Comparative study of initial stages of copper immersion deposition on bulk and porous silicon

Initial stages of Cu immersion deposition in the presence of hydrofluoric acid on bulk and porous silicon were studied. Cu was found to deposit both on bulk and porous silicon as a layer of nanoparticles which grew according to the Volmer-Weber mechanism. It was revealed that at the initial stages of immersion deposition, Cu nanoparticles consisted of crystals with a maximum size of 10 nm and inherited the orientation of the original silicon substrate. Deposited Cu nanoparticles were found to be partially oxidized to Cu₂O while CuO was not detected for all samples. In contrast to porous silicon, the crystal orientation of the original silicon substrate significantly affected the sizes, density, and oxidation level of Cu nanoparticles deposited on bulk silicon.     

Electrochemical activation and electrocatalytic enhancement of a hydride-forming metal alloy modified with palladium, platinum and nickel

The influence of the addition of polycrystalline Pt, Pd and Ni powders into hydride-forming metal alloy electrodes on the activation process, rate-capability and cycling stability has been evaluated. The metal powder additives were found to improve the activation rate and to decreased the overpotentials of the charge and discharge processes. The electrochemical properties of these modified electrodes were analysed in terms of a simplified form of a previously developed model. Electrochemical impedance spectroscopy measurements were performed to allow the validation of the model and the identification of kinetic and physicochemical parameters.     

Initial stages of electrodeposition of metal nanowires in nanoporous templates

This paper describes the initial stages of electrochemical growth of Cu and Ni nanowires in polycarbonate (PC) track-etched membranes as the template. The diameters of the wires ranged from 50 to 200 nm. A thin Pt-Pd layer (∼30 nm thick) was sputter-deposited onto one side of the membrane and used as the cathode. The layer was not thick enough to seal the pore mouths. Cathodic current in the early stages of both Cu and Ni electrodeposition abruptly decreased after a period proportional to the pore diameter. Growing Cu grains plugged the pore openings causing the current to decrease, while the Ni deposition initially yielded a hollow tube in each pore resulting in a nanostructure transition of the tube to the wire at the growth front and a decrease in the current.     

Spin localization for NO adsorption on surface O atoms of metal oxides

The adsorption of NO on the oxygen site of several metal oxide surfaces is discussed. It is shown that the strength of the interaction and the variation of the bond lengths are not always correlated to the electron transfer from NO to the surface atoms. In cases of irreducible metal oxides, NO₂²⁻ may be strongly adsorbed. The formation of NO₂⁻ on reducible metal oxide is difficult unless terminal oxygen is present on the surface. Then, the reduction of the surface by transferring the unpaired electron from the NO to the surface appears in DFT calculations (VASP code).     

The influence of the synthesis conditions of graphite/tin nanoparticle materials on their electrode electrochemical performance in Li-ion battery anodes

Electrochemical lithium insertion was carried out in tin-graphite composites obtained by two different preparation processes. In the first graphite was mixed with the products obtained by reduction of SnCl₄ with Na tert-Butanoate (t-BuONa)-activated NaH (two-step synthesis). The second used materials synthesized by reducing SnCl₄ with a graphite and (t-BuONa)-activated NaH suspension in THF (one-pot synthesis). Both composites were characterized by X-ray diffraction and transmission electron microscopy . It appeared that the tin particle size was controlled by the reduction time of SnCl₄. The stability of the electrochemical capacity of composites prepared by the two-step synthesis is dependent on the tin particle size: a stable capacity upon cycling was shown with subnanometer particles while a capacity fade was observed with larger nanoparticles. In materials prepared by the one pot synthesis, tin was present either as nanopartcles supported on graphite or as free aggregates. An initial reversible capacity of 630 mA hg⁻¹ decayed to a constant value of 415 mA hg⁻¹ after 12 charge/discharge cycles. It was hypothesized that the fraction of tin bound to graphite contributed to the stable reversible capacity while free tin aggregates were responsible for its decay.     

In situ detection and removal of metal ion by porous gold electrode

A sensing electrode for the detection of heavy metal ions in aqueous solution selectively measured the concentrations of target materials on its functionalized surface, which has affinity to target metal ions. Target ions were adsorbed simultaneously on the functionalized electrode during the sensing process. Therefore, to understand this, experiments on the amperometric response and isotherms with an initial concentration of Hg²⁺ were tested. Detection current was dependent on the concentration of Hg²⁺, and the equilibrium concentration of Hg²⁺ adsorbed to the electrode showed a Langmuirian shape. Correlation between the detection current and removal capacity for Hg²⁺ revealed that it is possible to estimate the adsorbed concentration on the electrode during the sensing step. Although the macroporous gold electrode prepared herein showed relatively low adsorption performance compared to conventional adsorbents, when we prepare nanoporous gold electrodes with a uniform nanopore structure and large surface area, in situ detection and simultaneously removal of metal ions by nanoporous gold electrode will be possible.     

Fabrication of patterned nanostructures with various metal species on Si wafer surfaces by maskless and electroless process

Maskless and electroless fabrication was demonstrated to form patterned nanostructures of various metal species, based upon the process previously developed by the authors. In this process, the metallic nanostructures were formed on the surface of clean, hydrogen terminated p-(1 0 0) Si wafer with pre-patterned nanoscopic defects, which were confirmed to possess higher activity for the reductive deposition reaction of the metal ion species. The deposition was achieved spontaneously and selectively at the defect sites on the wafer surface by immersing into dilute aqueous fluoride solution containing trace amount of metal ion species. By optimizing the formation condition of the patterned defects and composition of the solution, fabrication of patterned nanostructures of various metallic species such as Au, Ag, and Co, was achieved. Formation of the patterned nanostructures to 10 μm² in extent, as well as control of the feature size of the deposits by adjusting the formation condition of the patterned defects were also attempted.     

The electrochemical impedance of metal hydride electrodes

The electrochemical impedance responses for different laboratory type metal hydride electrodes were successfully modeled and fitted to experimental data for AB₅ type hydrogen storage alloys as well as one MgNi type electrode. The models fitted the experimental data remarkably well. Several AC equivalent circuits have been proposed in the literature. The experimental data, however, could not always be satisfactorily approximated. The approximation model presented here exhibits smooth fit to the experimental results for all frequencies in the whole range from 10 kHz to 0.1 mHz. Equivalent circuits, explaining the experimental impedances in a wide frequency range for electrodes of hydride forming materials mixed with copper powder, were obtained. Both charge transfer and spherical diffusion of hydrogen in the particles are important sub processes that govern the total rate of the electrochemical hydrogen absorption/desorption reaction. To approximate the experimental data, equations describing the current distribution in porous electrodes were needed. Indications of one or more parallel reduction/oxidation processes competing with the electrochemical hydrogen absorption/desorption reaction were observed. The impedance analysis was found to be an efficient method for characterizing metal hydride electrodes in situ.     

几种多孔电极材料镓电沉积性能的研究

在工业上,稀散金属镓通常是从碱性溶液中电解提取得到的。在镓电解过程中,由于析氢副反应和传质速率低的原因导致镓电沉积的电流效率很低。本工作采用三维多孔电极电沉积镓,利用三维多孔电极发达的表面积促进镓电沉积过程,研究了不同电极材料(泡沫金属和多孔碳)的析氢特性,结合不同电解温度和电流密度下各材料的镓电沉积行为,揭示三维多孔电极上镓电沉积的特性规律。结果表明,泡沫铜和石墨毡(GF)具有较低的析氢活性,但两种电极的镓电沉积性能差别很大。其中泡沫铜表现出最佳的镓电沉积性能,在温度为40℃、电流密度为0.1 A/cm²条件下镓电沉积的电流效率(QE)达到22.5%,远高于铜片电极(10.7%);而相同条件下,GF电极的QE值仅为9.6%,低于铜片,这与电极表面的疏水性有关。具有较高析氢活性的泡沫铁、泡沫镍和网状玻璃碳(RVC)电极的镓电沉积过程受电解温度和电流密度的影响较大。在高电流密度下,泡沫铁电极表现出仅次于泡沫铜的QE值,在低电流密度下难以发生镓的电沉积;泡沫镍和RVC电极仅在低于镓熔点(20℃)的条件下发生镓的电沉积,在高于镓熔点(40℃)的条件下,由于电沉积的液态镓...     

Study on surface modification of AB5-type alloy electrode with polyaniline by electroless deposition

A new polyaniline (PANI)-coated technique was adopted for a AB₅-type alloy (La_0.64Ce_0.25Pr_0.03Nd_0.08Ni_4.19Mn_0.31Co_0.42Al_0.23) in order to improve its electrochemical and kinetic properties. FE-SEM observation and FT-IR analysis results revealed that the PANI electroless deposited to the surface of alloy particles. Through the PANI-coating the initial discharge capacity increased from 299 to 331 mAh/g and the high rate discharge ability (HRD) increased from 8.5 to 45.0% at discharge current density of 1440 mA/g. For kinetic properties, linear polarization, EIS, anodic polarization and cyclic voltammetry measurements suggested that charge-transfer resistance decreased and the hydrogen absorption rate of the alloys increased after PANI-coating.     

Novel electrode materials based on ion beam induced deposition of platinum carbon composites

Untreated and thermally annealed platinum carbon (PtC) composites obtained by ion beam induced deposition (IBID) are physically and electrochemically characterized as novel patternable electrode materials. Energy dispersive X-ray spectroscopy (EDX) and Raman spectroscopy reveal that annealing in ambient atmosphere and at temperatures above 400 °C substantially reduces the amount of carbon within the deposited material. Raman spectra also show that at elevated temperatures carbon rearranges into a more structured graphitic-like phase. Atomic force microscopy (AFM) reveals that after the annealing procedure the surface structure appears more corrugated, while the dimensions of granular surface features decreases. Furthermore, it is shown that electrodes based on annealed PtC material show an improved heterogeneous electron transfer rate for the oxidation of potassium hexacyanoferrate(II) trihydrate by almost three orders of magnitude, whereas the reduction of hexaammineruthenium(III) trichloride proceeds at similar rates for both treated and untreated electrodes. The rate of electrochemical oxidation of H₂O₂, which is influenced by the composition of the electrode surface, is also improved at thermally annealed electrodes. Finally, cyclic voltammetry in sulfuric acid shows an increase in surficial platinum concentration after annealing of the material.     

Influence of tartaric acid on zinc electrodeposition from sulphate bath

The effect of tartaric acid on zinc electrodeposition from sulphate plating bath was investigated by electrochemical impedance spectroscopy (EIS), stationary polarization curves, X-ray diffraction and SEM imagery. The study shows that it is possible to obtain homogeneous, compact and dendrites-free zinc deposits from sulphate solutions containing tartaric acid. For various hydrodynamic methods (rotating disc electrode and static vertical or horizontal electrode), the results indicate that, the presence of only small quantity of tartaric acid, may induce significant changes on deposition rates and deposit quality.     

The electrochemical oxidation of sulfite on gold: UV-Vis reflectance spectroscopy at a rotating disk electrode

Certain aspects of the electrochemical oxidation of sulfite in buffered, mildly acidic aqueous solutions (pH 5.23) have been examined using in situ near normal incidence UV-Vis reflectance spectroscopy (NNI-UVRS) at a Au rotating disk electrode (RDE). The dependence of the limiting current, i_lim, on the rotation rate of the RDE was found to display classical Levich behavior up to potentials well within the range in which Au forms a surface oxide in the neat (sulfite-free) supporting electrolyte. However, simultaneous in situ NNI-UVRS measurements performed at λ=500 nm during sulfite oxidation failed to show any evidence for the presence of oxide on the Au surface within that entire potential range. Polarization of the Au RDE at more positive potentials led to a sudden drop in i_lim, ca. an order of magnitude, which correlated with an abrupt decrease in the intensity of the reflected light, consistent with formation of (one or more forms of) Au oxide on the surface. On the basis of these and other observations a model has been proposed in which sulfite reacts chemically with adsorbed oxygen on the surface (oxygen atom transfer) in the region that precedes partial inhibition. As the potential is increased, adsorbed oxygen undergoes Au-O place exchange forming two-dimensional nuclei on the surface, which undergo rapid (autocatalytic) growth, covering an area large enough to block significantly sulfite oxidation.     

Fabrication of integrated arrays of ultrahigh density magnetic nanowires on glass by anodization and electrodeposition

Integrated nanowire arrays of Fe-Pt, Co-Pt, and Ni-Pt alloys were successfully fabricated on glass substrates by successive anodization and electrodeposition. Porous alumina films, which were formed from an aluminum layers sputter-deposited on glass substrates covered with transparent oxide conductive films, were used as template-electrodes to deposit various magnetic alloys (Fe-Pt, Co-Pt, and Ni-Pt) in the nanopores by a cathodic electrodeposition, thus leading to integrated nanowire arrays with ultrahigh densities of (0.6-2.1) × 10¹⁵ wire m⁻². The as-deposited nanowires of Fe-Pt, Co-Pt, and Ni-Pt alloys are polycrystalline and composed of fine crystals (4-7 nm across) of chemically ordered tetragonal FePt, CoPt, or NiPt phase. The integrated nanowire arrays may be the promising candidate materials for ultrahigh density perpendicular magnetic recording media in terabits per square inch regime, due to the predictable enhanced perpendicular magnetic performance after appropriate annealing.     

Thiols deposition onto the surface of glassy carbon electrodes mediated by electrical potential

Electrochemical oxidation of thiols in acetonitrile and application of this process for modification of glassy carbon electrodes were studied. Addition of strong deprotonating agent, tetrabutylammonium hydroxide, was found to facilitate oxidation of thiols as well as their deposition onto the carbon surface. Thus, in the presence of 1 mM tetrabutylammonium hydroxide, glassy carbon electrode can be grafted with 1 mM 3-(nitrobenzyl)mercaptan at as low as +200 mV (vs. SCE). The modified electrodes were characterized by electrochemical methods and XPS confirming the stable binding of thiols which were absent on the surface of unmodified and control treated electrodes. Surprisingly, surface modification occurs independent of RS radicals formation and is explained by nucleophilic addition of deprotonated thiols to the surface of carbon electrode. The electrode potential plays an important role in this process presumably modulating electrophilic properties of the carbon surface.     

Fabrication and characteristics of Pd nanoparticles/nanofilms on ceramics toward catalytic electrodes

We report an approach of fabricating various palladium nanostructures with tailored morphologies in nanoparticles (Ø80-300 nm), nanoporous films (Ø50-200 nm), and integrated nanotubules arrays (Ø300 nm and 5 μm long) on different ceramic materials. Microporous titanate ceramics or nanoporous alumina films were first prepared through a solid-state synthesis or an anodic oxidization of aluminum sheets. The micro- and nanoporous ceramics were then used as supporting materials in an electroless deposition to deposit Pd nanoparticles or nanofilms over the porous substrates, thus leading to various Pd nanostructures with large surface areas and high corrosion resistance for many applications. EDX and EPMA analysis disclosed that the phosphor co-deposition in 5-11 at.% P occurred in the palladium electroless deposition. XRD analysis showed that the as-deposited Pd-P alloys were polycrystalline with a preferential orientation of (1 1 1) facet. The phosphor included in the Pd-P alloy films existed as a solid solution form, rendering as a single phase Pd-P alloy with nanocrystals (∼5 nm across) of cubic palladium.     

Adsorbate effects on the surface stress-charge response of platinum electrodes

The length change in response to changes in the surface stress during scans of the electrode potential was measured for nanoporous platinum samples immersed in aqueous NaF, an electrolyte with weak ion adsorption. The surface stress-charge response may be characterized separately for four different processes, selected by the potential range and by the surface pretreatment: hydrogen adsorption/desorption, oxygen adsorption/desorption (and/or surface oxidation/reduction), and nominally capacitive charging of the Pt surface in two different states, clean and oxide-covered. While each process exhibits a roughly linear response, the magnitude and even the sign of the slope, which determines the surface stress-charge coefficient, ζ, differ. We suggest that the sign of ζ depends on the penetration depth of the excess charge: for strong screening the electronic charge is located outside of the surface, and ζ is negative as found previously for clean metal surfaces. For weaker screening, the wider space charge layer implies a trend for the excess charge to fill bulk-like unoccupied states. These states are here antibonding, giving positive-valued ζ.     

Electrochemical behaviour of metal hexacyanoferrate converted to metal hydroxide films immobilized on indium tin oxide electrodes—Catalytic ability towards alcohol oxidation in alkaline medium

In this work, we demonstrate a simple method to modify indium tin oxide (ITO) electrodes in order to perform electro-catalytic oxidation of alcohols in alkaline medium. Metal hexacyanoferrate (MHCF) films such as nickel hexacyanoferrate (NiHCF) and copper hexacyanoferrate (CuHCF) were successfully immobilized on ITO electrodes using an electrochemical method. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the structural and morphological aspects of MHCF films. Cyclic voltammetry (CV) was used to study the redox properties and to determine the surface coverage of these films on ITO electrodes. Electrochemical potential cycling was carried out in alkaline medium in order to alter the chemical structure of these films and convert to their corresponding metal hydroxide films. SEM and XPS were performed to analyze the structure and morphology of metal hydroxide modified electrodes. Electro-catalytic oxidation ability of these films towards methanol and ethanol in alkaline medium was investigated using CV. From these studies we found that metal hydroxide modified electrodes show a better catalytic performance and good stability for methanol oxidation along with the alleviation of CO poisoning effect. We have obtained an anodic oxidation current density of ∼82 mA cm⁻² for methanol oxidation, which is at least 10 fold higher than that of any metal hydroxide modified electrodes reported till date. The onset potential for methanol oxidation is lowered by ∼200 mV compared to other chemically modified electrodes reported. A plausible mechanism was proposed for the alcohol oxidation based on the redox properties of these modified electrodes. The methodology adapted in this work does not contain costlier noble metals like platinum and ruthenium and is economically viable.     

Influence of initial surface condition of lithium metal anodes on surface modification with HF

Surface modification of as-received lithium foils was carried out using acid-base reactions of the native surface films on lithium metal with HF. Two types of as-received lithium foils covered with different native films were used as samples for this surface modification. One was a lithium foil having a very thin native surface film and the other one had a thicker native surface film. The surface condition of the lithium metal was analysed by X-ray photoelectron spectroscopy before and after the surface modification using HF, and the coulombic efficiency was measured electrochemically. The thickness of the surface film on the modified lithium foils was related to the Li₂O layer thickness in the native film on the as-received lithium foils. The modified lithium foil which had the thinner native surface film provided more uniform deposition of lithium and a higher coulombic efficiency during charge and discharge cycles when propylene carbonate electrolyte with 1.0 m LiPF₆ was used as the electrolyte. These results show that the initial condition of the native surface film plays an important role in surface modification with HF.