A novel method of electrodepositing highly dispersed nano palladium particles on glassy carbon electrode

The volumetric behavior of a chloride complex of palladium was studied at a glassy carbon electrode (GCE). The Pd-IV complex existing on the GCE surface was found, which was proposed to form an octahedral surface complex through coordination to the oxygen atom of an oxygen functional group on the pretreated GCE surface. The ferri/ferrocyanide redox couple was used as a probe to examine the activity of the GCE. X-ray photoelectron spectroscopy provided the evidence of the surface complex existing on the GCE. Highly dispersed Pd particles can be obtained when the surface complexes were reduced electrochemically to Pd atoms. The Pd particles obtained in this way were in nanometer scale and exhibit high catalytic activity towards the oxidation of hydrazine. (C) 1997 Elsevier Science Ltd.

ELECTROCHEMICAL DEPOSITION OF MAGNESIUM IN ETHEREAL GRIGNARD SALT SOLUTION WITH IONIC LIQUID ADDITIVE

The electrochemical deposition of magnesium was investigated in ethereal Grignard salt solution with tetraethylammonium bistrifluoro-methanesulfonimidate additive, using cyclic voltammetry, potentiostatic transients, and scanning electron microscope measurements. The voltammograms showed the presence of reduction and oxidation peaks associated with the deposition and dissolution of magnesium. From the analysis of the experimental current transients, it was shown that the magnesium deposition process was characterized as a three-dimensional nucleation. The deposited product obtained from potentiostatic reduction presented a generally uniform and dense film.

Assembly process of CuHCF/MPA multilayers on gold nanoparticles modified electrode and characterization by electrochemical SPR

Gold nanoparticles were deposited onto 2-mercaptoethylamine (MEA)-assembled planar gold thin film to construct gold nanoparticles modified electrode by virtue of a solution-based self-assembly strategy. Subsequently, 3-mercaptopropionic acid (MPA)-bridged copper hexacyanoferrate (CuHCF) multilayers were constructed on the as-prepared gold nanoparticles modified electrode. The resulted multilayer nanostructures were investigated by electrochemical surface plasmon resonance (EC-SPR) and atomic force microscopy (AFM) with primary emphasis upon the effect of the gold nanoparticles on the MPA/CuHCF multilayers growth and their surface morphology. Compared with the multilayer system on a planar gold electrode, the different electrochemical and optical properties might result from higher curvature effect and extraordinary surface-to-volume ratio characteristic of gold nanoparticles and the nanoparticle-selective growth of CuHCF. A dendrimer-like assembly process was proposed to explain the experiment results. This new motif of multilayer on the gold nanoparticles modified electrode was different from that of on a planar gold electrode, indicating a potential application of EC-SPR technique in the study of nanocomposite materials.

Electrochemical design of ultrathin platinum-coated gold nanoparticle monolayer films as a novel nanostructured electrocatalyst for oxygen reduction

The deliberate tailoring of nanostructured metallic catalysts at the monolayer-level is an ongoing challenge and could lead to new electronic and catalytic properties, since surface-catalyzed reactions are extremely sensitive to the atomic-level details of the catalytic surface. In this article, we present a novel electrochemical strategy to nanoparticle-based catalyst design using the recently developed underpotential deposition (UPD) redox replacement technique. A single UPD Cu replacement with Pt2+ yielded a uniform Pt layer on colloid gold surfaces. The ultrathin (nominally monolayer-level) Pt coating of the novel nanostructured particles was confirmed by cyclic voltammetry and X-ray photoelectron spectra (XPS). The present results demonstrate that ultrathin Pt coating effects efficiently and behaves as the nanostructured monometallic Pt for electrocatalytic oxygen reduction, and also shows size-dependent, tunable electrocatalytic ability. The as-prepared ultrathin Pt-coated Au nanoparticle monolayer electrodes reduce O-2 predominantly by four electrons to H2O, as confirmed by the rotating ring-disk electrode (RRDE) technique.

Electrochemical deposition of silver in room-temperature ionic liquids and its surface-enhanced Raman scattering effect

The use of room-temperature ionic liquids (RTILs) as media for electrochemical application is very attractive. In this work, the electrochemical deposition of silver was investigated at a glassy carbon electrode in hydrophobic 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) and hydrophilic 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) RTILs and in KNO3 aqueous solution by cyclic voltammetric and potentiostatic transient techniques. The voltammograms showed the presence of reduction and oxidation peaks associated with the deposition and dissolution of silver from AgBF4 in both BMIMPF6 and BMIMBF4, resembling the redox behavior of AgNO3 in KNO3 aqueous solution. A crossover loop was observed in all the cyclic voltammograms of these electrochemical systems, indicating a nucleation process. From the analysis of the experimental current transients, it was shown that the electrochemical deposition process of silver in these media was characteristic of 3D nucleation with diffusion-controlled hemispherical growth, and the silver nucleation closely followed the response predicted for progressive nucleation in BMIMPF6 and instantaneous nucleation in KNO3 aqueous solution, respectively.

Gold nanoparticles as fine tuners of electrochemical properties of the electrode/solution interface

Recently, a novel approach for preparing SERS and SPR substrates was developed, which indicates a potential application in tailoring the interfacial structure of an electrode surface. In this study, (3-mercaptopropyl)trimethoxysilane (MPTMS) was selected as a polymeric adhesive layer, and a low concentration of colloid Au solution was used to achieve a more accurate control over interface morphology at nanoscale dimensions due to slow self-assembling kinetics of gold nanoparticle's. Subsequent seeding growth of these MPTMS-supported submonolayers of gold nanoparticles in Au3+/NH2OH aqueous solution enlarges particle size and eventually results in the generation of conductive gold films (similar to previous (3-aminopropyl)trimethoxysilane-supported gold films). Such tunable interface structure was evaluated by atomic force microscopy (AFM). Also, ac impedance spectroscopy (ACIS) and cyclic voltammograms were performed to evaluate electrochemical properties of the as-prepared interfaces by using Fe(CN)(6) (3-/4-) couples as a probe. Furthermore, relevant theories of microarray electrodes were introduced into this study to explain the highly tunable electrochemical properties of the as-prepared interfaces. As a result, it is concluded that the electrochemical properties toward Fe(CN)(6) (3-/4-) couples are highly dependent on the active nanoelectrode (nanoparticles) area fraction and nanoparticles are fine-tuners of interfacial properties because the number density. (numbers/unit area) and size of nanoparticles are highly tunable by self-assembling and seeding growth time scale control. This is in agreement with the theoretical expectations for a microarray electrode if a single nanoparticle tethered to a blocking SAM is taken as a nanoelectrode and 2-D nanoparticle assemblies are taken as nanoelectrode arrays.

Controlled nucleation and growth of surface-confined gold nanoparticles on a (3-aminopropyl)trimethoxysilane-modified class slide: A strategy for SPR substrates

The thickness of the gold film and its morphology, including the surface roughness, are very important for getting a good, reproducible response in the SPR technique. Here, we report a novel alternative approach for preparing SPR-active substrates that is completely solution-based. Our strategy is based on self-assembly of the gold colloid monolayer on a (3-aminopropyl)trimethoxysilane-modified glass slide, followed by electroless gold plating. Using this method, the thickness of films can be easily controlled at the nanometer scale by setting the plating time in the same conditions. Surface roughness and morphology of gold films can be modified by both tuning the size of gold nanoparticles and agitation during the plating. Surface evolution of the Au film was followed in real time by UV-vis spectroscopy and in situ SPRS. To assess the surface roughness and electrochemical stability of the Au films, atomic force microscopy and cyclic voltammetry were used. In addition, the stability of the gold adhesion is demonstrated by three methods. The as-prepared Au films on substrates are reproducible and stable, which allows them to be used as electrodes for electrochemical experiments and as platforms for studying SAMs.

Electrochemical investigations of micro-droplets formed on metals during the deliquescence of salt particles in atmosphere

CORROSION; WATER; SPECTROSCOPY; CHLORIDE; ZINC; NUCLEATION; INTERFACE; ELECTRODE; SURFACES; GROWTH

Improving Nucleation in the Fabrication of High-Quality 3D Macro-Porous Copper Film through The Surface-Modification of A Polystyrene Colloid-Assembled Template

A new approach is developed to the fabrication of high-quality three-dimensional macro-porous copper films. A highly-ordered macroporous copper film is successfully produced on a polystyrene sphere (PS) template that has been modified by sodium dodecyl sulfate (SDS). It is shown that this procedure can change a hydrophobic surface of PS template into a hydrophilic surface. The present study is devoted to the influence of the electrolyte solution transport on the nucleation process. It is demonstrated that the permeability of the electrolyte solution in the nanochannels of the PS template plays an important role in the chemical electrodeposition of high-quality macroporous copper film. The permeability is drastically enhanced in our experiment through the surface modi. cation of the PS templates. The method could be used to homogeneously produce a large number of nucleations on a substrate, which is a key factor for the fabrication of the high-quality macroporous copper film.

Mechanism of nucleation and precipitation in Li containing Al-Zn-Mg-Cu alloys

Investigations on the aging hardening behavior of four Al-Li-Zn-Mg-Cu alloys were carried out using differential scanning calorimetry, transmission electron microscopy and hardness measurement. It is shown that the addition of Li inhibits the formation of Zn-rich G.P. zones in Al-Zn-Mg-Cu alloys. The dominant aging hardening precipitates is delta'(Al3Li) phase. Coarse T ((AlZn)(49)Mg-32) phase, instead of MgZn2, precipitates primarily on grain boundaries, and provides little strengthening. The multi-stop aging involving plastic deformation introduces in the matrix a high concentration of structural defects. These defects play different role on the nucleation of Zn-rich G.P. zones in different alloys. For the Li free alloy, structural defects act as vacancy sinks and tend to suppress the homogeneous precipitation of G.P. zones, while for the Li containing alloys, these defects promote the heterogeneous nucleation of G.P. zones and metastable MgZn2. A significant aging hardening effect is attained in deformed Li containing alloys due to the extra precipitation of fine MgZn2 in the matrix combined with deformation hardening.

Dislocation Propagation versus Dislocation Nucleation - Authors' Response

No abstract.

The effect of nucleation time on the growth of a microvoid in a viscoelastic material

In this paper, discussions are focused on the growth of a nucleated void in a viscoelastic material. The in situ tensile tests of specimens made of high-density polyethylene, filled with spherical glass beads (HDPE/GB) are carried out under SEM. The experimental result indicates that the microvoid nucleation is induced by the partially interfacial debonding of particles. By means of the Laplace transform and the Eshelby's equivalent inclusion method, a new analytical expression of the void strain at different nucleation times is derived. It can be seen that the strain of the nucleated void depends not only on the remote strain history, but also on the nucleation time. This expression is also illustrated by numerical examples, and is found to be of great usefulness in the study of damage evolution in viscoelastic materials.

Influence of Electrostatic Interaction on Fibrinogen Adsorption on Gold Studied by Imaging Ellipsometry Combined with Electrochemical Methods

Imaging ellipsometry was combined with electrochemical methods for studying electrostatic interactions of protein and solid surfaces. The potential of zero charge for gold-coated silicon wafer/solution interfaces wad determined by AC impedance method. The potential of the gold-coated silicon wafer was controlled at the potential of zero charge, and the adsorption of fibrinogen on the potential-controlled and non-controlled surfaces was measured in real time at the same time by imaging ellipsometry The effect of electrostatic interaction was studied by comparing the difference between the potential of controlled adsorption and the Potential of noncontrolled adsorption. It was shown that the rate of fibrinogen adsorption on the potentiostatic surface was faster than that on the nonpotentiostatic surface. The electrostatic influence on fibrinogen adsorption on the gold-coated silicon wafer was weak, so the hydrophobic interaction should be the major affinity.

Electrochemical, spectroscopic and SPM evidence for the controlled formation of self-assembled monolayers and organised multilayers of ferrocenyl alkyl thiols on Au(111)

Organised multilayers were formed from the controlled self-assembly of ferrocene alkyl thiols on Au(111) surfaces. The control was accomplished by increasing the concentration of the thiol solutions used for the assembly. Cyclic voltammetry, ellipsometry, scanning probe microscopy (STM and AFM) and in situ FTIR spectroscopy were used to probe the differences between mono- and multilayers of the same compounds. Electrochemical desorption studies confirmed that the multilayer structure is attached to the surface via one monolayer. The electrochemical behaviour of the multilayers indicated the presence of more than one controlling factor during the oxidation step, whereas the reduction was kinetically controlled which contrasts with the behaviour of monolayers, which exhibit kinetic control for the oxidation and reduction steps. Conventional and imaging ellipsometry confirmed that multilayers with well-defined increments in thickness could be produced. However, STM indicated that at the monolayer stage, the thiols used promote the mobility of Au atoms on the surface. It is very likely that the multilayer structure is held together through hydrogen bonding. To the best of out knowledge, this is the first example of a controlled one-step growth of multilayers of ferrocenyl alkyl thiols using self-assembly techniques.

Electrochemical Impedance Spectroscopy Of Peo Coating On Aluminum Alloy In Nacl Solution

Various Plasma Electrolytic Oxidation (PEO) ceramic coatings were prepared on LY12 aluminum alloy by adjusting the concentration of sodium silicate solution. Optical microscope (OM), XRD and EIS were used to study their morphology, composition and anti corrosion behavior in NaCl solution. Increasing concentration of sodium silicate leads to the increase of the total coating thickness while too high and too low concentration lead to the decrease of inner dense layer. The main composition of PEO coatings prepared in 20, 40 and above 60g/L concentration solution are correspondingly alumina, alumina with mullite, and amorphous phase. The corrosion resistance is determined by the inner dense layer. Increasing the thickness of inner dense layer can improve the anti-corrosion performance. PEO coating's corrosion resistance in acidic, alkaline and neutral NaCl solution is proved and the corrosion mechanism involved is also discussed.