingly, in the absence of any conventional reducing agent but in the presence of sunlight, silver ions were reduced by the carboxylate group of a gelator peptide that contains an aspartic acid residue. These clusters were investigated by using UV/Vis spectroscopy, photoluminescence spectroscopy, high-resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) studies. Mass spectrometric analysis shows the presence of a few atoms in nanoclusters containing only Ag(2). The reported fluorescent Ag nanoclusters show excellent optical properties, including a very narrow emission profile and large Stokes shift (>100 nm). The reported fluorescent Ag nanoclusters within hydrogel are very stable even after 6 months storage in the dark at 4 °C. The as-prepared hydrogel-nanocluster conjugate could have applications in antibacterial preparations, bioimaging and other purposes.     

Synthesis of Ag/Pd nanoparticles via reactive micelles as templates and its application to electroless copper deposition

Ag/Pd nanoparticles have been synthesized with a reactive alcohol-type surfactant, sodium dodecyl sulfate (SDS), without the presence of an external reducing agent. Both UV-vis absorption spectra and X-ray diffraction patterns for the bimetallic and physical mixtures of individual nanoparticles revealed the formation of a bimetallic structure. Based on this method, an ordered 3D grapelike nanostructure was formed, possibly due to transformation of the liquid crystal phase of the micelles. Data from the energy-dispersive X-ray analysis show that the composition of bimetallic nanoparticle is approximately equal to the feeing solution. Furthermore, the Ag/Pd nanoparticles exhibit distinct catalyst for electroless copper deposition and may be a substitute for the conventional palladium system, which is expensive and unstable in operation.     

Temperature-dependent structuring of Au-Pt bimetallic nanoclusters on a thin film of Al2O3/NiAl(100)

Au-Pt bimetallic nanoclusters on a thin film of Al(2)O(3)/NiAl(100) undergo significant structural evolution on variation of the temperature. Au and Pt deposited sequentially from the vapor onto thin-film Al(2)O(3)/NiAl(100) at 300 K form preferentially bimetallic nanoclusters (diameter ≦ 6.0 nm and height ≦ 0.8 nm) with both Au and Pt coexisting at the cluster surface, despite the order of metal deposition. These bimetallic clusters are structurally ordered, have a fcc phase and grow with their facets either (111) or (001) parallel to the θ-Al(2)O(3)(100) surface. Upon annealing the clusters to 400-500 K, the Au atoms inside the clusters migrate toward the surface, resulting in formation of a structure with a Pt core and an Au shell. Annealing the sample to 500-650 K reorients the bimetallic clusters--all clusters have their (001) facets parallel to the oxide surface--and induces oxidation of Pt. Such annealed bimetallic clusters become encapsulated with the aluminium-oxide materials and a few Au remain on the surface.     

Experiment and theoretical modeling of the luminescence of silver nanoclusters dispersed in oxyfluoride glass

Density functional theory (DFT) and complete active space perturbation theory (CASPT2) have been applied for modeling the configuration, charge, energy states, and spin of luminescent Ag nanoclusters dispersed within the bulk of oxyfluoride glass host. The excitation spectra of luminescence of the Ag nanoclusters have been measured and simulated by means of the DFT and CASPT2. Electron spin resonance spectra have been recorded and suggest diamagnetic state of Ag nanoclusters. The silver nanoclusters have been argued to consist mostly of pairs of Ag(2) (+) dimers, or Ag(4) (2+) tetramers, with different extent of distortion along the tetramer diagonal. The sites for the Ag nanoclusters have been suggested where the pairs of Ag ions substitute onto metal and hole cation sites and are surrounded by fluorine ions within a fluorite-type lattice.     

In-situ UV-visible study of Pd nanocluster formation in solution

The formation of Pd nanoclusters in solution is studied. This system has two types of light-absorbing species: Pd ions which absorb light via electronic transitions and Pd clusters and aggregates which absorb light via valence-conduction transitions and also scatter light due to their nanometric dimensions. Here we monitor these dynamic changes using UV-visible spectroscopy. The reduction and clustering concentration profiles are extracted from the raw data using a combination of net analyte signal (NAS) and principal component analysis (PCA) methods. PdCl2, Pd(OAc)2 and Pd(NO3)2 are used as Pd2+ precursors and various tetra-n-octylammonium carboxylates are applied as reducing and stabilising agents. This in situ approach enables the quantification of both the reduction of the Pd2+ ions and the growth of the Pd clusters. Kinetic models that account for ion reduction, cluster growth and aggregation are presented and the influence of the counteranions and the reducing agents on these processes is discussed.     

Palladium nanoclusters deposited on single-walled carbon nanohorns

This study reports a direct route for deposition of Pd nanoclusters on single-walled carbon nanohorns (SWNHs) in a one step reaction involving chemical reduction of metal ions in the presence of a polymer-stabilizer. The applied strategy provides small Pd nanoclusters with an average diameter of approximately 2.3 nm robustly attached to the nanotubular carbon. The attachment is mediated by the polymer (poly(vinylpyrrolidone), PVP) used to stabilize the nanoclusters.     

Interaction between Pd and Ag on the surface of silica

Palladium, silver and palladium–silver catalysts supported on silica were prepared by coimpregnation of support with solution of AgNO₃ and Pd(NO₃)₂. The catalysts were characterized by X-ray powder diffraction (XRD), temperature programmed reduction (TPR), time of flight ion mass spectrometry (ToF-SIMS), chemisorption of carbon monoxide and were tested in the reaction of selective oxidation of glucose to gluconic acid.

XRD and TPR studies have shown that an interaction between Pd and Ag on the surface of silica after oxidation at 500 °C and reduction at 260 °C leads to the formation of solid solutions.

ToF-SIMS images of the surface of 5% Ag/SiO₂ catalyst after oxidation at 500 °C and reduction at 260 °C show that Ag atoms supported on silica are not distributed homogenously but tend to form regions of enhanced Ag concentration. Positive ions images of the surface of 5% Pd/SiO₂ catalyst also display regions of enhanced concentration of Pd atoms, but they are more homogenously distributed on silica.

ToF-SIMS peak intensity ratio ¹⁰⁸Pd⁺/¹⁰⁷Ag⁺ for bimetallic 5% Pd–5% Ag/SiO₂ catalysts has a lower value than that obtained for physical mixture 5% Pd/SiO₂–5% Ag/SiO₂ which indicates that the surface of bimetallic catalyst is enriched with silver atoms.     

Insight of the photoluminescence of atomically precise bimetallic nanoclusters with free electrons

Noble-metal nanoclusters with emission properties are promising candidtes for cell imaging, biosensing, photo-therapy applications due to their ultra-small size, good photostability, and high biocompatibility. It is of great importance to realize the atomic precision of such metal nanoclusters (NCs) because they allow us to investigate the origin of fluorescence at the atomic level. However, compared to quantum dots (QDs) and organic dyes, noble metal nanoclusters usually suffered from low quantum yield, which significantly limited their applications. Doping with other metal atoms is an effective strategy to enhance the fluorescent properties of metal NCs. Therefore, bimetallic nanoclusters possess enhanced emission properties relative to their monometallic counterparts. Although a couple of reviews have existed for bimetallic nanocluster, few of them concern their emissive properties. In this context, the emissive properties of atomically precise bimetallic nanoclusters are summarized in this minireview. Synergistic effect, state of aggregation, assembly, and isomerism on the fluorescence of bimetallic clusters and structure-photoluminescence property correlations are also discussed.     

Structures of bimetallic clusters

We report an optimization algorithm for studying bimetallic nanoclusters. The algorithm combines two state-of-the-art methods, the genetic algorithm and the basin hopping approach, widely employed in the literature for predicting structures of pure metallic and nonmetallic clusters. To critically test the present algorithm and its use in determining the lowest-energy structures of bimetallic nanoclusters, we apply it to study the bimetallic clusters Cu(n)Au(38-n) (0< or =n< or =38). It is predicted that the Au atoms, being larger in size than the Cu atoms, prefer to occupy surface sites showing thus the segregating behavior. As the atom fraction of Cu increases, the bimetallic cluster Cu(n)Au(38-n), as a whole, first takes on an amorphous structure and is followed by dramatic changes in structure with the Cu atoms revealing hexagonal, then assuming pentagonal, and finally shifting to octahedral symmetry in the Cu-rich range.     

Au/Ag核一壳结构复合纳米粒子形成机制的研究

在已制备好的Au纳米粒子表面,通过化学还原的方法沉积生长Ag包覆层,通过 控制Au, Ag的比列,制备了粒度均匀且粒径可控的Au/Ag核-壳结构纳米粒子。利用 UV-vis吸收光谱和透射电子显微镜（TEM）对SAu, Ag摩尔比为1：10的复合纳米粒 子的光学性质和形态进行随时监测,直接观察了核-壳结构纳米粒子的生长过程： 一部分Ag+在Au核表面还原生长,溶液中其余Ag+还原形成银的纳米团簇向粒子表面 的继续沉积生长,壳层增厚。     

Photochemically controlled electrochemical deposition and dissolution of Ag0 nanoclusters on au electrode surfaces

A photoisomerizable thiolated nitrospiropyran SP, (1a), monolayer is assembled on a Au electrode by the primary deposition of thiolated nitromerocyanine isomer 1b as a monolayer on the electrode, followed by the irradiation of the surface with visible light, lambda > 475 nm. The surface coverage of nitrospiropyran units (1a) on the electrode is 2 x 10-10 mole cm-2. Irradiation of the electrode with UV light, 320 nm < lambda < 360 nm, results in the nitromerocyanine, MR, monolayer on the electrode that binds Ag+ ions to the phenolate units. The Ag+ ions associated with the MR monolayer undergo cyclic reduction to surface-confined Ag0 nanoclusters, and reoxidation and dissolution of the Ag0 nanoclusters to Ag+ ions associated with the monolayer are demonstrated. The electron-transfer rate constants for the reduction of Ag+ to Ag0 and for the dissolution of Ag0 were determined by chronoamperometry and correspond to ketred = 12.7 s-1 and ketox = 10.5 s-1, respectively. The nanoclustering rate was characterized by surface plasmon resonance measurements, and it proceeds on a time scale of 10 min. The size of the Ag0 nanoclusters is in the range of 2 to 20 nm. The electrochemically induced reduction of the MR-Ag+ monolayer to the MR-Ag0 surface and the reoxidation of the MR-Ag0 surface control the hydrophilic-hydrophobic properties of the surface. The advancing contact angle of the MR-Ag0-functionalized surface is 59 degrees , and the contact angle of the MR-Ag+-monolayer-functionalized surface is 74 degrees . Photoisomerization of the Ag0-MR surface to the Ag0-SP state, followed by the oxidation of the Ag0 nanoclusters, results in the dissolution of the Ag+ ions into the electrolyte solution.     

纳米结构的钯与金-钯薄膜的制备及其电催化活性

应用电位扫描法将Pd(II)离子沉积到玻碳电极表面,形成纳米结构的金属钯薄膜电极.然后在酸性溶液中控制适当的阴极电位,使该薄膜电极的钯吸收足量的活性氢,进而以吸收的氢作还原剂将Au(III)离子还原,制得Au-Pd双金属薄膜电极.扫描电镜、循环伏安法等测试表明,该电极Au-Pd沉积层对乙醇的氧化具有很高的电催化活性.     

Kinetic control and thermodynamic selection in the synthesis of atomically precise gold nanoclusters

This work presents a combined approach of kinetic control and thermodynamic selection for the synthesis of monodisperse 19 gold atom nanoclusters protected by thiolate groups. The step of kinetic control allows the formation of a proper size distribution of initial size-mixed Au(n)(SR)(m) nanoclusters following the reduction of a gold precursor. Unlike the synthesis of Au(25)(SR)(18) nanoclusters, which involves rapid reduction of the gold precursor by NaBH(4) followed by size focusing, the synthesis of 19-atom nanoclusters requires slow reduction effected by a weaker reducing agent, borane-tert-butylamine complex. The initially formed mixture of nanoclusters then undergoes size convergence into a monodisperse product by means of a prolonged aging process. The nanocluster formula was determined to be Au(19)(SC(2)H(4)Ph)(13). This work demonstrates the importance of both kinetic control of the initial size distribution of nanoclusters prior to size focusing and subsequent thermodynamic selection of stable nanoclusters as the final product.     

New algorithm in the basin hopping Monte Carlo to find the global minimum structure of unary and binary metallic nanoclusters

The basin-hopping Monte Carlo algorithm was modified to more effectively determine a global minimum structure in pure and binary metallic nanoclusters. For a pure metallic Ag55 nanocluster, the newly developed quadratic basin-hopping Monte Carlo algorithm is 3.8 times more efficient than the standard basin-hopping Monte Carlo algorithm. For a bimetallic Ag42Pd13 nanocluster, the new algorithm succeeds in finding the global minimum structure by 18.3% even though the standard basin-hopping Monte Carlo algorithm fails to achieve it.