Dissolution electrochimique des films anodiques du titane dans l''acide sulfurique

Electrochemical dissolution of anodic oxide films on Ti in H₂SO₄ is studied by the use of an optical—electrolytic cell adapted for in situ ellipsometric and electrochemical measurements. Films were grown on electropolished Ti surfaces by anodic oxidation in 0.5 mol dm⁻³ H₂SO₄ for duration of 30 s, in the potential range from 0 to 100 V. Electrochemical dissolution of these films was performed in the potential range between −0.4 and −0.9 V sce. The potential at which electrochemical dissolution is fastest and homogeneous is determined. In addition it is shown that for potentials more cathodic than −0.8 V, TiH₂ is formed on the electrode surface, if polarization lasts sufficiently long. THe commencement of formation and dissolution of anodic films was monitored by potentiostatic j-E curves and variations of ellipsometric azimuths P and A. by potentiostatic and ellipsometric measurements it was confirmed that complete reduction of anodic films is possible. A possibility is indicated for calculating the refractive index of anodic film during its dissolution by observing the time of successive diminution of film thickness and using the variations of ellipsometric azimuths P and A.     

Potentiodynamic behaviour of mechanically polished titanium electrodes

The behaviour of titanium electrodes mechanically polished and/or anodically polarized at low positive potential in solutions at constant ionic strength between pH 0.3 and 11.0 is reported. The oxide electroformation potential on a mechanically polished electrode shows a complex dependence on the bulk solution pH. This dependence is similar to that obtained through acid-base titration with titanium as the indicating electrode. The formation of hydroxo-complexes on the spontaneously formed titanium oxide offers a possible explanation for the oxide electroformation potential dependence on pH. Anodic and cathodic wide current peaks are obtained between the potential of the hydrogen evolution and that of the massive oxide electroformation; the corresponding redox system becomes evident at pH 4.0 from the first potentiodynamic cycle. An interpretation of these processes involving the participation of non stoichiometric oxides and hydrogen ions is attempted.     

Correlation of electrochemical and ellipsometric data in relation to the kinetics and mechanism of Cu2O electroformation in alkaline solutions

The kinetics of copper anodization were studied in the potential range of Cu₂O electroformation in different alkaline solutions by using voltammetric, rotating disc electrode, rotating ring-disc electrode and ellipsometric techniques. Thin layer and massive copper electrodes were employed. Results indicate the formation of soluble Cu(I) species at the early stage of copper anodization. Other soluble Cu(II) species are produced after the Cu₂O layer electroformation. Data are discussed on the basis of a reaction mechanism involving different reaction products and the influence of the copper surface on the initial electrochemical reaction.     

Nature and stability of anodic oxide films formed on molybdenum in chloride solutions

The formation and stability of anodic oxide films on molybdenum in chloride solutions was tested using impedance and polarization measurements. The efficiency of oxide formation increases as the acidity of the formation medium increases. The film is highly stable and resistive to attack and dissolution regardless of the chloride concentration, pH or film thickness. The corrosion potential did not vary with variation of immersion time, solution composition or film thickness and recorded 0.000V vs SCE indicating the high insulating properties of the film. Polarization measurements on previously anodized molybdenum electrode showed that the electrode is ideally polarized over a potential region not less than 2V. The magnitude of that potential region increases as the film thickness increases. The anodic film cannot be reduced or removed by galvanostatic cathodic polarization. The impedance behaviour of the anodized molybdenum electrode was found to be purely capacitive and the oxide film may be treated approximately as a perfect dielectric material.     

Electrochemical reduction of chemically passivated iron

Iron passivated chemically in chromate solutions over a range of pH was electrochemically reduced in phosphate-borate buffer solution of pH 8.5. According to the chronopotentiometry, the passive film became thinner as the pH diminished, which was in agreement with the ellipsometric result. The rest potential became more positive with decreasing pH, and the pH dependence was ?0.11 V/pH and ?0.07 V/pH in acid and alkaline solutions, respectively. The shift of the rest potential towards more positive values did not lead to an increase in the thickness of the passive film, and in this it differs from the behaviour of the passive film formed anodically. This discrepancy can be rationalized by the idea that most of the potential drop appears not across the passive film, but at the passive film-solution interface. In chemical passivation, a positive shift of the electrode potential is not associated with the growth of the passive film, provided that the rest potential is more positive than the Flade potential. The most influential factor for passive film growth is the environment, in which the iron initially dissolves readily and the passive film retains its stability.     

Nitric oxide reduction at noble metal electrodes: a voltammetric study in acid solution

Features of the electrochemical reduction of nitric oxide on platinum, palladium, rhodium and ruthenium in aqueous perchloric acid solutions (0.33–1.0 M) are compared. The results from voltammetric studies (ie linear potential sweep and rotating disc electrode) using the bulk metal electrodes are described and compared with residual current voltage plots in acid electrolyte alone. In general, three nitric oxide reduction peaks are observed on the metals. The most anodic peak, at ca E = 0.15 V vs sce is attributed to the one-electron reduction of nitric oxide to an adsorbed NOH intermediate on a bare metal surface (ie one free of oxides or adsorbed hydrogen). The other two peaks occur in potential regions where adsorbed hydrogen is present on the metal surface (ca E = 0.0 and −0.20 V, respectively). The co-adsorbed hydrogen complicates the analysis and precludes an unambiguous interpretation of these two peaks. However, they apparently reflect nitric oxide reduction to nitrogen, hydroxylamine and/or ammonia. In a cathodic scan on the rhodium electrode, a current plateau is seen instead of the first (most anodic) peak, a probable consequence of oxide film formation with subsequent chemical complications. On the ruthenium electrode the first two (most anodic) peaks are not observed probably due to a relatively stable oxide layer. Reaction selectivities at metal black gas diffusion cathodes operating in an electrogenerative (ie galvanic) mode with perchloric acid electrolyte are compared with the voltammetric results at the corresponding bulk electrodes. Dinitrogen formation is observed on the platinum and rhodium black electrodes as suggested from voltammetric results. A series-parallel reaction sequence is proposed to explain the results. Limitations of using simple voltammetric techniques for predicting behavior of large scale preparative electrochemical reactors are discussed.     

In situ ellipsometric study of the growth and electrochemical cycling of polypyrrole films on platinum

The growth and potential cycling of polypyrrole films on platinum has been examined using time-resolved in situ ellipsometry. The optical properties of the films produced depend critically on the experimental conditions used to grow the films. Films grown from “wet” acetonitrile, or acidic ( n (1.25–1.35) at 633 nm, indicating the presence of a very strong absorption band in the near-infra-red (Lorentz oscillator model). Films grown in less optimal conditions (neutral aqueous solution, or with Fe(CN)³⁻₆-containing electrolyte) have higher n values (1.45–1.5). Comparison of calculated (from charge per unit area data) and measured (ellipsometric) film thickness shows that films grown in aqueous media are somewhat denser than those grown in acetonitrile. On reduction, the film thickness increases for films grown under all conditions, but the change is greater for films grown from aqueous solution. Changes in n and absorbance, k, are, as expected, wavelength-dependent, but in general n greatly increases (to 1.65–1.80); this is also rationalized using the Lorentz oscillator model, since the wavelengths employed are to low energy of a strong absorption in neutral polypyrrole at ca 390 nm. On potential cycling from the reduced to the oxidized form, the film thickness decreases between ca −0.6 and −0.2 V, but thereafter, although charge is still being passed, changes much more slowly.     

Electrooxidation of alcohols at a nickel oxide/multi-walled carbon nanotube-modified glassy carbon electrode

Electrocatalytic oxidation of methanol and some other primary alcohols on a glassy carbon electrode modified with multi-walled carbon nanotubes and nano-sized nickel oxide (GCE/MWNT/NiO) was investigated by cyclic voltammetry and chronoamperometry in alkaline medium. The results were compared with those obtained on a nickel oxide-modified glassy carbon electrode (GCE/NiO). Both the electrodes were conditioned by potential cycling in the range of 0.1–0.6 V versus Ag/AgCl in a 0.10 M NaOH solution. The effects of various parameters such as scan rate, alcohol concentration, thickness of NiO film, and real surface area of the modified electrodes were also investigated and compared. It was found that the GCE/MWNT/NiO-modified electrode possesses an improved electrochemical behavior over the GC/NiO-modified electrode for methanol oxidation.     

The anodic oxide film on iron in neutral solution

The composition of the anodic passive oxide film on iron in neutral solution has been investigated by cathodic reduction, chemical analysis and ellipsometry. The cathodic reduction using a borate solution of pH 6·35 containing arsenic trioxide as inhibitor estimates iron in the film to be all iron (III), indicating that no magnetite layer is present. Oxygen in the film is estimated from the ellipsometric thickness to be in excess of the stoichiometric ferric oxide, suggesting the presence of bound water. The average composition is represented as Fe₂O₃.0·4H₂O, in which hydrogen may be replaced partly with iron-ion vacancy. The anodic oxide film is composed of an inner anhydrous ferric oxide layer, which thickens with the potential and an outer layer of hydrous ferric oxide whose thickness depends on the condition of passivation and environment.     

Electrosorption and inhibition properties of p-norborn2-yl phenolate ions at the mercury/solution interface

The electrosorption properties of p-norborn-2-yl phenolate ions in alkaline solutions were investigated by ac polarographic and electrocapillary measurements.

Two adsorption regions were found. At low bulk surfactant concentrations the adsorption at the positively charged electrode (−0.2 E −0.6 V) is predominant while at higher surfactant concentrations the adsorption at the negatively charged electrode (−0.6 E −1.0 V) is more pronounced. At E = −0.40 V the adsorption parameters were determined (a ≈ 2; ΔG°_A = −32.5 ± 1 kJ mol⁻¹. Between −0.6 E −1.0 V one potential of maximum adsorption for all concentrations does not exist and therefore the adsorption parameters could not be calculated.

At E = −0.40 V progressive two-dimensional nucleation with a nucleation order of 3 was observed which corresponds well with the high attraction constant.

The electrode reaction S₂O²⁻₈ + 2e⁻ → 2 SO²⁻₄ is inhibited by norborn-2-yl phenolate ions in the potential range −0.2 E −0.6 V. In the second potential range of capacity decrease the electrode process is much less retarded. At E = −0.40 V, in a similar manner as described for neutral molecules, a linear dependence of the log k_s (k_s apparent rate constant) on ln c_A and π (π = surface film pressure), respectively, has been found.     

Synthesis of electrochemically-reduced graphene oxide film with controllable size and thickness and its use in supercapacitor

An electrochemical synthesis method of reducing graphene oxide (GO) under constant potential is reported. Electrochemical technique offers control over reaction parameters such as the applied voltage, electrical current and reduction time; whereas the desired size and thickness of the film can be pre-determined by controlling the amount of precursor GO deposited on the electrode with defined shape and surface area. This synthesis technique produces high quality electrochemically reduced GO (ERGO) film with controllable size and thickness. Electrochemical symmetrical supercapacitors based on ERGO films achieved a specific capacitance of 128 F/g with an energy density of 17.8 Wh/kg operating within a potential window of 1.0 V in 1.0 M NaNO₃. The supercapacitor was shown to be stable, retaining ca. 86% of the original specific capacitance after 3500 charge–discharge cycles. The results indicate that this simple synthesis technique for providing graphene-like materials has great potential in various applications such as energy storage.     

Electrochemical reduction of thermally prepared oxides of iron and iron-chromium alloys studied by in situ Raman spectroscopy

Pure Fe and Fe/Cr alloys (3% and 12% Cr) were oxidized at 250–260°C and subsequently electrochemically reduced in borate buffer, pH 8.4. The reduction was followed by in situ Raman spectroscopy as well as chronopotentiometric and chronoamperometric measurements. At several time intervals ex situ Raman control investigations and ESCA analyses were undertaken. Although at −0.7 V vs sce partial reduction of the oxide film was observed, -Fe₂O₃ remained unchanged and reduced at −0.9 V. A mixture of spinel structured oxide, possibly Fe₃O₄, and a ferrous deposit were observed when the oxide film was galvanostatically reduced at 100 μA cm⁻²; after prolonged reduction the bare metal resulted. The thermally created oxide of the Cr alloy possessed an inner Cr rich layer which during the galvanostatic reduction of the oxide film at 50 μA cm⁻² is most likely responsible for an increase in the overpotential of more than 80 mV.     

Electrochemical and ellipsometric study of the oxide films formed on copper in borax solution: Part I: Effect of oxygen

The formation and reduction of passive layers on copper in weakly alkaline solutions saturated with N2 and O2 were studied. Voltammetric and ellipsometric techniques were employed to examine the structural characteristics of the layers formed in the –0.32 to 0.75 V vs RHE potential region. Optical measurements at open circuit potentials (Eoc) were also made to simulate operational conditions. The passive layer consists of a duplex structure: an outer hydrated copper oxide film and an inner dehydrated film. This inner layer is composed of Cu2O with a surface excess of Cu(ii) ions. The growth rate of the oxide layers at controlled potentials is higher in O2 saturated solution. The corrosion resistance of copper depends on the presence of O2 in the electrolyte, on the stirring rate and on the Eoc value.     

The electrochemical behaviour of copper in alkaline solutions containing sodium sulphide

The electrochemical behaviour of copper in NaHCO₃ solution (pH 9) and NaOH solutions (pH 14) in the presence of sodium sulphide (10^–3 to 5×10^–2m) was investigated by using rotating disc electrode and rotating ring-disc techniques, triangular potential scanning voltammetry and potentiostatic steps. When the potential increases from –1.2V upwards, copper sulphide layers are firstly formed at potentials close to the equilibrium potentials of the Cu/Cu₂S and Cu/CuS reversible electrodes. When the potential exceeds 0.0 V (NHE), the copper oxide layer is electroformed. Pitting corrosion of copper is observed at potentials greater than –0.3 V. The charateristics of copper pitting are also determined through SEM optical microscopy and EDAX analysis. There are two main effects in the presence of sodium sulphide, namely, the delay in the cuprous oxide formation by the presence of the previously formed copper sulphide layer and the remarkable increase of copper electrodissolution when the potential exceeds the cuprous oxide electroformation threshold potential. These results are interpreted on the basis of a complex structured anodic sulphide layer and on a weakening of the metal-metal bond by the presence of adsorbed sulphur on the copper surface.     

Electrical and electroluminescent properties of poly(p-phenylene vinylene) LB films based LEDs using aluminum metal as the electrode

The electrical properties of poly(p-phenylene vinylene) (PPV) Langmuir-Blodgett (LB) films were investigated, wherein transparent indium-tin oxide (ITO) and aluminum (Al) were used as the electrodes. Their I–V characteristics depended strongly on the thickness of PPV LB film, and the electric conductivity of the PPV LB film was in the range of 10⁻²–10⁻¹⁵ (S/cm). Their C–V characteristics showed that the capacitance was reversibly proportional to the thickness of PPV LB film and was kept constant when the applied voltage changed from −1.0 V to +1.0 V. These results indicated that PPV LB film was an insulator in this range of applied voltage without doping. Under forward bias, yellow-green light emission was observed in PPV LB film based light emitting diodes (LEDs), the highest light emission reached more than 100 cd/m² in the case that PPV LB film was deposited for 80 layers, i.e. a ITO/PPV(80L)/Al device.     

Surface and bulk processes at oxidized iridium electrodes—II. Conductivity-switched behaviour of thick oxide films

The electrochemical reversibility of thick oxide films that are formed on Ir electrodes by potential cycling is examined in relation to the initial monolayer surface oxidation processes. The unusual properties of thick oxide films on Ir, eg, as electrode surfaces for O₂ or Cl₂ evolution and with regard to H pseudocapacitance and double-layer capacitance being almost independent of oxide film thickness, arise because of a major increase of conductivity of the oxide as the oxidation state of Ir in the film is changed in a potential sweep between ca. 0.05 and 1.4 V E_H. In a cyclic sweep this has the effect of switching “on” or “off” the large real area of a microporous, hydrated oxide structure of the thick oxide films for electron transfer processes at their surfaces or within their bulk or pores.It is proposed that film growth which occurs on cycling is the result of accumulation of oxide produced in an underlying monolayer during each anodic sweep but which is left in an incompletely reduced state on each following cathodic sweep, due to irreversibility.     

Electrochemical reduction of thick oxide film on platinum electrode in alkaline solutions

The electrochemical reduction of the thick oxide film formed on Pt electrode by severe preanodization has been studied in LiOH, NaOH and KOH solutions of different concentrations (0.001 ～ 1.0 M) using a galvanostatic technique.An outermost monolayer oxide and an inner multilayer oxide of the thick oxide film exhibit different potential behaviors in the cathodic reduction. In dilute solution, both the oxides are completely reduced in a potential range of 0.6-0.4 V (vs rhe in the test solution) in a single step. As the concentration is increased, however, the reduction potential of the inner oxide only shifts rapidly into a H-electrosorption potential region and the amount of the oxide reduced at this potential decreases. The remaining oxide is slowly reduced at H₂-evolution potential. The retardation of the reduction of the inner oxide is related to cations adsorbed on Pt electrode. This retardation effect increases in the order, K⁺ < Na⁺ < Li⁺.     

紫铜海水管焊接部位在人工海水中的腐蚀行为

通过阳极极化曲线、交流阻抗测试、扫描电镜研究了紫铜海水管焊接部位在人工海水中的腐蚀行为.结果表明：紫铜、白铜焊缝和黄铜焊缝在人工海水中的阳极过程类似,相同电位下,白铜焊缝的电流密度最小,耐蚀性最佳,与阻抗测试结果一致.黄铜焊缝在电位-0.012 V时出现电流峰,腐蚀产物膜多孔、疏松,随后电极进入钝化区,钝化膜由Cu₂O、CuCl和ZnO组成;随电位升高,钝化膜溶解,发生铜锌置换反应,沉积的Cu导致活性电对的形成,增加了合金的腐蚀速度;当电位为＋0.87 V时,电极表面富集了针状锡和锡的氧化物.随后,电极表面积累的锡和锡的氧化物及腐蚀产物层对脱锌腐蚀有一定的阻碍作用,电流密度有所下降,最后腐蚀达到一种动态平衡,腐蚀机制为溶解-再沉积机理.     

Continuous activation in a rotating bipolar electrode cell—I via control of the surface oxide thickness

A recently developed rotating bipolar electrode cell, equipped with wiper blades, is described as a continuous activator of the electrode surface; the thickness of the oxide film is easily controlled and at a particular potential the rate of processes occurring on the oxide film can be greatly increased. Furthermore, at a particular current density the reaction potential can be significantly altered, and the products of electrolysis changed. The oxygen evolution reaction and the competing Kolbe dimerization reactions, taking place at Pt in aqueous acid electrolyte, provide specific illustrations of the operating principles.     

Optical and electrochemical evaluation of colloidal Au nanoparticle-ITO hybrid optically transparent electrodes and their application to attenuated total reflectance spectroelectrochemistry

Colloidal Au nanoparticle monolayers covalently deposited on conductive layers of indium tin oxide (ITO) were fabricated and evaluated as optically transparent electrodes (OTEs) for spectroelectrochemical applications. Specifically, the electrodes were characterized using UV-Vis spectroscopy and cyclic voltammetry; comparisons are made with other types of hybrid ITO optically transparent electrodes. The optical modulation of surface-bound colloidal Au in response to potential cycling over a wide potential window (0.6 to −1.0 V) was acquired in an attenuated total reflectance (ATR) spectroelectrochemical cell. Finally, uptake of a model analyte, tris-(2,2′-bipyridyl)ruthenium(II) chloride, into a Nafion charge selective film spin coated onto the colloidal Au-ITO hybrid electrode was examined using ATR absorbance spectroelectrochemistry. Dependence of uptake on film thickness is addressed, and non-optimized detection limits of 10 nM are reported.