A Reference Electrode for Electrochemical and Cryoelectrochemical Use in Tetrahydrofuran Solvent

We report a reference electrode for direct use in tetrahydrofuran (THF) at low temperatures. A reference solution containing equimolar amounts of ferrocene/ferrocenium hexafluorophosphate (Fc/Fc⁺) are prepared to give a 4 mM solution in THF that contains tetrabutylammonium hexafluorophosphate (TBAF) supporting electrolyte thus, minimizing liquid junction potentials. The reference solution is added to a sealed glass tube with a porous frit at one end, and a platinum wire is inserted into the tube. The reference electrode assembly is then inserted into a THF test solution. Potentiometric measurements show that the system responds in the expected Nernstian fashion over the concentration and temperature ranges, 4 mM to 40 μM and 20 °C to ?45 °C respectively. In addition, it is shown by steady–state cyclic voltammetry at a platinum microelectrode that the chemical reactivity of ferrocenium hexafluorophosphate (Fc⁺) otherwise seen in THF is suppressed by ion‐pairing with PF using tetrabutylammonium hexafluorophosphate (TBAF) as the supporting electrolyte.     

Faradaic electrochemistry at microcylinder,band, and tubular band electrodes

Current-time relationships of faradaic processes at microcylinder, band, and tubular band electrodes have been evaluated. Microcylinder electrodes were fabricated from platinum wires (5 μm radius) sealed in glass capillaries. Band and tubular electrodes were constructed with platinum sheets (～ 20 μm width) or thin pieces of graphite (～ 5 μm width) sealed between insulating mateials. The temporal response of the current at a microcylinder electrode for the reduction of ferricyanide in aqueous potassium chloride solutions is in excellent agreement with that predicted by equations derived for heat flux to a cylinder. An estimation of the magnitude and temporal properties of the measured current at a band electrode can be obtained when a hemicylinder geometry is assumed. The current respone is identical at band and tubular band electrodes even for the smallest tubular radius investigated, 0.54 mm. Cyclic voltammograms at electrodes of all three geometries show significant contributions from radial diffusion at slow scan rates (< 20 mV s^?1). The current at a graphite tubular band electrode was found to be independent of flow of solution through the electrode at flow rates up to 3 ml min^?1.     

Background subtraction for rapid scan voltammetry

Methods for the elimination of residual current in fast scan (> 300 V s⁻¹) voltammetry have been evaluated at microvoltammetric electrodes. Staircase voltammetry is found to give only a modest improvement in the ratio of the faradaic current to the residual current. Supeior results are obtained when the residual current, obtained in supporting electrolyte solution, is digitally subtracted from the voltammogram obtained in the presence of the electroactive species. The subtraction process is facilitated by conducting the whole experiment in a flow injection apparatus so that the electrode remains in solution while the two voltammograms are obtained. Undistorted voltammograms have been obtained for the reduction of anthracene (∼ 2 mM) at scan rates up to 10,000 V s⁻¹. At 300 V s⁻¹, virtually undistorted voltammograms are obtained for the reduction of Tl⁺ at low concentration (20 μM) in aqueous solution at a mercury microvoltammetric electrode. Analog offset of the residual current was used to improve the dynamic range. The limits of this technique are caused by the electronic noise in the ideal case where flat residual current curves are obtained.     

非水体系中单分子层保护团簇在超微铂电极上的量子化充电

非水体系中单分子层保护团簇在超微铂电极上的量子化充电;单层保护团簇;量子化电容充电     

Ferrocene as a Reference Redox Couple for Aprotic Ionic Liquids

The electrochemical behavior of ferrocene has been studied in a number of room temperature ionic liquids. Diffusion‐controlled, well‐defined anodic and cathodic peaks were found for the Fc/Fc⁺ (ferrocene/ferrocenium) oxidation/reduction on the gold electrode. Ohmic resistance R between working and auxiliary electrodes was deduced from impedance measurements. Cyclic voltammograms were corrected for the base line current as well as for the ohmic drop (IR). The formal potential 1/2(E_pa+E_pc) for ferrocene reduction/oxidation in aprotic ionic liquids tested is within a relatively narrow range and may be approximated by the value of 0.527±0.018 V (against the cryptate Ag/Ag⁺222 in acetonitrile reference). Ferrocene diffusion coefficients, calculated from the peak current dependence on the sweep rate, were of the order of 10^?7 cm² s^?1.     

Formation of negative oxidation states of platinum and gold in redox ionic liquid: Electrochemical evidence

The electrochemical reduction of noble metal electrodes in the presence of redox ionic liquid, 1-ferrocenylethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [FcEMIM][TFSI], was investigated by cyclic voltammetry. Our experiments suggest the formation of metal with negative oxidation states, in the cases of platinum and gold electrodes [M_n⁻, FcEMIM⁺]. By analogy with the previous work, the formation of these phases is concomitant with the insertion of the supporting electrolyte; which correspond in our experimental condition to the redox cation of the ionic liquid. As an exciting result, the electrochemical investigations of the reduced electrode in electrolytic solution, containing solvent and supporting electrolyte, evidence the presence of the ferrocene groups at the electrode surface. Moreover, the reduced electrode exhibits the presence of the ferrocene even after, contact with air, after ultrasound, and after physical polishing, highlighting the large stability of this organo-metallic phases formed in this media. The AFM investigations demonstrate the morphological change of the platinum surface after the reduction process. Finally, our works bring a formal electrochemical proof of the presence of the ionic liquid cation inside the electrode material after the cathodic treatment in this media.     

Voltammetric examinations of ferrocene on microelectrodes and microarrayelectrodes

Voltammetric investigations of ferrocene in organic media with planar, disk and band shaped microelectrodes (ME) and microarrayelectrodes (MAE) were carried out in stationary solutions and under flow-through conditions with flow-injection analysis (FIA). The electrodes were embedded in cylindrical electrode bodies made of epoxy resin. During the FIA experiments miniaturized flow-through cells with a three electrode configuration (wall-jet, thin-layer principle) were used. As detectors microelectrodes and microarrayelectrodes consisting of platinum wires (radius: 10 μm), gold wires (radius: 12.5 μm), carbon fibres (radius: 3.5 μm) and gold foils (foil thickness: 30 μm) were constructed using fine precision manufacturing methods by sealing the electrode materials in insulating resins.     

Bioactive Hydrogel Layers on Microdisk Electrode Arrays: Cyclic Voltammetry Experiments and Simulations

Poly(hydroxyethylmethacrylate)‐based hydrogel membranes were applied to microfabricated, microdisk electrode arrays (MDEAs) of 50 μm (5184 disks), 100 μm (1296 disks) and 250 μm (207 disks) (d/r=4; A= 0.1 cm²) and studied by cyclic voltammetry (CV) in 1.0 mM ferrocene monocarboxylic acid (FcCO₂H). The membrane produced an order of magnitude decrease in current densities and a shift to quasi reversibility due to a decrease in the D_appt of FcCO₂H, from 4.51×10^?6 cm² s^?1 to 1.42×10^?8 cm² s^?1, (2.18×10^?8 cm² s^?1 from release experiments). The MDEA050 (comprising 50 μm disks) maintained its enhanced current density attributes confirming its value as an effective electrode for biosensors. Finite element modeling (FEM) simulations successfully replicated the voltammograms of the MDEAs.     

Electrochemical Response of Polyaniline (PANI)/Thiokol Rubber (TR) Films in Cysteine Solution

The electrochemical character of polyaniline/thiokol rubber (PANI/TR) composite film on a Pt electrode was investigated in a cysteine sulphuric acid solution by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The significant change of the peak current and peak potential in the cyclic voltammograms was observed. The irreversible peaks of cyclic voltammetry for cysteine/cystine redox couple at a platinum electrode have turned into one pair of nearly reversible peaks at the above electrode; the reversibility of the redox couple has been greatly improved. We found that thiokol rubber could improve the electrocatalysis of the PANI film to the electrochemical reaction with S‐S bonds, as well as the adhesion of the PANI film to the Pt substrate. Several effective factors, such as the concentration of thiokol rubber in the nonaqueous electrodeposition solution, different potential scan rate, immersing time of the film electrode in the studied electrolyte were all taken into account.     

Voltammetry at microcylinder electrodes: Part I. Linear sweep voltammetry

An expression for reversible linear sweep voltammograms at stationary microcylinder electrodes is presented. From numerical calculations theoretical voltammograms are obtained for various values of the dimensionless parameter, p=(nFa²v/RTD)^{$\text{1}\text{2}$}, where a is the radius of the electrode, v the potential sweep rate and D the diffusion coefficient. The peak current and the peak potential are evaluated from the voltammograms as functions of p and are expressed by approximate equations with high precision. In order to examine the validity of the equations, an experimental study was made at platinum wire micro-electrodes (a=10?10) μm). The experimental voltammograms were in good agreement with the ones predicted theoretically for various values of the sweep rates and for several different radii of the electrodes.     

Mesoporous platinum hosts for electrodeliquidliquid – Triple phase boundary redox systems

Mesoporous metal hosts are attractive electrode materials for complex electrode reactions, for example those involving a system of two immiscible liquids. Here we show that a solution of tetraphenylporphyrianto manganese (MnTPP) in 4-(3-phenylpropyl)-pyridine (PPP) organic liquid can be immobilized into mesoporous platinum thin films electrodeposited from a liquid crystalline template. When immersed in an aqueous solution, the organic liquid remains immobilized inside the mesoporous platinum framework. Well-defined, stable, and reproducible ion transfer voltammograms are recorded. The effects of mesoporous platinum membrane thickness (volume), scan rate, and the type of aqueous electrolyte anion (for Cl⁻, , , CN⁻, SCN⁻ and ) are investigated. Mesoporous platinum is proposed as a very effective electrode material for liquidliquid anion sensing and for other applications of electrochemically driven liquidliquid redox systems.     

Preparation of Pt/polypyrrole-ferrocene hydrogen peroxide sensitive electrode for the use as a biosensor

A polypyrrole electrode with ferrocene mediator is prepared and its sensitivity to hydrogen peroxide is investigated. The polypyrrole is deposited upon a 0.5 cm² Pt plate by the polymerization of pyrrole by scanning the electrode potential between 0.0 and 0.9 V at a scan rate of 50 mV/s. The platinum/polypyrrole-ferrocene (Pt/PPy-Fc) electrode is prepared by adding ferrocene to the coverage medium. The electrode’s sensitivity to hydrogen peroxide is investigated at room temperature using 0.025 M phosphate buffer at pH 7. The working potential is 0.7 V, the concentrations of pyrrole and ferrocene are 0.2 M and 10 mM. Polypyrrole was coated on the electrode surface within 26 cycles. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 2, pp. 160–164. The text was submitted by the authors in English.     

Électrochimie dans l'oxydipropionitrile: Comportement électrochimique du solvant. Stabilité des complexes argent(I) halogénures. Solvatation des anions

Electrochemical possibilities of oxydipropionitrile have been shown. The system Ag(s)/Ag⁺ has been used to make a reference electrode in this medium. The electroactivity range which depends on the electrolyte and the kind of electrode used has been specified. At a platinum electrode, in LiClO₄ medium, the electroactivity range is very large. At a mercury electrode, water does not interfere but at a platinum electrode it is oxidizable; the electroactivity range depends on its concentration. The second part treats the complexes with silver ion and halides. Stability constants of complexes and solubility products have been obtained from potentiometric titration curves. The determination of the transfer parameters for ionic species is based on the Strehlow assumption that the potential of the ferrocene/ferricinium couple is constant in all solvents. The results show that the silver ion is more strongly solvated in oxydipropionitrile than in water; on the other hand halide ions are little solvated in this solvent.     

Acidité dans le nitrométhane: III. Détermination électrochimique de la basicité du nitrométhane — Corrélation Dn/Eo(Hs+/H2/

The use of the complex acid HAlCl₄ (HCl+AlCl₃) permits the detemrination of the standard potential of the hydrogen electrode in nitromethane. The result (E₀(H_s⁺/H₂)=0.5 V vs. Fc/Fc⁺, Fc=ferrocene) shows that nitromethane is very weakly basic. This measurement is confirmed by showing that the standard potential of the hydrogen electrode in various solvents is linked to Gutmann's donor numbers of these solvents. The E₀(H_s⁺/H₂) value obtained in nitromethane belongs to the correlation line.     

Reversibility of platinum voltammograms in aqueous electrolytes,ionic product and dissociative adsorption of water

Well-known reversibility of platinum voltammograms in supporting aqueous electrolytes formally contradicts the equilibrium defined by the ionic product of water: K_w = [H⁺] · [OH⁻] ≅ 1 × 10¹⁴, since at any pH value, concentration of one of these ions should be too low (⩽10⁷ M) to ensure reversibility in the whole potential region at usual scan rates. This contradiction could be overcome by allowing dissociative water adsorption on platinum. All available relevant data obtained by in situ physical methods appear to provide indirect experimental evidences for this hypothesis.     

碳纤维微电极研究(Ⅴ)——高阻介质中二茂铁及其衍生物的动力学研究

固体微电极的应用,使高阻溶液中的电化学动力学的研究及异相快电子迁移速率常数k^o′的测定成为可能,用微铂电极对二茂铁在乙腈溶液中电化学行为的研究以及k^o′的测定已有报道,但结果差异甚大,难以引用,鉴于二茂铁及其衍生物的重要性。     

Electrochemical Behavior of the Li+/Li Couple and Stability of Lithium Deposits in Tri‐1‐Butylmethylammonium Bis((Trifluoromethyl)Sulfonyl)Imide Room Temperature Ionic Liquid

The electrochemical behavior of the Li⁺/Li couple was studied at polycrystalline tungsten, platinum, copper and aluminum electrodes in tri‐1‐butylmethylammonium bis((trifluoromethyl)sulfonyl)imide ionic liquid mixed with a little propylene carbonate at 30 °C. Lithium cations were introduced into the ionic liquid by dissolution of lithium bis((trifluoromethyl)sulfonyl)imide which is highly soluble in ionic liquid. Propylene carbonate was used to reduce the viscosity of this ionic liquid in order to enhance the mass transfer and to additionally improve the stability of lithium deposits. At the tungsten and copper electrodes, the cyclic voltammetric behavior of a Li⁺/Li couple is a quasi‐reversible reaction. At the platinum electrode, the behavior becomes very complicated because of the alloy formation. Coulombic efficiency was used to evaluate the stability of lithium deposits at each electrode. The aluminum electrode showed the best efficiency due to the formation of Li‐Al alloy. However, lowest efficiency was obtained at the platinum electrode because of the low redox reversibility of the lithium in the Li‐Pt alloy. The diffusion coefficient of lithium cation in this solution was 1.0 ± 0.1 × 10^?;7 cm² s^?;1 as determined by chronopotentiometry. The best coulombic efficiency obtained at the Al electrode is 97% but dropped to about 90% after 12 hours. The self‐discharge current of the lithium deposits at the Al electrode was 0.4 μA/cm² during the experimental period.     

Charge Density Overcomes Steric Hindrance of Ferrocene Surfactant in Switchable Oil-in-Dispersion Emulsions

A ferrocene surfactant can be switched between single and double head form (FcN⁺C₁₂/Fc⁺N⁺C₁₂) triggered by redox reaction. FcN⁺C₁₂ can neither stabilize an O/W emulsion alone nor an oil-in-dispersion emulsion in combination with alumina nanoparticles due to the steric hindrance of the ferrocene group. However, such steric hindrance can be overcome by increasing the charge density in Fc⁺N⁺C₁₂, so that oil-in-dispersion emulsions can be co-stabilized by Fc⁺N⁺C₁₂ and alumina nanoparticles at very low concentrations (1×10⁻⁷ M (≈50 ppb) and 0.001 wt %, respectively). Not only can reversible formation/destabilization of oil-in-dispersion emulsions be achieved by redox reaction, but also reversible transformation between oil-in-dispersion emulsions and Pickering emulsions can be obtained through reversing the charge of alumina particles by adjusting the pH. The results provide a new protocol for the design of surfactants for stabilization of smart oil-in-dispersion emulsions.     

Electrochemical behavior of [UO_2Cl_4]~(2-) in 1-ethyl-3-methylimidazolium based ionic liquids

In order to examine the chemical form of uranyl species in 1-ethyl-3-methylimidazolium(EMI) based ionic liquids,UV-visible absorption spectra of solutions prepared by dissolving [EMI] 2 [UO2Cl4] into a mixture of EMICl and EMIBF 4(50:50 mol%) were measured.As a result,it was confirmed that uranyl species in the mixture of EMICl and EMIBF 4 existed as [UO2Cl4]2-.Cyclic voltammograms(CVs) of [UO2Cl4]2-in the mixture were measured at 25 ℃ using a Pt working electrode,a Pt wire counter electrode,and an Ag/Ag + reference electrode(0.01 M AgNO 3,0.1 M tetrabutylammonium perchlorate in acetonitrile) in a glove box under an Ar atmosphere.Peaks corresponding to one redox couple were observed around-1.05 V(Epc) and-0.92 V(Epa) vs.ferrocene/ferrocenium ion(Fc/Fc +).The potential differences between two peaks(Ep) increased from 101 to 152 mV with an increase in the scan rate from 50 to 300 mV s-1,while the(Epc+Epa)/2 value was constant,-0.989 V vs.Fc/Fc + regardless of the scan rate.Furthermore,the diffusion coefficient of [UO2Cl4]2-and the standard rate constant were estimated to be 3.7 × 10-8 cm 2 s-1 and(2.7-2.8) × 10-4 cm s-1 at 25 oC.By using the diffusion coefficient and the standard rate constant,the simulation of CVs was performed based on the reaction,[UO2Cl4]2-+ e = [UO2Cl4]3-.The simulated CVs were found to be consistent with the experimental ones.From these results,it is concluded that [UO2Cl4]2-in the mixture of EMICl and EMIBF 4 is reduced to [UO2Cl4]3-quasi-reversibly at-0.989 V vs.Fc/Fc +.     

Proton Medium Effect Based on the Ferrocinium Assumption in 80 Mass-% Propylene Carbonate + 20 Mass-% <Emphasis Type="Italic">p</Emphasis>-Xylene Medium

Conventional electrochemical studies on the ferrocinium–ferrocene (Fc⁺–Fc) redox system in 80 mass-% propylene carbonate (PC) + 20 mass-% p-xylene (PX) medium are reported, leading to a calculation of the proton medium effect. The dissociation constant of ferrocinium picrate in this medium was determined by conductivity measurements. The value of E_{Fe⁺ /Fe}^oE_{\mathrm{Fe^{+} /Fe}}^{\mathrm{o}} against the Hg/HgCl₂(s) reference electrode in 80 mass-% PC + 20 mass-% PX was determined potentiometrically in conjunction with conductivity data, and found to be 0.133±0.001 V versus the SHE at 25 °C. The E_{Fe⁺ /Fe}^oE_{\mathrm{Fe^{+} /Fe}}^{\mathrm{o}} value has also been calculated using cyclic voltammetric data obtained in 80 mass-% PC + 20 mass-% PX at a micro platinum working electrode against the Ag/AgCl (nonaq.) reference electrode, and found to be comparable with the value obtained by potentiometry. The proton medium effect for transfer from water to the present mixed solvent medium was calculated using the value of E_Fe⁺/Fe^oE_{\mathrm{Fe^{+}/Fe}}^{\mathrm{o}} versus SHE at 25 °C and found to be 4.5. Based on values of proton medium effect reported in the literature, it is inferred that the present mixed solvent medium is slightly more basic than pure PC.