The pH-dependence of oxygen reduction on quinone-modified glassy carbon electrodes

The electrochemical reduction of oxygen has been studied on quinone-modified glassy carbon (GC) electrodes as a function of solution pH using the rotating disk electrode (RDE) technique. The surface of GC was grafted with anthraquinone (AQ) and phenanthrenequinone (PQ) by electrochemical reduction of their diazonium derivatives and the oxygen reduction measurements were carried out at different pHs (pH 7-14). The redox-potentials of surface-bound quinones were determined using cyclic voltammetry (CV). The kinetic parameters of oxygen reduction on GC/AQ and GC/PQ electrodes were determined considering a surface redox catalytic cycle model for quinone-modified electrodes.     

Direct methanol alkaline fuel cells with catalysed anion exchange membrane electrodes

Membrane electrodes prepared by chemical deposition of platinum directly onto the anion exchange membrane electrolyte were tested in direct methanol alkaline fuel cells. Data on the cell voltage against current density performance and anode potentials are reported. The relatively low fuel cell performance was probably due to the low active surface area of Pt deposits on the membrane comparing to other membrane electrode assembly (MEA) fabrication methods. However, the catalysed membrane electrode showed good performance for oxygen reduction. A reduction in cell internal resistance was also obtained for the catalysed membrane electrode. By combining the catalysed membrane electrodes with a catalysed mesh, maximum current density of 98 mA cm^–2 and peak power density of 18 mW cm^–2 were achieved.     

Electrochemical and oxygen reduction behaviour of solid silver-bismuth/antimony electrodes in KOH solutions

Oxygen reduction behaviour at silver-low bismuth/antimony electrodes was investigated by electrochemical methods in KOH solutions. The electrochemical redox characteristics such as peak multiplicity, peak currents and peak potentials on these electrodes under both potentiostatic steady state and cyclic voltammetric conditions were obtained. The anomalies associated with the redox peak potential values both in the anodic and cathodic branches of the cyclic voltammograms were attributed to the distinct electrochemical behaviour of bismuth/antimony on the electrode surface along with silver. The behaviour of these electrodes for the electrocatalytic cathodic reduction of oxygen was also investigated both by potentiostatic steady state and cyclic voltammetric techniques under rotating conditions. The kinetic parameters corresponding to the electrochemical reduction of oxygen on these electrodes were obtained. These electrodes were ranked with respect to their electrocatalytic activity both for the oxygen reduction and evolution reactions.     

Electrocatalytic Reduction of Oxygen on a Pd Ad-Layer Modified Au(111) Electrode in Alkaline Solution

Oxygen reduction was studied on palladium, cadmium and zinc ad-atom modified single crystal Au(111) electrodes. The electrodes were modified by underpotential deposition process and their activity towards oxygen reduction was studied in alkaline media by voltammetry. The reduction peaks obtained were compared with those of bare Au(111), Pd disc and bulk deposited Cd electrodes. Enhanced catalytic activity of the Au(111) electrode in the presence of Pd, Cd and Zn ad-layer can be attributed to a change in surface charge and energy by ad-layer formation. In oxygen saturated medium a well defined sharp reduction peak was observed at ?0.12 V for 1/5 ML Pd ad atom modified Au(111) electrode while it was positioned at ?0.18 V on a Pd disk electrode. The best shift in reduction peak potential was obtained with 2/5 ML Pd ad atom modified Au(111) electrode with similar current density of Pd disc electrode.     

The effect of polypyrrole-bound anthraquinonedisulphonate dianion on cathodic reduction of oxygen

Functionalized polypyrrole (PPy) films were prepared by incorporation of anthraquinonedisulphonate (AQDS) as doping anion during the electropolymerization of pyrrole (Py) monomer at a glassy carbon electrode from aqueous solution. The electrochemical behavior of the PPy-bound AQDS modified electrode and cathodic reduction of oxygen on the resulting polymer film were studied. An obvious surface redox reaction corresponding to AQ/H₂AQ was observed and the dependence of this reaction on the solution pH was also illustrated. The electrocatalytic ability of the PPy-bound AQDS modified electrode was demonstrated by the electroreduction of oxygen at the optimized pH of 6.3 in a phosphate buffer. The reduced AQDS (H₂AQ) is responsible for the extraordinary catalytic activity to the oxygen reduction reaction. The PPy layers not only act as an electron mediator, but also facilitate the stability of the modified electrode. It was found that the catalytic reaction occurred in the presence of the bound AQDS and O₂ is in agreement with an electrochemical–chemical (EC) mechanism. The kinetic parameters of oxygen reduction were determined using Koutecky–Levich equation and Tafel polarization technique.     

Electrochemical study of chitosan films deposited from solution at reducing potentials

We report the electrochemical characterization of chitosan films deposited at gold electrodes from an acidic solution at reducing potentials. Cyclic voltammetry was used to characterize the deposition and electroactivity of chitosan coated gold electrodes. Chitosan films were found to deposit at gold electrodes at potentials more negative than −1.0 V versus Ag/AgCl, a potential associated with the onset of water reduction and increase in pH near the electrode. The chitosan films are electrochemically inactive; similar background charging currents are observed at bare gold and chitosan coated electrodes. The chitosan films are permeable to both cationic [Ru(NH₃)₆^3+/2+] and anionic [Fe(CN)₆^3−/4−] redox couples, but anionic complexes are retained in the chitosan film. Semiintegral analysis was used to examine adsorbed redox species at the chitosan coated electrode surface. Electrochemical parameters, including apparent diffusion coefficients for the redox probes at the electrodeposited chitosan modified electrodes are presented and are comparable to values reported for cast chitosan films.     

Electroreduction of oxygen on glassy carbon electrodes modified with in situ generated anthraquinone diazonium cations

The electrochemical reduction of oxygen on glassy carbon (GC) electrodes modified with in situ generated diazonium cations of anthraquinone (AQ) has been studied using the rotating disk electrode (RDE) technique. The electrografting of the GC electrodes was carried out in two different media: in acetonitrile and in an aqueous acidic solution (0.5 M HCl). 1- and 2-Aminoanthraquinone were used as starting compounds for the formation of the corresponding diazonium derivatives. The anthraquinone diazonium cations were generated by reaction of the aminoanthraquinones with tert-butyl nitrite and sodium nitrite in acetonitrile and in 0.5 M HCl, respectively. For comparison purposes, the previously synthesised and crystallised diazonium tetrafluoroborates of anthraquinone were used for the GC surface modification. Cyclic voltammetry was employed to determine the surface concentration of AQ in O₂ free 0.1 M KOH. The electrocatalytic behaviour towards O₂ reduction was similar for all the AQ-modified electrodes studied. The kinetic parameters of oxygen reduction were determined using a surface redox catalytic cycle model. The rate constant of the reaction between the semiquinone radical anion of AQ and molecular oxygen was virtually independent of the point of attachment of the quinone to the electrode surface.     

Conducting polymer electrodes modified by metal tetrasulfonated phthalocyanines: Preparation and electrocatalytic behaviour towards dioxygen reduction in acid medium

Polypyrrole (Au/PPy) and polyaniline (Au/PAni) electrodes were prepared and their activities towards oxygen reduction in acid medium were examined. The insertion of iron or cobalt phthalocyanines into the conducting polymer during the electropolymerisation process was carried out and the modified electrodes were characterised by esr and uv-visible differential reflectance spectroscopies. The electrocatalytic behaviour of such electrodes towards oxygen reduction was examined.The influence of the central metal of the macrocycle and of the kind of polymer was investigated. It appears that the modified electrodes containing iron tetrasulfonated phthalocyanine are the most active ones but they are less stable than electrodes containing cobalt tetrasulfonated phthalocyanine. The comparison of the electrocatalytic behaviour of the Au/polymer-FeTsPc electrode with that of a bare platinum electrode towards oxygen reduction indicates that the reduction process is the same for both electrodes. The Au/polymer-FeTsPc electrode allows then to reduce the oxygen molecule mainly via the 4-electron process into water as main product.In the case of the Au/polymer-CoTsPc electrode, the role of the conducting polymer in the whole reduction process is demonstrated. The Au/PAni-CoTsPc electrode allows to reduce the oxygen molecule mainly via the 2-electron reaction into hydrogen peroxide, whereas the Au/PPy-CoTsPc electrode allows it to reduce into water via the hydrogen peroxide formation for potentials lower than 0.4 V rhe.     

Voltammetric behavior study of folic acid at phosphomolybdic-polypyrrole film modified electrode

The electrochemical behavior of folic acid at the Keggin-type phosphomolybdate (PMo₁₂) doped polypyrrole (PPy) film modified glassy carbon electrode (PMo₁₂-PPy/GCE) was studied. PMo₁₂ doped PPy modified electrodes were achieved during the electrochemical preparation of the polymer films in aqueous solution. The redox behavior of the modified electrode was described by cyclic voltammetry. The electrochemical behavior of folic acid at PMo₁₂-PPy/GCE was studied by 0.5 order differential voltammetry. Numerous factors affecting the reduction peak currents of folic acid at PMo₁₂-PPy/GCE were optimized to maximize the sensitivity. The results showed that folic acid had high inhibitory activity toward the reduction of modified electrode in 0.01 M H₂SO₄. The reduction peak currents were directly proportional to the concentration of folic acid from 1.0 × 10⁻⁸ to 1 × 10⁻⁷ M with correlation coefficient of 0.9976, a detection limit of 1.0 × 10⁻¹⁰ M of folic acid was estimated. From the inhibitory effect of folic acid on PMo₁₂-PPy/GCE, the apparent formation constant of folic acid with the modified film was estimated. This modified electrode showed excellent sensitivity and stability for the determination of folic acid. The response mechanism of folic acid at PMo₁₂-PPy/GCE was discussed in detail.     

Fabrication of palladium coated nanoporous gold film electrode via underpotential deposition and spontaneous metal replacement: A low palladium loading electrode with electrocatalytic activity

An electrochemical approach to nanoporous film-based gold catalyst design using the underpotential deposition and redox replacement technique is presented. The procedure consisted of the underpotential deposition (UPD) of copper on the gold nanoporous film, with subsequent replacement of the copper by palladium at open circuit in a palladium containing solution. The resulting electrode was studied using cyclic voltammetry and scanning electron microscopy. The electrocatalytic activity of as-prepared palladium nanoporous gold film electrodes toward the oxygen reduction reaction is presented.     

Redox polymers based on polyamines

Conditions of formation of redox polymers based on quinones were studied. The ways of synthesis of macromolecules containing primary amino group via nitration and reduction of polymers, chemical modification and polymerization are discussed. Some pecularities of reduction of nitrated high molecular compounds in comparison with low molecular weight analogs were established. The effect of the polymer matrix on the reactivity of the amino group in nucleophilic substitution has been studied. The ways of increasing the activity of the primary amino group in the initial polyamines by changing the substituent are discussed, as well as the effect of the type of quinoid compound on the yield and properties of polymers formed. Polyaminoquinones were used for the preparation of ion-selective film electrodes without an inner liquid compartment. The redox polymer provided thermodynamic reversibility on the membrane-electron conductor interface. As a result a stable functioning ion-selective electrode with an inner contact has been prepared.     

Bioelectrocatalytic mediatorless dioxygen reduction at carbon ceramic electrodes modified with bilirubin oxidase

Carbon ceramic electrodes were prepared by sol-gel processing of a hydrophobic precursor - methyltrimethoxysilane (MTMOS) - together with dispersed graphite microparticles according to a literature procedure. Bilirubin oxidase (BOx) was adsorbed on this electrode from buffer solution and this process was followed by atomic force microscopy (AFM). The electrodes exhibited efficient mediatorless electrocatalytic activity towards dioxygen reduction. The activity depends on the time of adsorption of the enzyme and the pH. The electrode remains active in neutral solution. The bioelectrocatalytic activity is further increased when a fraction of the carbon microparticles is replaced by sulfonated carbon nanoparticles (CNPs). This additive enhances the electrical communication between the enzyme and the electronic conductor. At pH 7 the carbon ceramic electrode modified with bilirubin oxidase retains ca. half of its highest activity. The role of the modified nanoparticles is confirmed by experiments in which a film embedded in a hydrophobic silicate matrix also exhibited efficient mediatorless biocatalytic dioxygen reduction. Scanning electrochemical microscopy (SECM) of the studied electrodes indicated a rather even distribution of the catalytic activity over the electrode surface.     

Electrochemical reactivity at graphitic micro-domains on polycrystalline boron doped diamond thin-films electrodes

This paper deals with the electrochemical reactivity of boron doped diamond (BDD) electrodes. A comparative study has been carried out to show the influence of the presence of graphitic micro-domains upon the surface of these films. Those graphitic domains are sometimes present on as-grown boron doped diamond electrodes. The effect of doping a pure Csp³ diamond electrode is established by highly oriented pyrolytic graphite (HOPG) abrasion onto the diamond surface. In order to establish the effect of doping on a pure Csp³ diamond electrode, the amount of graphitic domains was increased by means of HOPG crystals grafted onto the BDD surface. Indeed that method allows the enrichment of the Csp² contribution of the electrode.The presence of graphitic domains can be correlatively associated with the presence of kinetically active redox sites. The electrochemical reactivity of boron doped diamond electrodes shows a distribution of kinetic constants on the whole surface of the electrode corresponding to different active sites. In this paper, we have studied by cyclic voltammetry and electrochemical impedance spectroscopy the kinetics parameters of the ferri/ferrocyanide redox couple in KCl electrolyte. A method is proposed to diagnose the presence of graphitic domains on diamond electrodes, and an electrochemical “pulse cleaning” procedure is proposed to remove them.     

The characterization and bioelectrocatalytic properties of hemoglobin by direct electrochemistry of DDAB film modified electrodes

Direct electrochemistry of hemoglobin can be performed in acidic and basic aqueous solutions in the pH range 1-13, using stable, electrochemically active films deposited on a didodecyldimethylammonium bromide (DDAB) modified glassy carbon electrode. Films can also be produced on gold, platinum, and transparent semiconductor tin oxide electrodes. Hemoglobin/DDAB films exhibit one, two, and three redox couples when transferred to strong acidic, weak acidic and weak basic, and strong basic aqueous solutions, respectively. These redox couples, and their formal potentials, were found to be pH dependent. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ deposition of DDAB on gold disc electrodes and hemoglobin deposition on DDAB film modified electrodes. A hemoglobin/DDAB/GC modified electrode is electrocatalytically reduction active for oxygen and H₂O₂, and electrocatalytically oxidation active for S₂O₄²⁻ through the Fe(III)/Fe(II) redox couple. In the electrocatalytic reduction of S₄O₆²⁻, S₂O₄²⁻, and SO₃²⁻, and the dithio compounds of 2,2′-dithiosalicylic acid and 1,2-dithiolane-3-pentanoic acid, the electrocatalytic current develops from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in neutral and weakly basic aqueous solutions. Hemoglobin/DDAB/GC modified electrodes are electrocatalytically reduction active for trichloroacetic acid in strong acidic buffered aqueous solutions through the Fe(III)/Fe(II) redox couple. However, the electrocatalytic current developed from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in weak acidic and basic aqueous solutions. The electrocatalytic properties were investigated using the rotating ring-disk electrode method.     

Nitrate reduction on Pt single crystals with Pd multilayer

Nitrate reduction on palladium multilayers deposited on platinum single crystal electrodes was studied by cyclic voltammetry and FTIR spectroscopy in acid and alkaline media. The results are compared with those obtained with bulk palladium single crystals. The reaction is sensitive to the electrode surface structure, the reactivity depending on the solution pH. In acid solution nitrate was reduced at potentials below the potential of zero total charge (pztc), when the electrode is negatively charged. Competition between nitrate, hydrogen and anion adsorption and NO formation and accumulation at the surface are proposed as the main reasons for the slow reaction rate. On the bulk palladium single crystal electrodes, NO formation leads to a fast blockage of the surface resulting in a very low activity for nitrate reduction. In alkaline solution, nitrate is reduced at more positive potentials with significantly higher current being measured on the Pd multilayer on Pt(1 0 0) electrode.     

Electrochemical study of isopoly- and heteropoly-oxometallates film modified microelectrodes —vi. preparation and redox properties of 12-molybdophosphoric acid and 12-molybdosilicic acid modified carbon fiber microelectrodes

The redox behaviours of 12-molybdophosphoric acid (12-MPA) and 12-molybdosilicic acid (12-MSA) in aqueous acid media are characterized at the carbon fiber (CF) microelectrode. The preparation of CF microelectrode modified with 12-MPA or 12-MSA monolayer and the oxidation-reduction properties of the modified electrode in aqueous acid media or 50% (v/v) water-organic media containing some inorganic acids are studied by cyclic voltammetry. 12-MPA or 12-MSA monolayer modified CF microelectrode with high stability and redox reversibility in aqueous acidic media can be prepared by simple dip coating. The cyclic voltammograms of 12-MPA and 12-MSA and their modified CF microelectrodes in aqueous acid solution exhibit three two-electron reversible waves with the same half-wave potentials, which defines that the species adsorbed on the CF electrode surface are 12-MPA and 12-MSA themselves. The acidity of electrolyte solution, the organic solvents in the electrolyte solution, and the scanning potential range strongly influence on the redox behaviours and stability of 12-MPA or 12-MSA monolayer modified electrodes. On the other hand, the catalytic effects of the 12-MPA and 12-MSA and chlorate anions in aqueous acidic solution on the electrode reaction processes of 12-MPA or 12-MSA are described.     

Oxygen reduction on poly(4-vinylpyridine)-modified ordinary pyrolytic graphite electrodes with adsorbed cobalt tetra-sulphonated phthalocyanine in acid solutions

Poly(4-vinylpyridine) (PVP) has been used to modify ordinary pyrolytic graphite (OPG) electrodes with adsorbed cobalt tetra-sulphonated phthalocyanine (CoTsPc) in acid solutions. These modified electrodes were prepared in different manners and characterized by cyclic voltammetry. Their electrocatalytic activity for oxygen reduction and stability in 0.05M H₂SO₄ solutions was examined at room temperature. The OPG/CoTsPc/PVP modified electrodes were found to be more active for oxygen reduction in 0.05M H₂SO₄ solutions as compared to the electrode with adsorbed CoTsPc on OPG without PVP. The increase in activity is due to the formation of an adduct between PVP and CoTsPc. U.v.-visible and FTIR studies provide evidence for such adduct formation. Over a 10 h period the activity of the OPG/CoTsPc/PVP system was essentially constant while that of OPG/CoTsPc without polymer decreased by a substantial amount (about 37%). The PVP layer inhibits the diffusion of the CoTsPc and/or Co out of the complex into the solution phase. The stability of the OPG/CoTsPc/PVP system may also be due to low solubility of the adduct between PVP and CoTsPc in a 0.05M H₂SO₄ solution. Thicker films of PVP decreased the diffusion limiting oxygen reduction current. The effect of pH of the electrolyte solution on the activity of such PVP-modified electrodes for oxygen reduction has also been investigated.     

Azobenzene-modified oxygen-fed graphite/PTFE electrodes for hydrogen peroxide synthesis

The performance of a catalyzed H₂O₂ electrogeneration process using a modified oxygen-fed graphite/PTFE electrode is reported. The organic redox catalyst chosen for incorporation into the graphitic mass was azobenzene. The yield of the hydrogen peroxide is related to the applied potential and to azobenzene concentration. Modification of the gas diffusion electrode with azobenzene improved hydrogen peroxide production, and the overpotential for oxygen reduction was shifted to less negative values compared to the performance of a non-catalyzed electrode, indicating that these modified electrodes have good electro-activity.     

Influences of metal oxides on carbon corrosion under imposed electrochemical potential conditions

Graphite electrodes, whose surface is partially covered with metal oxides, are prepared by the electrochemical deposition of MoO_x, WO_x, and SnO₂ particles, and their corrosion behaviors under the imposed electrochemical potential conditions are investigated. Scanning electron microscopy observation shows that highly oriented pyrolytic graphites (HOPGs) modified with MoO_x and WO_x particles (MoO_x|HOPG and WO_x|HOPG) suffer from carbon corrosion and show pits formation on the surface of HOPG after an electrochemical potential cycling in a range of 0.8–1.0 V. In contrast, SnO₂-modified HOPG (SnO₂|HOPG) exhibits superior tolerance to electrochemical oxidation. Cyclic voltammograms show that the SnO₂ modification prevents an increase in the redox currents for quinone/hydroquinone reactions and the electrochemical double layer capacitances on the HOPG electrode. These results indicate that the influence of metal oxides on carbon corrosion varies depending on the kind of metal oxides, and that SnO₂ is a proper choice to protect the surface of HOPG from carbon corrosion, under electrochemical potentials.     

Surface-modified reusable gold electrode for detection of dissolved oxygen

The behavior of gold electrodes for the detection of dissolved oxygen was studied by the method of cyclic voltammetry in a phosphate-buffered solution with physiological pH. Surface modification with electropolymerized poly (o-phenylenediamine) film was performed to improve electrode antifouling properties. The voltammetric signature of oxygen was considered in terms of film electropolymerization conditions and post-deposition conditioning of the electrodes. The changes in the chemical structure of the poly (o-phenylenediamine) films as a result of these factors were confirmed by X-ray photoelectron spectroscopy analysis. Following long post-deposition conditioning in a phosphate-buffered solution, the modified electrodes exhibited stable voltammetric signatures in repeated tests and during storage as well as in the presence of a dense population of Escherichia coli (characterized by negligible metabolic activity) in the buffer. The results are indicative of the improved electrode antifouling properties.