Cyclic Voltammetry of a Fluoride-Selective Electrode in Contact with Metals

Electrochemical behavior of the interface between a LaF₃ : Eu²⁺ single-crystal fluoride-selective membrane and Bi, Sn, Pb, Sb, and Cd metallic microelectrodes is considered with the aim to apply a fluoride-selective electrode in solid-state voltammetry. The ionization-discharge processes on the metals in air, involving mobile fluoride ions from the LaF₃ membrane, were studied by cyclic voltammetry.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005, pp. 265–272.Original Russian Text Copyright © 2005 by Turaeva, Pegova, Vasilevskii.     

Kinetics of intermediate phase growth at the interface of fluoride-conducting solid electrolytes with metal electrodes

The effect of the reference electrode (Ag, AgCl∣KF + KCl or Sn, SnF₂) on the kinetics of new phase growth at interfaces formed by LaF₃:Eu²⁺ or CeF₃:Sr²⁺ single crystal solid electrolytes with metal electrodes of Ag and Bi is studied by chronoamperometry and linear scan voltammetry. It is shown that when a solid-phase reference electrode is used, the current transients reflect hindrances associated with instantaneous two- or three-dimensional nucleation as well as limitations for fluoride ion diffusion in the solid electrolyte.     

Effect of the Electrode Material on the Reduction of La<Superscript>3+</Superscript> and Ce<Superscript>3+</Superscript> in Fluoride-Conducting Solid Electrolytes

The reduction of immobile cations La³⁺ and Ce³⁺ in fluoride-conducting solid electrolytes (FSE) LaF₃ (Eu²⁺ 0.8 mol %), LaF₃ (Sr²⁺ 5 mol %), and CeF₃ (Sr²⁺ 5 mol %) in contact with Ag, Bi, Si, La, Ce, and Sm working electrodes is studied by chronoamperometry and voltammetry with linear potential scan. Discovered is linear dependence of initial segments of potentiostatic transients of cathodic current on t ^1/2 at FSE interfaces with Ag, Bi, La, Ce, and Sm. The dependence is due to diffusion-controlled instantaneous nucleation of Ln and Ce. The La³⁺ and Ce³⁺ reduction at the FSE/Ag interface is reversible in a narrow region. The reduction and oxidation of La³⁺ and Ce³⁺ (cations of the FSE rigid lattice) at the FSE/Me (Me = La, Ce and Sm, Bi, Si) interface is irreversible and involves a chemical reaction.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 662–672.Original Russian Text Copyright © 2005 by Turaeva, Kot, Urchukova, Murin.     

Effect of the electrode material on the oxygen reduction at the nonstoichiometric lanthanum fluoride/electrode interface

The voltammetry method with a linear potential scan is used for investigating the effect the electrode material (Ni, Co, electrodes on the basis of cobalt oxides modified with carbon) exerts on the reduction of gaseous oxygen at interfaces solid fluoride-conducting electrode LaF₃:Eu²⁺/electrode, O₂, and conjugated processes. Properties of the modified electrodes are characterized by the impedance spectroscopy, scanning electron microscopy, and x-ray photoelectron spectroscopy methods. The oxygen reaction is irreversible at the LaF₃:Eu²⁺|Ni (or Co) interfaces. At the interface of LaF₃:Eu²⁺ with modified electrodes Co (C n at %), where n = 5 and 9, mobile forms of oxygen are reversible and the reduction of gaseous and chemisorbed oxygen is controlled by diffusion with different effective kinetic parameters.     

Galvanostatic investigation of electrochemical processes at the LaF<Subscript>3</Subscript>/M (M: Ag,Bi) interface

The electrochemical processes at the interface between solid fluorine-conducting electrolyte LaF₃(Eu²⁺ 0.8 mol %) and silver or bismuth electrodes in the two-electrode cell with nonpolarizable reference electrode are studied using the galvanostatic method. The anodic galvanostatic transients of LaF₃: Eu²⁺/Ag and LaF₃: Eu²⁺/Bi interfaces are linearized on the log(η ? η_max), vs. t coordinates, i.e. the rate of LaF₃|MF _n |M electrode formation is limited by slow surface diffusion of metal adions. The initial portions of cathodic galvanostatic transients in the range of solid-electrolyte lanthanum reduction are approximated by the linear dependence of η on log(1 ? √t/τ). The plots of logI vs. 1/η are linear both for the lanthanum reduction and for silver and bismuth oxidation involving mobile fluoride ion of solid electrolyte, which is typical for two-dimensional growth of new phase.     

Electrochemical behavior of single crystals of nonstoichiometric cerium(III) fluorides

The electrochemical properties of single crystals of cerium fluoride alloyed with bivalent cations Sr²⁺, Ca²⁺, Ba²⁺, Sr²⁺ + Ca²⁺, Sr²⁺ + Ba²⁺, Ba²⁺ + Ca²⁺ and also with La³⁺ and La³⁺ + Ba²⁺ cations are studied using the dynamic voltammetry and impedance spectroscopy. The conductivity of symmetrical cells with Ag electrodes is determined using the method of impedance spectroscopy in the frequency range from 450 to 5 kHz at the temperatures from 20 to 100°C: for CeF₃: Sr²⁺ (0.5 mol %) + Ba²⁺ (0.5 mol %), σ = σ₀ exp[(?0.284 ± 0.005/kT]; for CeF₃:Ca²⁺ (0.5 mol %) + Sr²⁺ (0.5 mol %), σ = σ₀ exp[(?0.292 ± 0.017/kT]. The steady-state and dynamic voltammogams of symmetrical electrochemical cells with nonpolarizable reference electrodes and CeF₃ single crystals alloyed with Sr²⁺, Ca²⁺, and Ba²⁺ bivalent cations exhibited ohmic polarization. For cells with CeF₃ containing La³⁺ as an admixture, a hysteresis was observed, which could not be eliminated by chemical and electrochemical treatment of crystals. In the dynamic voltammetric curves of asymmetric cells with nonpolarizable and silver electrode and CeF₃ crystals alloyed with Sr²⁺, Ca²⁺, and Ba²⁺, a range of ideal polarizability (from 0 to ～?2.7 V), and also cerium redox processes and silver fluorination-boundary regeneration were observed. In the dynamic voltammetric curves of asymmetric cells with CeF₃ containing La³⁺ admixture, no range of ideal polarizability was observed; however, the reactions of silver fluorination and reduction of solid-electrolyte cerium were well pronounced at the corresponding potentials.     

Oxygen reduction at the interface of nonstoichiometric fluoride single crystals with metal electrodes

Electrochemical measurements are carried out on three-phase boundaries LaF₃:Eu²⁺/Me, oxygen gas, where Me = Ti, Be, Ta, Au and also on the boundaries of CeF₃:Sr²⁺ with Ag-supported Ag and Bi microelectrodes by the methods of linear scan voltammetry, chronoamperometry, and cyclic voltammetry. The conditions beneficial for reduction of oxygen gas, transformations of chemisorbed oxygen, and the appearance of its mobile forms are considered. Results on the interaction of gaseous oxygen with metals in contact with LaF₃:Eu²⁺ single crystals are generalized. The correlation is found between the oxygen reduction potential and the difference of electronegativities Δχ Me-O. The relationship is revealed between the oxygen reduction potential and the Me-Me bond energy by taking into account the structural factor f/k _n, where f is the number of binding electrons and k _n is the coordination number.     

Sensitive and Simple Electrochemical Detection of Lead(II) with Carbon Ionic Liquid Electrode

In this paper a carbon ionic liquid electrode (CILE) was fabricated by using ionic liquid 1‐ethyl‐3‐methylimidazolium ethylsulphate ([EMIM]EtOSO₃) as the modifier and further used as the working electrode for the sensitive anodic stripping voltammetric detection of Pb²⁺. The characteristics of the CILE were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In pH 4.5 NaAc‐HAc buffer Pb²⁺ was accumulated on the surface of CILE due to the extraction effect of IL and reduced at a negative potential (‐1.20 V). Then the reduced Pb was oxidized by differential pulse anodic stripping voltammetry with an obvious stripping peak appeared at ?0.67 V. Under the optimal conditions Pb²⁺ could be detected in the concentration range from 1.0 × 10^?8 mol/L to 1.0 × 10^?6 mol/L with the linear regression equation as I_p(μA) = ?0.103 C (μmol/L) + 0.0376 (γ = 0.999) and the detection limit as 3.0 × l0^?9 mol/L (3σ). Interferences from other metal ions were investigated and Cd²⁺ could be simultaneously detected in the mixture solution. The proposed method was further applied to the trace levels of Pb²⁺ detection in water samples with satisfactory results.     

An improved selective fluoride electrode

The major cause of failure for an Orion Research 9409A fluoride-selective electrode observed in routine use in our laboratory is loss of contact with the LaF₃ crystal. Opening the electrode and replacing the electrolyte restores electrodes that suffer from this effect.     

Electrochemical Behavior of the LaF3:Eu2+/Me Interface (Me = Sm,Ce, Gd,V, Ag)

The electrochemical behavior of the LaF₃ : Eu²⁺| interface (Me = Sm, Ce, Gd, V, Ag) is studied using stripping voltammetry. Current–voltage curves for cells Ag, AgCl|KCl and KF|LaF₃ : Eu²⁺|Sm (or Ce) may be viewed as background curves for analyzing solid-phase reactions with other metallic electrodes. The substrate material is found to affect properties of interfaces LaF₃ : Eu²⁺/Gd (or V), which are characterized either by solid-phase reactions involving the fluoride ion of a solid electrolyte or by reactions involving oxygen. Regularities, obtained for silver in contact with LaF₃ : Eu²⁺, link electrochemical signals of the reaction of the silver fluoride formation with the contact area.     

Enzymatic detection of glucose using fluoride-selective electrodes with polymeric membranes

The feasibility of using polymeric membrane fluoride-selective electrodes based on zirconium(IV) 5,10,15,20-tetraphenylporphyrin as a detector in a flow-injection analysis (FIA) system for glucose determination was examined. The optimization of enzymatic reactions, FIA system configuration and enzyme-immobilization process was performed. It was shown that the resulting flow-injection system exhibits good working parameters, such as reproducibility, linear range of glucose concentration (3 × 10⁻³–10⁻¹ M), sampling rate (60 samples per minute) and lifetime (over 1 month). The performance of the polymeric membrane electrode was similar to that of a crystalline LaF₃ electrode. The results of glucose determination in synthetic samples with the proposed system show good agreement with real glucose concentrations.     

Voltammetric response of the interface between single-crystal cerium fluoride and metallic microelectrodes

The processes occurring at the interface between single-crystal fluoride-conducting solid electrolyte CeF₃: Sr²⁺ and metallic microelectrodes of Bi, Sn, Sb, and Ag are studied by the method of cyclic voltammetry with use of traditional silver-silver chloride electrode or solid-phase reference electrode Sn, SnF₂. Responses of solid-phase reactions involving mobile fluoride ions of the solid electrolyte and the microelectrode material are obtained. It is suggested that signals relating to the reduction of fluorinated metals be used for local qualitative assay of metal traces contained in quantities of about a few nanograms on the surface of conducting solids in air.     

Anodic Stripping Voltammetric Determination of Lead（Ⅱ） Using Glassy Carbon Electrode Modified with Novel Calix[4] arene

A new glassy carbon electrode modified with novel calix[4]‐arene derivative was prepared and then applied to the selective recognition of lead ion in aqueous media by cyclic and square wave voltammetry. A new anodic stripping peak at ? 0.92 V (vs. Ag/Ag⁺) in square wave voltammogram can be obtained by scanning the potential from ? 1.5 to ? 0.6 V, of which the peak current is proportional to the concentration of Pb²⁺. The modified electrode in 0.1 mol/L HNO₃ solution showed a linear voltammetric response in the range of 2.0 × 10–⁸–1.0 × 10–⁶ mol/L and a detection limit of 6.1 × 10–⁹ mol/L. In the modified glassy carbon electrode no significant interference occurred from alkali, alkaline and transition metal ions except Hg²⁺, Ag⁺ and Cu²⁺ ions, which can be eliminated by the addition of KSCN. The proposed method was successfully applied to determine lead in aqueous samples.     

Electrochemical Behaviour of Poly(benzopyrene) Films Doped with Eriochrome Black T as a Pb2+‐Sensitive Sensors

Poly(benzopyrene) films were electrosynthesized on glassy carbon disk electrodes from benzo(a)pyrene by cyclic voltammetry in the presence of eriochrome black T, which forms strong complexes with lead ions. In consequence, by conditioning the films in high concentration of lead (0.1 mol dm^?3 Pb(NO₃)₂) potentiometric sensitivity to lead ions down to 10^?5 mol dm^?3 Pb²⁺ was induced, and a novel type of lead‐sensitive electrode was obtained. The electrode is characterized by high stability of the potential readouts, good reproducibility of the calibration curves as well as a minor hysteresis effects. The performance of our lead‐sensitive electrode was favourable compared to PEDOT and PPy‐based electrodes doped with eriochrome black T. We conclude that poly(benzopyrene) doped with eriochrome black T is a new electroactive material that may be applied in sensor technology.     

Adsorptive Stripping Voltammetric Determination of Phenol at an Electrochemically Pretreated Carbon-Paste Electrode with Solid Paraffin as a Binder

An adsorptive stripping voltammetric method for determination of phenol at an electrochemically pretreated carbon-paste electrode has been developed. Solid paraffin was used as the binder of the carbon-paste electrode. The carbon-paste electrode was pretreated in the solution of 0.001 mol L⁻¹NaOH by holding it at +1.8 V (versus an Ag/AgCl electrode) for 5 min. On the pretreated electrode, the adsorption of phenol was greatly enhanced. Phenol was accumulated in NH₃–NH₄Cl (pH 9.25) medium at the potential of +0.1 V (versus Ag/AgCl electrode) for a certain time and then determined by second order differential anodic stripping voltammetry. An oxidative peak was observed at about +0.66 V. The relationship between second order peak current and phenol concentration was linear in the range of 2.5 × 10⁻⁷–5.0 × 10⁻⁶mol L⁻¹phenol, and the detection limit was 5.0 × 10⁻⁸mol L⁻¹. The method has been applied to the determination of phenol in tap water and waste water. The relative standard deviation (six determinations) was less than 3.5%.     

Synthesis of highly fluorescent LaF3:Ln/LaF3 core/shell nanocrystals by a surfactant-free aqueous solution route

A surfactant-free aqueous solution route has been established for the synthesis of LaF₃:Ln³⁺/LaF₃ core/shell nanocrystals (Ln=Ce, Tb, Nd) heated at 75 °C at ambient pressure. All the as-prepared nanocrystals with spherical shape have an average size around 20 nm, and consist of well crystallized hexagonal phases. The X-ray photoelectron spectra was used to confirm that the LaF₃ shells have coated the LaF₃:Ce³⁺, Tb³⁺ cores. Compared with that of the original cores under the same conditions, the emission intensity of the LaF₃:Ce³⁺, Tb³⁺/LaF₃ and LaF₃:Nd³⁺/LaF₃ core/shell nanocrystals increased significantly of 120% and 60%, respectively. The quantum yield of the LaF₃:Ce³⁺, Tb³⁺/LaF₃ core/shell nanocrystals reached about 27% in aqueous solution. These results indicate that a significant reduction of the quenching from the surface of the core nanocrystals can be obtained by the synthesis of the core/shell structures, and this method can provide more desirable lanthanide-doped nanocrystals for potential biological applications.     

Adsorption behaviors of strontium using macroporous silica based hexagonal tungsten oxide

A novel macroporous silica-based hexagonal tungsten oxide (h-WO₃/SiO₂) with exchangeable sodium cations located in hexagonal tunnel structure was synthesized by a facile hydrothermal treatment of sodium tungstate dihydrate with 1 mol/L HCl solution. Utilization of the h-WO₃/SiO₂ adsorbent to remove aqueous strontium was investigated under the condition of various pH values, contact time, the initial concentration of metal ions, salt ion concentration, and coexisting ions. According to the experimental data, Sr²⁺ adsorption equilibrium was achieved within 15 min in acidic solution, and the maximum removal capacity of Sr²⁺ occurred at pH 4. The kinetic adsorption of Sr²⁺ on h-WO₃/SiO₂ was controlled by pseudo second-order model, and the saturated adsorption of Sr²⁺ on h-WO₃/SiO₂ was better described by Langmuir and Redlich-Peterson isotherm models compared with the Freundlich isotherm model. The distribution coefficient of Sr²⁺ was more than 2000 cm³/g in the presence of Ca²⁺, Mg²⁺, La³⁺, and Eu³⁺, indicating that the h-WO₃/SiO₂ showed excellent selectivity towards Sr²⁺ in pH 4.     

Interphase-exchange processes at the interface of fluorine-conducting solid electrolyte with alkaline solutions

Kinetics of fluorideion exchange at the interface between a LaF₃:Eu²⁺ single crystal and solution with different pF and pH is studied by the galvanostatic and potentiometric methods and also by impedance spectroscopy. Anodic galvanostatic transients are linearized in the coordinates ln (η–η_max) vs. t, which suggests that the exchange rate in alkaline solutions is limited by surface diffusion of fluorine adions. The surface concentration of fluorine adions с ₀ and the surface diffusion flow ν ₀ are assessed. Impedance spectroscopy studies of the exchange processes indicate that the charge-transfer resistance R _F and the heterogeneous reaction resistance R _P increase with the increase in the рН of the fluoride-containing solution and also with the increase in the time of exposure of the fluoride-selective electrode membrane in a neutral solution with pH 6.4 and the high (pF 2) content of fluorides.     

Selective method for the determination of gold by anodic stripping voltammetry

A highly selective method for the deter- mination of gold by anodic stripping voltammetry is described. For preconcentration a glassy carbon electrode, activated by deposition of small amounts of gold before the measurement, is proposed. The Au³⁺ reduction process at such an electrode is effective starting with the potential +0.4 V vs. Ag/AgCl electrode. A linear dependence of the current of the gold stripping peak on the gold concentration was obtained in the range from 5×10^–8 to 1×10^–6 mol/l. The relative standard deviation for 2×10^-7 mol/l HAuCl₄ was 4.2% (n=5). The detection limit was 4×10^-9 mol/l. The accuracy of the method was verified by the determination of gold in reference materials.     

Selective method for the determination of gold by anodic stripping voltammetry

A highly selective method for the deter- mination of gold by anodic stripping voltammetry is described. For preconcentration a glassy carbon electrode, activated by deposition of small amounts of gold before the measurement, is proposed. The Au³⁺ reduction process at such an electrode is effective starting with the potential +0.4 V vs. Ag/AgCl electrode. A linear dependence of the current of the gold stripping peak on the gold concentration was obtained in the range from 5×10⁻⁸ to 1×10⁻⁶ mol/l. The relative standard deviation for 2×10^-7 mol/l HAuCl₄ was 4.2% (n=5). The detection limit was 4×10^-9 mol/l. The accuracy of the method was verified by the determination of gold in reference materials.