Acetate adsorption and metal overlayers on electrode surfaces

Acetate adsorbs onto platinum surfaces under moderate conditions and the presence of acetate on the electrode surface is apparent by voltammetric studies. The adsorption of acetate lends an unusual stability to layers of zinc acetate on the electrode surface. The reduction of an oxidized platinum surface under a zinc acetate coating is sensitive to polar organic molecules in the bulk solution. This sensitivity may provide an avenue to a new class of analytical sensors.     

Electrocatalytic reduction of nitrite on tetraruthenated metalloporphyrins/Nafion glassy carbon modified electrode

This paper describes the electrochemical reduction of nitrite ion in neutral aqueous solution mediated by tetraruthenated metalloporphyrins (Co(II), Ni(II) and Zn(II)) electrostatically assembled onto a Nafion film previously adsorbed on glassy carbon or ITO electrodes. Scanning electron microscope (SEM-EDX) and transmission electron microscopy (TEM) results have shown that on ITO electrodes the macrocycles forms multiple layers with a disordered stacking orientation over the Nafion film occupying hydrophobic and hydrophilic sites in the polyelectrolyte. Atomic force microscopy (AFM) results demonstrated that the Nafion film is 35 nm thick and tetraruthenated metalloporphyrins layers 190 nm thick presenting a thin but compacted morphology. Scanning electrochemical microscopy (SECM) images shows that the Co(II) tetraruthenated porphyrins/Nf/GC modified electrode is more electrochemically active than their Ni and Zn analogues.These modified electrodes are able to reduce nitrite at −660 mV showing enhanced reduction current and a decrease in the required overpotential compared to bare glassy carbon electrode. Controlled potential electrolysis experiments verify the production of ammonia, hydrazine and hydroxylamine at potentials where reduction of solvent is plausible demonstrating some selectivity toward the nitrite ion. Rotating disc electrode voltammetry shows that the factor that governs the kinetics of nitrite reduction is the charge propagation in the film.     

The effect of alkali metal ions on the electrochemical behavior of ferrocene-peptide conjugates immobilized on gold surfaces

We have immobilized a series of cyclic and acyclic Fc-peptides on the gold microelectrode in order to investigate peptide interactions with alkaline metals. The solutions used for alkaline metal-peptide film interaction studies were: 50 mM HClO₄ and 25 mM XClO₄, where X = Li, Na, K, Rb, and Cs. Our study indicates that the formal potential is influenced with shifts of up to 100 mV. The peak separation ΔE values are also influenced by the presence of the alkaline metal cations. Changes up to 90 mV were observed. The observed changes were attributed to the variations of orientation of ferrocene on the gold surface.     

Countercation intercalation and kinetics of charge transport during redox reactions of nickel hexacyanoferrate

The dynamics of charge propagation in nickel hexacyanoferrate, a model metal-substituted analogue of Prussian Blue-type cyanide-bridged systems, was considered in electrolytes containing potassium and other alkali metal cations. The apparent (effective) diffusion coefficients for charge transport were determined using a large-amplitude potential-step chronocoulometry and small-amplitude potential-step chronocoulometric potentiostatic intermittent titration. The dependence of diffusion coefficient on the potential applied is consistent with the intercalation like model of the counter-cation sorption/desorption during redox processes of nickel hexacyanoferrate. Some differences in diffusion coefficients may originate from distinct charge densities (membrane properties) of the oxidized and reduced metal hexacyanoferrate structures. The existence of strong attractive interactions between an alkali metal cation and the cyanometallate matrix is also expected. The overall dynamics of charge propagation seems to be controlled by transport of electrolyte cations within the film rather than by electron self-exchange (hopping) between the mixed-valence hexacyanoferrate(III,II) ionic sites.     

Electro-oxidation of chlorophenols on poly(3,4-ethylenedioxythiophene)-poly(styrene sulphonate) composite electrode

The electrochemical behaviour of chlorinated phenols on Pt/poly(3,4-ethylenedioxy)thiophene,LiClO₄ and on Pt/poly(3,4-ethylenedioxy)thiophene,poly(sodium-4-styrenesulphonate) electrodes has been investigated in phosphate buffer solution. Poly(sodium-4-styrenesulphonate) exerts remarkable effect against the electrode fouling induced by oxidation of chlorophenols, allowing us to record the relevant anodic response even after repeated potential cycles. Hypotheses about the role exerted by poly(sodium 4-styrenesulphonate) are made, on the basis of evidences provided by several techniques, such as cyclic voltammetry, electrochemical impedance spectroscopy, electrochemical microgravimetry and atomic force microscopy. Thanks to the fact that different chlorophenols show differences in the voltammetric responses, depending on number and position of the chloro substituents on the aromatic ring, applications of the modified electrode in the analysis of mixtures of chlorinated phenols are possible.     

A model of charge transport and electromechanical transduction in ionic liquid-swollen Nafion membranes

Ionomeric polymer transducers (sometimes called “ionic polymer-metal composites,” or “IPMCs”) are a class of electroactive polymers that are able to operate as distributed electromechanical actuators and sensors. Traditionally, these transducers have been fabricated using water-swollen Nafion membranes. This work seeks to overcome the hydration dependence of these transducers by replacing water with an ionic liquid. In the current work, two ionic liquids are studied as diluents for ionomeric polymer transducers based on Nafion membranes. The two ionic liquids used are 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf) and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-Im). These two ionic liquids were chosen for their low viscosity and high conductivity. Furthermore, although many of the physical properties of the two ionic liquids are similar, the EMI-Tf ionic liquid is water miscible whereas the EMI-Im ionic liquid is hydrophobic. These important similarities and differences facilitated investigations of the interactions between the ionic liquids and the Nafion polymer.This paper examines the mechanisms of electromechanical transduction in ionic liquid-swollen transducers based on Nafion polymer membranes. Specifically, the morphology and relevant ion associations within these membranes are investigated by the use of small-angle X-ray scattering (SAXS), Fourier transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. These results reveal that the ionic liquid interacts with the membrane in much the same way that water does, and that the counterions of the Nafion polymer are the primary charge carriers in the ionic liquid-swollen films. The results of these analyses are compared to the macroscopic transduction behavior in order to develop a molecular/morphological model of the charge transport mechanism responsible for electromechanical coupling in these membranes.     

Effect of annealing temperature on mixed proton transport and charge transfer-controlled oxygen reduction in gas diffusion electrode

The effect of annealing temperature T_ann on mixed proton transport and charge transfer-controlled oxygen reduction in gas diffusion electrodes used in polymer electrolyte membrane fuel cells (PEMFCs) was investigated in 1 M H₂SO₄ solution using AC-impedance spectroscopy and potentiostatic current transient technique. For this purpose, the gas diffusion electrodes were annealed at different temperatures ranging from 140° to 180 °C in order to control the proton transport resistance distribution across the active catalyst layer (ACL). For the annealed gas diffusion electrodes with different proton transport resistance distributions, the measured impedance spectra exhibited a straight line inclined at a constant angle higher in absolute value than 45° to the real axis at high frequencies, followed by a depressed arc at low frequencies.From the quantitative analysis of the measured impedance spectra based upon the transmission line model (TLM) modified with the proton transport resistance distribution, it was found that as T_ann increased, the average proton transport resistance R_ave and the standard deviation σ of the proton transport resistance distribution increased as well. Furthermore, as T_ann rose, the charge transfer resistance R_ct increased and simultaneously the double layer capacitance C_dl decreased due to the smaller electrochemical active area A_ea. From the analysis of the cathodic current transients measured during nitrogen blowing, it was noted that as T_ann increased, the current decayed more rapidly with time, suggesting that the larger values of R_ave and σ kinetically impede proton transport through the Nafion membrane within the ACL due to the wider RC time constant distribution.     

Electrocatalytic oxidation of deoxyguanosine on a glassy carbon electrode modified with a ruthenium oxide hexacyanoferrate film

The electrocatalytic oxidation of deoxyguanosine on a ruthenium hexacyanoferrate (RuOHCF) glassy carbon (GC) modified electrode was investigated in acid medium by using rotating disc electrode (RDE) voltammetry. Chronoamperometric experiments allowed information on the charge transport rate through the RuOHCF film and at a very short time window a diffusion-like behavior was observed with a D_ct value of 2.7 × 10⁻¹¹ cm² s⁻¹ for a film with Γ = 4.47 × 10⁻⁹ mol cm⁻². The influence of systematic variation of rotation rate, film thickness and the electrode potential indicates that the rate of cross-chemical reaction between Ru(IV) centers immobilized into the film and deoxyguanosine controls the overall electrodic process and the value of the rate constant was found to be 3.2 × 10⁶ mol⁻¹ L¹ s⁻¹. The relatively high rate constant of the cross-reaction, the facile penetration of the substrate through the film and the fast transport of electrons suggest that the electrocatalytic process occurs throughout the film layer.     

Enhanced mass transport to a reticulated vitreous carbon rotating cylinder electrode using jet flow

The mass transport characteristics of a porous, rotating cylinder electrode (RCE, 1.0 cm diameter; 0.5, 0.9 or 1.2 cm long; 1.25, 2.25, 3.00 cm³ overall volume; 250-2000 rpm speed) fabricated from reticulated vitreous carbon (RVC, 60 ppi or 100 ppi) were investigated. The deposition of copper from an acid sulfate electrolyte (typically, deoxygenated 1 mM CuSO₄ in pH 2, 0.5 M Na₂SO₄ at 298 K) was used as a test reaction. The effect of a jet flow of electrolyte towards the electrode and the introduction of polypropylene baffles in the electrochemical cell were studied at controlled rotation rates of the RCE. The product of mass transport coefficient and volumetric electrode area (k_mA_e) is related to the rotation speed of the electrode. For the 60 ppi RVC RCE, the jet electrolyte flow (3.5 cm³ s⁻¹) enhanced the mass transport rates by a factor of 1.46 at low rotation speeds; this factor was reduced to 1.08 at high rotation speeds. For a 100 ppi electrode, the enhanced mass transport decreased from 1.26 to 1.03 at low and high rotation rates, respectively. Under the experimental conditions, baffles showed little effect on the mass transport rates to the RVC RCE. Mass transport to jet flow at an RVC RCE is compared to other RCEs using dimensionless group correlation.     

A study of the electro-catalytic oxidation of methanol on a cobalt hydroxide modified glassy carbon electrode

Cobalt hydroxide modified glassy carbon electrodes (CHM/GC) prepared by the anodic deposition in presence of tartrate ions have been used for the electro-catalytic oxidation of methanol in alkaline solutions where the methods of cyclic voltammetery (CV), chronoamperometry (CA) and impedance spectroscopy (IS) have been employed. In CV studies, in the presence of methanol the peak current of the oxidation of cobalt hydroxide increase is followed by a decrease in the corresponding cathodic current. This suggests that the oxidation of methanol is being catalysed through the mediated electron transfer across the cobalt hydroxide layer comprising of cobalt ions of various valence states. A mechanism based on the electro-chemical generation of Co(IV) active sites and their subsequent consumptions by methanol have been discussed and the corresponding rate law under the control of charge transfer has been developed and kinetic parameters have been derived. In this context the charge transfer resistance accessible both theoretically and through the IS studies have been used as a criteria. Under the CA regimes the reaction followed a Cottrellian behaviour.     

Mediator and catalytic effects of porphyrin modified electrodes on redox LB films

In this work, the mediator and/or catalytic properties of modified ITO electrodes by oxidative electrodeposition of Ni-porphyrins have been analyzed. Thus, monolayers containing viologen or azobenzene derivatives, have been transferred onto the porphyrin modified electrodes by using the Langmuir-Blodgett (LB) technique. Following, the redox processes of these compounds forming the LB films and deposited on the modified electrode and the bare ITO have been investigated.The obtained results reveal not only the excellent mediator character of the porphyrinic electrodeposit throughout the viologen redox processes, but also its the catalytic action over the azobenzene kinetics. Specifically, for the last case, the NiTMPyP films accelerate the azobenzene kinetics up to 100 times with respect to those results obtained in absence of porphyrin.     

AC impedance study of a synthetic hydrotalcite-like compound modified electrode in aqueous solution

This paper deals with the electrochemical characterisation of Ni/Al-Cl hydrotalcite modified electrodes. The electrochemical impedance spectroscopy technique has been used in order to study the electronic and ionic conduction, both inside and on the surface of the material. The electronic and ionic contributions have been separated and the behaviour of the respective parameters has been studied as a function of the potential. In order to determine the kinetic limiting step of the overall electrochemical process we performed experiments at different temperatures, and calculated the activation energies of the electron hopping process and ion transport process. In addition we studied the behaviour of the system at different OH⁻ concentrations (pH 9.7-12.8) with the aim of clarifying the role of OH⁻ ions in the electrochemical process.     

Fabrication of Fc-SWNTs modified glassy carbon electrode for selective and sensitive determination of dopamine in the presence of AA and UA

The electrochemistry of dopamine (DA) was investigated by cyclic voltammetry (CV) and differential pulse voltammograms (DPV) at a glassy carbon electrode modified by the hybridization adducts of Fc-SWNTs. The electro-oxidation of DA could be catalyzed by Fc/Fc⁺ couple as a mediator and had a higher electrochemical response due to the unique carbon surface of carbon nanotubes. The anodic peaks of DA, ascorbic acid (AA) and uric acid (UA) in their mixture can be well separated by the prepared electrode. Under optimum conditions linear calibration graphs were obtained over the DA concentration range 5.0 × 10⁻⁶ to 3.0 × 10⁻⁵ M with a correlation coefficient of 0.9998 and a detection limit of 5.0 × 10⁻⁸ M based on the equation C_m = 3s_b1/m. The modified electrode has been successfully applied for the assay of DA in human blood serum. This work provides a simple and easy approach to selectively detect DA in the presence of AA and UA.     

Charge distribution effects in polyatomic reactants involved in simple electron transfer reactions

The role of charge distribution in a polyatomic reactant in determining its effective charge in the double layer is discussed. It is shown that the use of a corrected Tafel plot (cTp) requires knowledge of the effective charge on both the reactant and product of a simple electron transfer process. This leads to the use of so called apparent corrected Tafel plots. Data obtained in this laboratory for six different simple electron transfer reactions involving transition metal ions are reviewed, and discussed in terms of their kinetic parameters, namely, the effective charge on the reactant and the apparent Tafel coefficient.     

Charge transport properties of poly(N-vinylimidazole) containing [Os(N)6]2+/3+ moieties

The rate of charge transport of electrodes modified with osmium containing poly(N-vinylimidazole) has been examined as a function of the nature of the contacting electrolyte solution and of temperature. Heterogeneous electron transfer from the electrode into the polymer film has also been investigated. The charge transport parameters show that the nature of the electrolyte anion and its concentration have a large impact on the polymer morphology. In sulfuric acid the films appear significantly swollen, hydrated, and porous, while in perchlorate-containing solutions they are rather compact. Activation energies for the rate-determining step of charge transport show that, depending on the electrolyte, segmental chain motion or ion movement represents the rate-limiting process.     

Charge carrier transport in polyimides based on 9,10-bis(p-aminophenyl)anthracene

Transient currents were measured by the time-of-flight technique in films of aromatic polyimides based on 9,10-bis(p-aminophenyl)anthracene and a series of diimide fragments. The electric field and temperature dependences of the hole and electron drift mobilities were detected. In amorphous films of the soluble polyimide with a phthalide group in the diimide fragment, the drift mobility was found to reach the value of 10^-4cm²V^-1s^-1 at 5·5×10⁵Vcm^-1 and 291K. In the insoluble polyimide films including the crystalline phase, the mobility was lower by one or two orders of magnitude. This is attributed to the presence of cavities in the films of the insoluble polyimides. The applicability of known theoretical models describing temperature and electric field dependences of the drift mobility is discussed. © 1998 Society of Chemical Industry     

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.     

Electrochemical properties of modified copper-thallium hexacyanoferrate electrode in the presence of different univalent cations

The preparation of copper(II) hexacyanoferrate (CuHCF) films on the surface of gold electrodes as well as their characterization in solutions of various alkali metal and NH₄⁺ cations and in the presence of thallium(I) are described. The electrochemical quartz crystal microbalance and cyclic voltammetric techniques were used. In 0.50 M lithium nitrate, even at submillimolar concentration of Tl(I), the formal potential of CuHCF was shifted to more positive values. At higher Tl(I) concentrations, the formal potential of the CuHCF redox reaction changed linearly with the logarithm of Tl(I) concentration (in the 0.50 M solution of lithium or another alkali metal nitrate). From such dependencies, selectivity coefficients K_Tl/M were calculated, and they show that the CuHCF film on the gold electrode interacts preferentially with Tl(I). High affinity of Tl(I) to copper hexacyanoferrate, that was observed in the presence of alkali metal cations, was explained by relatively strong donor-acceptor interactions of Tl(I) ions with nitrogen in CN groups of the CuHCF film.It was also shown for simple M₄[Fe(CN)₆] metal ferrocyanate salts (where M = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and Tl⁺) that there is a preferential interaction of Tl⁺ with CN group consistent with formation of a Tl-NC-Fe bridge.     

Multipin EHD dryer: Effect of electrode geometry on charge and mass transfer

Electrohydrodynamic (EHD) drying is considered as energy-efficient nonthermal technology suitable for dewatering of heat-sensitive materials. This technology relies on the ionic discharge from the vertical pin or fine horizontal wire, impinging wet material deposited on the plate electrode of opposite polarity. The critical issue for the scaling of EHD dryer is the geometry of a multipin/wire discharge and collecting electrodes, in particular the spacing between pins/wires and the gap between discharge electrode and material surface. This paper presents the results of experimental study and mathematical simulation of multipin discharge current to maximize total charge and mass transfer at the material surface. A mathematical model for discharge current based on Poisson’s and Warburg fundamental equations was developed and validated in experiments with multipin electrodes of different spacing (1, 2, 3, 4, and 6?cm) and gaps from 2 to 4?cm. It was demonstrated that linear relationship between total electric current and drying rate is valid for any spacing and any gap with the range from 2 to 4?cm. It was experimentally documented that the judiciously selected geometry of the multipin discharge electrode could mitigate adverse effect of interference between neighboring ionic jets and bring the concept of EHD dryer to industrial practice.     

Simulation studies on the fuel electrode of a H2---O2 polymer electrolyte fuel cell

The macro-homogeneous porous electrode theory is used to develop a model which describes the catalyst layer of the hydrogen electrode formed by catalyst particles that are bonded to the membrane. The water transport in the catalyst layer and polymer electrolyte membrane is considered. The effects of catalyst layer structure parameters such as polymer volume fraction, catalyst layer thickness, platinum loading and reactant gas humidity as well as CO poison on the hydrogen electrode behavior are examined. The results show that the catalyst layer thickness has a significant effect on the electrode performance. A thicker catalyst layer will result in a larger ohmic voltage loss and higher catalyst cost. The optimal polymer volume fraction and catalyst layer thickness are 0.5 and 1.5–4 μm, respectively, for this electrode. An optimal platinum surface coverage on carbon need not exceed 20% (20 wt% Pt/C). Larger platinum coverage will increase the cost, but only slightly enhance the electrode performance.