Epitaxial growth of heterogeneous metal nanocrystals: from gold nano-octahedra to palladium and silver nanocubes

With octahedral Au nanocrystals as seeds, highly monodisperse Au@Pd and Au@Ag core-shell nanocubes were synthesized by a two-step seed-mediated method in aqueous solution. Accordingly, we have preliminarily proposed a general rule that the atomic radius, bond dissociation energy, and electronegativity of the core and shell metals play key roles in determining the conformal epitaxial layered growth mode.     

Electrochemical absorption and oxidation of hydrogen on palladium alloys with platinum, gold and rhodium

Thin layers of Pd and its alloys with Pt, Au and Rh were prepared by electrodeposition on a Au substrate. Hydrogen electrosorption by the obtained electrodes was studied in 0.5 M H(2)SO(4) solution using cyclic voltammetry and chronoamperometry. The influence of the alloying process on selected thermodynamic (the amount of absorbed hydrogen, the stability of the β-phase, the extent of the absorption/desorption hysteresis) and kinetic aspects (the rate of hydrogen absorption and absorbed hydrogen oxidation) of hydrogen absorption and desorption was examined. It was found that the addition of the non-absorbing elements to Pd results in faster kinetics of the hydrogen electrosorption process and a smaller absorption/desorption hysteresis.     

Electrochemical synthesis and properties of gold nanomaterials

Approximately two decades ago, gold catalyst opened up a new view of their properties when they are introduced in the form of nanomaterials, since at that time, many approaches to preparation and use of gold nanoparticles started to be used in many practical applications. Today, the research activity relating to gold nanomaterials is becoming systematic and goes further to make connections between their surface structure, chemical and physical properties, and possible applications. Since electrodeposition is one of the most controllable methods used to prepare nanoparticles, nanowires, and nanoclusters of gold, the present review gives preference on their electrochemical synthesis. The relationship between catalytic activity, size, morphology and stability of gold nanomaterials is discussed in detail. Based on the properties of the prepared gold nanocatalysts, their new applications in chemical, photochemical, and electrochemical reactions have been observed.     

Electrochemical properties of a gold electrode modified with a mixed monolayer

The electrochemical properties of a gold electrode modified with a mixed thiol monolayer containing both a polar and a non-polar head group have been investigated in aqueous Fe(CN)₆⁴⁻, flavin adenine dinucleotide (FAD) and ubiquinone-0 (2,3-dimethoxy-5-methyl-1,4-benzoquinone, UQ₀) solutions. The cyclic voltammetric current-potential (i-E) response of Fe(CN)₆⁴⁻ was found to be affected considerably by the polarity of the head group contained in the mixed monolayer assembly, as compared with those of FAD and UQ₀. It was also found that in the cases of UQ₀ and FAD the i-E responses for the modified electrode were affected by their own molecular size rather than the polarity of the mixed monolayer head group. Furthermore, compared with Fe(CN)₆⁴⁻ ion, these biologically related molecules are able to permeate readily into the well-organized and hydrophobic alkyl chains of the monolayer assembly. The voltammetric profile of UQ₀ was improved by the modification of aminoethanethiol, as compared with those of bare gold and the electrode modified with other polar thiols. Further, two different permeation paths of the electrode species into the mixed monolayer are suggested from the variation of the i-E response with the cycle of the potential scan.     

Electrochemical properties of sulfur adsorbed on gold electrodes

The electrochemical properties of sulfur adsorbed on gold electrodes were studied in 10^?5M solutions of S^2? in 1 M NaOH. In general, ∵_S is less than a monolayer. At E=0.05 V only, a monolayer will be formed after long times. The sulfur layer is stable in the potential range between ?0.6 and +0.4 V. At lower potentials, sulfur can be desorbed cathodically (charge Q_red), but at higher potentials, where layers of gold oxide are formed, the sulfur is oxidized anodically (charge Q_ox). From the ratio Q_red·6/Q_ox=γ, the electrosorption valency γ=?2 is obtained. This means, that the sulfide ions are almost completely discharged during adsorption. The same layer can be formed by adsorption from polysulfide solutions, which can be explained by a break of the sulfur bond and adsorption of single sulfur atoms. The double layer capacity decreases during adsorption of sulfur indicating the formation of an insulating sulfur layer with a dielectric constant of about 2. The anodic adsorption of sulfide ions is limited by diffusion only. For longer polarisation times, the coverage is independent of time, i.e. place exchange reactions between Au and S can be excluded. The cathodic desorption as well as the anodic oxidation of the adsorbed sulfur are potential dependent charge transfer processes, as can be concluded from potentiodynamic measurements with various sweep rates.     

Dithizonates of gold and palladium

Contrary to some previous reports, it has been found that gold reacts with dithizone in the ratio 1:1 forming a red-brown complex, and in the ratio 2:1 forming a yellow complex, both extractable into chloroform. The proportion of these two complexes in the organic extract depends critically on several factors. Therefore, the use of dithizone as a spectrophotometric reagent and especially as an extractive titrant for gold cannot be recommended. Previous reports on the composition and colour of the dithizonates of palladium are confirmed, except that PdDz is soluble in carbon tetrachloride and in chloroform.     

Adsorption properties of aluminium oxide modified with palladium,gold, and cerium oxide nanoparticles

The adsorption properties of nanocomposites based on γ-Al₂O₃ modified with CeO_x, Au/CeO_x, and Pd/CeO_x nanoparticles with contents of deposited metals ranging from 0.07 to 1.71 wt % are investigated by means of dynamic sorption method. n-Alkanes (C₆–C₈), acetonitrile, diethyl ether, tetrahydrofuran, and dioxane are used as test adsorbates. Adsorption isotherms are measured, and the isosteric heats of adsorption of a number of test adsorbates are calculated. Electron-donor and electron-acceptor characteristics of the surfaces of γ-Al₂O₃-based nanocomposites are estimated. It is shown that Au(0.1%)/CeO_x(0.07%)/γ-Al₂O₃ nanocomposite, which has the lowest content of nanoparticles of the deposited metals, has the highest adsorption activity.     

Aqueous synthesis of copper nanocubes and bimetallic copper/palladium core-shell nanostructures

We have synthesized copper nanocubes with uniform shape and size and copper/palladium core-shell bimetallic nanostructures in high yield by a two-stage procedure in the presence of dodecyl benzene sulfonic acid sodium. The copper nanocubes with a slight hole in the centers of the six {100} surfaces was prepared at the first stage. Later, the bimetallic copper/palladium core-shell nanostructures formed on the basis of the successive reduction of H2PdCl4 and the Pd growth on the surfaces of the Cu seeds.     

Electrochemical properties of composite films based on poly-3,4-ethylenedioxythiophene with inclusions of metallic palladium

The electrochemical behavior of composite Pd-PEDOT films is studied. These films are obtained by chemical deposition of Pd particles in the polymeric matrix of PEDOT (poly-3,4-ethylenedioxythiophene). Characteristics of the films are determined by means of cyclic voltammetry, faradaic impedance, microgravimetry, and energy-dispersive x-ray fluorescence analysis. Impedance spectra of composite Pd-PEDOT films, compared to the original PEDOT film, reveal a new response at potentials of −0.3 and −0.4 V in the form of a distinct semicircle, which results from processes in the electrochemical sorption-desorption of hydrogen. Weight gain during the chemical deposition of palladium in the polymer structure is estimated by mircrogravimetry. It is shown that the mass of palladium loaded in the film depends on the time of synthesis and the initial concentration of palladium ions in solution. The size of the actual surface and the average radius of dispersed palladium particles in the film are also estimated.     

Electrochemical properties of palladium(0) complexes coordinated by quinone derivatives

The polagrophic and cyclic voltammetric behavior of quinone derivatives (Q) and their palladium(0) complexes, (Q)₁ or ²Pd(PPh₃)₂, has been studied. All free quinone derivatives except 5,8,9,10-tetrahydro-1,4-naphthoquinone (THNQ) showed two reversible waves, and all palladium(0) complexes showed irreversible waves. The reduction half-wave potentials for free quinone derivatives lie in the following order:7,7,8,8-tetracyanoquinodimethane (TCNQ) ? p-benzoquinone (BQ) ? 5,8-dihydro-1,4-naphthoquinone (DHNQ) ? 1,4-naphthoquinone (NQ) ? THNQ. The reduction potentials for quinone derivatives shifted toward the negative or coordination to palladium(0). The extents of the shifts depended on the electron-withdrawing ability of the free quinone derivatives. On the other hand, the oxidation potentials for the central palladium(0) in their complexes showed more positive values in comparison with the potential for Pd(PPh₃)₄. However, the oxidation potentials were almost constant for all complexes of the quinone derivatives. On the basis of these facts, the phenomena of charge transfer in the complexes are discussed.     

Electrochemical properties of mesoporous iron phosphate in lithium batteries

Mesoporous iron phosphate containing CTAB as templating agent was synthesized and characterized by means of X-ray diffraction, Fourier transform infrared spectroscopy and TGA techniques. The mesoporous material shows a highly ordered structure, that collapses when submitted to extraction with acetate ions. The treatment of the exchanged samples at 573 K under nitrogen atmosphere leads to amorphous phases with an electrochemical behaviour typical of carbon-coated iron phosphate electrodes. The existence of this coating, proceeding from incomplete pyrolysis of the organic exchange agent, enhances the electronic properties of the system, as evidenced by galvanostatic experiments and impedance spectroscopy measurements.     

Nanocrystalline gold and gold palladium alloy catalysts for chemical synthesis

Catalysis by gold has become one of the most studied new topics in chemistry in recent years, and yet for many gold acting as a catalyst is, perhaps, a most unlikely possibility since bulk gold is a relatively non-reactive, immutable, ductile metal that is prized for its great beauty and value rather than for the depth of its chemistry. However, when prepared in nanocrystalline form, as a collection of a few hundreds of atoms, it displays remarkable activity as a heterogeneous catalyst for a broad range of redox reactions. Of particular note is the ability of gold, either alone or alloyed with palladium, to catalyse selective oxidation reactions, e.g. alkene epoxidation, alcohol oxidation, and the direct synthesis of hydrogen peroxide by the hydrogenation of molecular oxygen. In this article the recent advances in this exciting new field are explored.     

Chiral bisphosphine BINAP-stabilized gold and palladium nanoparticles with small size and their palladium nanoparticle-catalyzed asymmetric reaction

The reduction of tetrachloroaurate or potassium tetrachloropalladate with sodium borohydride in the presence of optically active 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [BINAP] gave the chiral (S)- or (R)-BINAP-stabilized gold or palladium nanoparticles which showed the small core (1.7 nm for BINAP-Au and 2.0 nm for BINAP-Pd) with narrow size distribution and remarkably high stability. Asymmetric hydrosilylation of styrene with trichlorosilane in the presence of chiral BINAP-Pd nanoparticles afforded an optically active 1-phenyl-1-trichlorosilylethane which was converted into an optically active 1-phenylethanol (95% enantiomeric excess) by oxidative cleavage of the carbon-silicon bond.     

Facile synthesis of hollow palladium/copper alloyed nanocubes for formic acid oxidation

Hollow PdCu alloyed nanocubes were successfully synthesized by a novel one-pot template-free strategy through tuning the surface energy difference of the crystal planes by alloying. Compared with the solid nanoparticles, the hollow nanocubes exhibit superior electrocatalytic activity and stability for formic acid oxidation.     

Electrochemical genosensing properties of gold nanoparticle–carbon nanotube hybrid

We have investigated the electrochemical genosensing properties of gold nanoparticle–carbon nanotube hybrid. Thiolated oligonucleotide probes and mercaptohexanol were self-assembled onto the Au–CNT hybrid. The hybridization events of target oligonucleotides are monitored using electrochemical impedance spectroscopy, cyclic voltammetry and a.c. voltammetry techniques. A redox-active mediator is used to detect the oxidation of guanine residues. The as-fabricated genosensor is able to differentiate between complementary and mismatched hybridizations, relying on the oxidation current of the guanine residues mediated via .     

Electrochemical properties of a polycrystalline gold electrode in propylene carbonate solutions

The adsorption of 1,6-hexanediol at the Hg—aqueous solution interface was investigated. The differential capacity, interfacial tension and the zero charge potential were measured. Analysis of the results were carried out both at constant charge and at constant potential. Good congruence with respect to the potential and noncongruence with respect to the charge was found. It was shown that the hexanediol molecules orientate flat against the surface and the adsorption could be described equally well by the Frumkin or Flory—Huggins isotherms. Adsorption parameters for the hexanediol were compared with the literature data on adsorption of ethanediol and 1,4-butanediol. It was concluded that adsorption of diols does not affect the thickness of the inner layer. Thus, this adsorption is well described by the model of two parallel capacitors.     

Sorption of silver,gold and palladium with a polythioether foam

Silver, gold and palladium can be sorbed by a thiopolymer of the type [HO(CH₂CH₂CH₂SS)_nCH₂CH₂OH]. The distribution coefficient for palladium increases with halide concentration, with iodide having the largest effect. Silver can be extracted from chloride, nitrate or picrate media. The different distribution coefficients for gold in hydrochloric acid and in sodium chloride suggest that different sorption mechanisms predominate.