Segmented All-Platinum Nanowires with Controlled Morphology through Manipulation of the Local Electrolyte Distribution in Fluidic Nanochannels during Electrodeposition

Synthesis of segmented all-Pt nanowires is achieved by a template-assisted method. The combination of a suitably chosen electrolyte/template system with pulse-reverse electrodeposition allows the formation of well-defined segments linked to nanowires. Manipulation of the morphology is obtained by controlling the electrokinetie effects on the local electrolyte distribution inside the nanochannels during the nanowire growth process, allowing a deviation from the continuously cylindrical geometry given by the nanoporous template. The length of the segments can be adjusted as a function of the cathodic pulse duration. Applying constant pulses leads to segments with homogeneous shape and dimensions along most of the total wire length. X-ray diffraction demonstrates that the preferred crystallite orientation of the polycrystalline wires varies with the average segment length. The results are explained considering transitions in texture formation with increasing thickness of the electrodeposit. A mechanism of segment formation is proposed based on structural characterizations. Nanowires with controlled segmented morphology are of great technological importance, because of the possibility to precisely control their substructure as a means of tuning their electrical, thermal, and optical properties. The concept we present in this work for electrodeposited platinum and track-etched polycarbonate membranes can be applied to other selected materials as well as templates and constitutes a general method to controlled nanostructuring and synthesis of shape controlled nanostructures.

Magnet-assisted assembly of 1-dimensional hollow PtCo nanomaterials on an electrode surface

In this work, rapid and controllable confinement of one-dimensional (1D) hollow PtCo nanomaterials on an indium tin oxide (ITO) electrode surface was simply realized via magnetic attraction. The successful assembly was verified by scanning electron microscopy (SEM) and cyclic voltammetry, which showed that a longer exposure time of the electrode to the suspension of these 1D hollow nanomaterials (magnetic suspension) led to a larger amount of attached 1D hollow PtCo nanomaterials.

Platinum-coated gold nanoporous film surface: Electrodeposition and enhanced electrocatalytic activity for methanol oxidation

This report describes the preparation of Pt-nanoparticle-coated gold-nanoporous film (PGNF) on a gold substrate via a simple "green" approach. The gold electrode that has been anodized under a high potential of 5 V is reduced by freshly prepared ascorbic acid (AA) solution to obtain gold nanoporous film electrode. Then the Pt nanoparticle is grown on the electrode by cyclic voltammetry (CV).

Electrodeposition of platinum nanoclusters on type I collagen modified electrode and its electrocatalytic activity for methanol oxidation

We firstly reported a novel polymer matrix fabricated by type I collagen and polymers, and this matrix can be used as nanoreactors for electrodepositing platinum nanoclusters (PNCs). The type I collagen film has a significant effect on the growth of PNCs. The size of the platinum nanoparticles could be readily tuned by adjusting deposition time, potential and the concentration of electrolyte, which have been verified by field-emitted scanning electron microscopy (FE-SEM). Furthermore, cyclic voltammetry (CV) has demonstrated that the as-prepared PNCs can catalyze methanol directly with higher activity than that prepared on PSS/PDDA film, and with better tolerance to poisoning than the commercial E-TEK catalyst. The collagen-polymer matrix can be used as a general reactor to electrodeposit other metal nanostructures.

Layer-by-layer electrodeposition of redox polymers and enzymes on screen-printed carbon electrodes for the preparation of reagentless biosensors

Layer-by-layer electrodeposition of redox polymer/enzyme composition films on screen-printed carbon electrodes for fabrication of reagentless enzyme biosensors has been proposed and the resulting films were found to be very stable and rigid.

Polyamidoamine dendrimers-assisted electrodeposition of gold-platinum bimetallic nanoflowers

Novel Au-Pt bimetallic flower nanostructures fabricated on a polyamidoamine dendrimers-modified surface by electrodeposition are reported. These polyamidoamine dendrimers were stable, and they assisted the formation of Au-Pt bimetallic nanoflowers during the electrodeposition process. These nanoflowers were characterized by field-emitted scanning electron microscopy (FE-SEM), energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction, and electrochemical methods. FE-SEM images showed that the bimetallic nanoflower included two parts: the "light" and the "pale" part. The two parts consisted of many small bimetallic nanoparticles, which was attributed to the progressive nucleation process. Moreover, the "light" part contained more bimetallic nanoparticles. The morphologies of bimetallic nanoflowers depended on the electrodeposition time and potential and the layer number of assembled dendrimers. The average size of nanoflowers increased with the increase in electrodeposition time. The layer number of assembled dendrimers obviously affected the size and morphologies of the "pale" parts of deposited nanoflowers.

In situ electrochemical SERS studies on electrodeposition of aniline on 4-ATP/Au surface

The electrochemical polymerization of 0.01 M aniline in 1 M H2SO4 aqueous solution on roughened Au surface modified with a self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) has been investigated by in situ electrochemical surface-enhanced Raman scattering spectroscopy (SERS). The repeat units and possible structures of the electrodeposited polyaniline (PANI) film were proposed; i.e., aniline monomer is coupled in head-to-tail predominately at the C-4 of aniline and amine of 4-ATP, and the thin PANI film is orientated vertically to substrate surface. Simultaneous Raman spectra during potential scanning indicate clearly that the ultrathin PANI film (in initial growth of the film) consists of semiquinone radical cation (IP+), para-disubstituted benzene (IP and IP+) and quinine diimine (NP) while it is oxidized, and without quinine diimine and semiquinone radical cation while reduced. Meanwhile, the results confirm that 4-ATP monolayer shows a strong promotion on the electrodeposition of aniline monomer, and a possible polymerization mechanism was proposed.

IN-SITU SCANNING TUNNELING MICROSCOPIC STUDY OF NICKEL ELECTRODEPOSITION ON HOPG

The early stages of the electrodeposition of nickel on highly oriented pyrolytic graphite (HOPG) were investigated by in situ scanning tunnelling microscopy, scanning electron microscopy and electrochemical measurements. Experimental results showed that t

CHOLESTEROL SENSOR-BASED ON ELECTRODEPOSITION OF CATALYTIC PALLADIUM PARTICLES

A layer of palladium particles was electrodeposited on a glassy carbon electrode. The dispersed Pd particles resulted in a large decrease in overvoltage for the electrochemical oxidation of H2O2 down to +0.4 V vs. Ag/AgCl, based on which a new kind of cholesterol sensor was fabricated. Cholesterol oxidase was immobilized on the Pd-dispersed electrode by cross-linking with glutaraldehyde and a layer of poly(o-phenylenediamine) (PPD) film was electropolymerized on the enzyme layer. The sensor shows a linear response in the concentration range 0.05-4.50 mmol l-1 with a rapid response of less than 20 s. The polymer film can prevent interference from uric acid and ascorbic acid and also increases the thermal stability of the sensor. The sensor can be used for 200 assays without an obvious decrease in activity.

PHOTOELECTROCHEMISTRY OF ELECTRODEPOSITED POLYCRYSTALLINE CUINSE2 THIN-FILMS .1. ELECTRODEPOSITION OF CUINSE2 FILMS

Electrodeposition of CuInSe2 was investigated in acidic solutions containing Cu2+, In3+ and HSeO2+ ions. The electrodeposition condition was optimized with the aim of obtaining uniform thin films on titanium substrate. The mechanism of the electrodeposition process is discussed. Structure analysis of the deposited film shows a typical polycrystalline chalcopyrite structure, good crystallinity and homogeneous dispersion. The photoelectrochemical cells made of these kinds of deposited films in polysulfide redox solution give distinct photoresponse.

ELECTRODEPOSITION OF PLATINUM PARTICLES ON GLASSY-CARBON MODIFIED WITH COBALT PORPHYRIN AND NAFION FILM AND THEIR ELECTROCATALYTIC REDUCTION OF DIOXYGEN

In this paper, five types of chemically modified electrode (CMEs) prepared with the deposition of platinum particles on various surfaces of glassy carbon (GC) modified with cobalt porphyrin and Nafion(R) solution are characterized using the electron scanning microscope (SEM). Their activities in the four-electron reduction of dioxygen to water on the basis of their electrochemical data from cyclic voltammetric and rotating ring-disk electrode (RRDE) experiments are examined and compared. Platinum particles dispersed on the GC surface adsorbed with the cobalt porphyrin exhibit the highest activity for the electrocatalytic reduction of dioxygen. However it is interesting that the cobalt ion is lost from the center of the porphyrin ring during the preparation of the cobalt porphyrin + Nafion mixture solution, while the porphyrin ring still remains in the Nafion film, as shown by EDX analysis. The incorporation of the porphyrin may change the structure of the Nafion film into a looser form, since the platinum particles dispersed in the film are more readily exposed, resulting in more favourable mass transfer and higher activity for the electrocatalytic reduction of dioxygen.

ELECTRODEPOSITION OF POLYCRYSTALLINE CD-RICH HG1-XCDXTE AND PHOTOELECTRO-CHEMICAL BEHAVIOR OF HG0.09CD0.91TE THIN-FILM

Electrodeposition process of polycrystalline Cd-rich Hg_(1-z)Cd_xTe (x>0.5) in acidic bath of CdSO_4+HTeO_2~+HgCl_2 was investigated. The simultaneous electrodeposition technique of three kinds of ions at the same potential has been achieved. The XRD, SEM and EDAX analysis of the thin film electrodeposited on titanium substrate showed a typical cubic zinc blende polycrystalline structure and homogeneous dispersion. The photoelectrochemical behavior of (1-x)=0.09 polycrystalline thin film in a polysulfide re...

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.

The Key Factors In Fabrication Of High-Quality Ordered Macroporous Copper Film

The template-directed fabrication of highly-ordered porous film is of significant importance in implementation of the photonic band gap structure. The paper reports a simple and effective method to improve the electrodeposition of metal porous film by utilizing highly-ordered polystyrene spheres (PSs) template. By surface-modification method, the hydrophobic property of the PSs template surfaces was changed into hydrophilic one. It was demonstrated that the surface modi. cation process enhanced the permeability of the electrolyte solution in the nanometer-sized voids of the colloidal template. The homogeneously deposited copper film with the highly-ordered voids in size of less than 500 nm was successfully obtained. In addition, it was found that large defects, such as microcracks in the template, strongly influenced the macroporous films quality. An obvious preferential growth in the cracked area was observed. (C) 2008 Elsevier B. V. All rights reserved.

Cyclic Deformation Of Nanocrystalline And Ultrafine-Grained Nickel

The cyclic deformation behavior Of ultrafine-grained (UFG) Ni samples synthesized by the electrodeposition method was studied. Different from those made by severely plastic deformation, the UFG samples used in this study are characterized by large-angle grain boundaries. Behaviors from nanocrystalline Ni and coarse-grained Ni samples were compared with that Of Ultrafine-grained Ni. With in situ neutron diffraction. unusual evolutions of residual lattice strains as well as cyclic hardening and softening behavior were demonstrated during the cyclic deformation. The microstructural changes investigated by TEM are discussed with respect to the unusual lattice strain and cyclic hardening/softening. (C) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.