Electrocatalytic reduction of dioxygen at glassy carbon electrodes modified with polypyrrole/anthraquinonedisulphonate composite film in various pH solutions

Functionalized polypyrrole (PPy) film with anthraquinonedisulphonate (AQDS) incorporated as dopant was prepared by anodic polymerization of pyrrole (Py) at a glassy carbon electrode from aqueous solution. The electrochemical behavior of AQDS in PPy matrix and the electrocatalytic reduction of dioxygen on the resulting composite film were investigated in various pH solutions. The formal potential of AQDS and the reduction potential of dioxygen both exhibit pH dependence. In all pH solutions employed, the electrocatalytic reduction of dioxygen at the PPy/AQDS composite film establishes a pathway of irreversible two-electron reduction to form hydrogen peroxide. The pH 6.0 buffer solution is a more suitable medium for the reduction of dioxygen, where the PPy/AQDS composite film showed a more efficient electrocatalytic performance. It was found that AQDS is an effective mediator for the reduction of dioxygen and the reduced AQ is responsible for the enhanced catalytic activity. The catalytic current is under mixed kinetic-diffusion control. The number of electrons transferred and kinetic parameters of dioxygen reduction were determined using cyclic voltammetry, rotating disk voltammetry and Tafel polarization technique.     

Electrocatalytic reduction of dioxygen at a modified glassy carbon electrode based on Nafion-dispersed single-walled carbon nanotubes and cobalt–porphyrin with palladium nanoparticles in acidic media

Cathodic dioxygen (O₂) reduction was performed at a modified glassy carbon electrode (GCE) by single-walled carbon nanotubes (SWCNT)/Nafion^® (NF) film with cobalt (II) tetra (2-amino-phenyl) porphyrin (CoTAPP) and palladium (Pd) nanoparticles incorporated and employed as doping agents. Both the electrochemical behavior of SWCNT with a P(CoTAPP)–Pd nanoparticle matrix and the electrocatalytic reduction of O₂ were investigated using transmission electron microscopy (TEM), cyclic voltammetry (CV) and rotating ring-disk electrode (RRDE) techniques in 0.1 mol l⁻¹ H₂SO₄ aqueous solutions. The electrocatalytic reduction of O₂ at the SWCNT/NF/P(CoTAPP)–Pd composite film established a pathway of four-electron transfer reductions into H₂O. Hydrodynamic voltammetry revealed that the modified electrode was catalyzed effectively by the four-electron transferred reduction of dioxygen into H₂O with minimal generation of H₂O₂. The SWCNT/NF/P(CoTAPP)–Pd composite film showed a highly efficient electrocatalytic performance. P(CoTAPP)–Pd was an effective mediator for the reduction of dioxygen and was responsible for the enhanced catalytic activity.     

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.     

The pH-dependence of oxygen reduction on multi-walled carbon nanotube modified glassy carbon electrodes

The pH-dependence of oxygen electroreduction has been investigated on multi-walled carbon nanotube (MWCNT) modified glassy carbon (GC) electrodes. Various surfactants were used in the electrode modification: dihexadecyl hydrogen phosphate, cetyltrimethylammonium bromide, sodium dodecyl sulfate and Triton X-100. Electrochemical experiments were carried out in 0.5 M H₂SO₄ solution, acetate buffer (pH 5), phosphate buffers (pH 6, 7 and 8), borate buffer (pH 10), 0.01 M KOH, 0.1 M KOH and in 1 M KOH solution, using the rotating disk electrode (RDE) method. The oxygen reduction behaviour of MWCNT-modified GC electrodes at different pHs was compared. The RDE results revealed that the half-wave potential (E_1/2) of oxygen reduction was higher in solutions of high pH. At lower pHs (pH < 10) the value of E_1/2 did not essentially depend on the solution pH. A comparison with previous studies on bare GC showed that the pH-dependence of the half-wave potential of oxygen reduction on MWCNT-modified GC electrodes follows a similar trend to that observed for bare GC.     

Electrochemical reduction of imazamethabenz methyl on mercury and carbon electrodes

This paper presents polarographic and voltammetric studies of the reduction of the herbicide imazamethabenz methyl (2/3-methyl-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluate), on mercury and carbon electrodes. The electrochemical studies were performed in strongly acidic media (0.1-2.7 M H₂SO₄) as well as in the pH range of 1-12. The overall reduction process involves the uptake of two electrons. The results obtained in polarography show that there is the reduction of two species, related via an acid-base equilibrium, and having very close reduction potentials. The voltammetric results obtained with a glassy carbon electrode were very similar to those observed on mercury electrodes. The reducible group in the molecule is the imidazolinone ring. In strongly acidic media (pH < pK_a), the reaction mechanism proposed is the reduction of the protonated herbicide by an electrochemical-chemical-electrochemical (ECE) process, being the r.d.s. the second electron transfer. At pH > pK_a the neutral form of the herbicide is reduced and the second electron transfer becomes reversible or quasi-reversible. In basic media, the species reduced is the deprotonated imazamethabenz methyl and the r.d.s. is the second electron transfer.     

Electrocatalytic reduction of tert-butyl hydroperoxide at iron electrodes

The electrochemical reduction of tert-butyl hydroperoxide has been investigated in dimethylformamide and 1,2-dichloroethane. Voltammograms at platinum or at glassy carbon electrodes were indistinguishable from the background, whereas at iron electrodes a well-defined cathodic peak was observed. The electrocatalytic reduction of tert-butyl hydroperoxide was enhanced at freshly electrodeposited iron. A study of the reduction mechanism at iron electrode showed that both the electron transfer and the cleavage of the peroxidic bond occurred in a single step, consuming two electrons per mole with the production of tert-butanol. The electrocatalytic effect of iron was also observed for the cumyl hydroperoxide reduction. Organic peroxides are not implicated in an electrocatalytic reduction at iron surfaces.     

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.     

Cathodic reduction of acids in dimethylformamide on platinum

A linear correlation was shown to exist between the acidity and the cyclic voltammetric half-potential of the reduction of acids in DMF for carboxylic and N-acids in the pK_a range of 6-16. Chlorophenols are reduced at slightly lower potentials giving a separate parallel line. Applying the obtained equation and employing the same method to literature data in DMSO, the pK_a values for conjugate aids of DMF and DMSO can be calculated, showing DMSO·H⁺ to be more acidic (pK_a = 2.9) than DMF·H⁺ (pK_a = 5.7). The analysis of cyclovoltammetric data demonstrated that a CE mechanism operates in the reduction of strong acids, including the conjugate acid of DMF. Weaker acids are reduced by direct discharge or a mixed mechanism.     

Electrocatalytic oxidation of some amino acids on a nickel-curcumin complex modified glassy carbon electrode

This study investigated the electrocatalytic oxidation of alanine, l-arginine, l-phenylalanine, l-lysine and glycine on poly-Ni(II)-curcumin film (curcumin: 1,7-bis [4-hydroxy-3-methoxy phenyl]-1,6-heptadiene-3,5-dione) electrodeposited on a glassy carbon electrode in alkaline solution. The process of oxidation and its kinetics were established by using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy techniques. Voltammetric studies indicated that in the presence of amino acids the anodic peak current of low valence nickel species increased, followed by a decrease in the corresponding cathodic current. This indicates that amino acids were oxidized on the redox mediator which was immobilized on the electrode surface via an electrocatalytic mechanism. Using Laviron's equation, the values of α and k_s for the immobilized redox species were determined as 0.43 ± 0.03 and 2.47 ± 0.02 × 10⁶ s⁻¹, respectively. The rate constant, the electron transfer coefficient and the diffusion coefficients involved in the electrocatalytic oxidation of amino acids were determined.     

Electrocatalytic reduction of NO2: Platinum modified glassy carbon electrode

Platinum particles were electrochemically deposited over glassy carbon (GC) to prepare GC-Pt electrodes. The electrocatalytic behaviors of this electrode have been compared with that of an ordinary polycrystalline(OPC) Pt and GC electrode in reducing NO₂⁻ at neutral medium. The as prepared GC-Pt electrode reduced NO₂⁻, exhibiting double-peak reduction waves. The reduction performance of this electrode was noticed at least 7.8 times higher than that of an OPC Pt electrode. The sensitivity of the GC-Pt electrode was found to be enhanced by the temperature rise. A consecutive mechanism, NO₂⁻ → NO → NH₄⁺, over the as prepared GC-Pt electrode has been investigated.     

Electrocatalytic oxidation of hydrazine at overoxidized polypyrrole film modified glassy carbon electrode

Electrocatalytic oxidation of hydrazine (HZ) was studied on an overoxidized polypyrrole (OPPy) modified glassy carbon electrode using cyclic voltammetry and chronoamperometry techniques. The OPPy-modified glassy carbon electrode has very high catalytic ability for electrooxidation of HZ, which appeared as a reduced overpotential in a wide operational pH range of 5-10. The overall numbers of electrons involved in the catalytic oxidation of HZ, the number of electrons involved in the rate-determining and diffusion coefficient of HZ were estimated using cyclic voltammetry and chronoamperometry. It has been shown that using the OPPy-modified electrode, HZ can be determined by cyclic voltammetry and amperometry with limit of detection 36 and 3.7 μM, respectively. The results of the analysis suggest that the proposed method promises accurate results and could be employed for the routine determination of HZ.     

Electrocatalytic oxidation of NADH on a glassy carbon electrode modified with MWCNT-Pd nanoparticles and poly 3,4-ethylenedioxypyrrole

An NADH biosensor based on MWCNTs-Pd nanoparticles and polymerized 3,4-ethylenedioxypyrrole (PEDOP) was developed and characterized. PEDOP/MWCNTs-Pd/GCE was prepared quickly and simply and showed improved sensitivity to NADH. Comparable results were obtained by cyclic voltammetric (CV) and amperometric methods for NADH determination. The amperometric method gave short response times, and linear regression was observed at concentrations below 1.0 mM. The proposed NADH biosensor exhibited a wide linear response range of 1 μM–13 mM during amperometric testing using an applied potential of 0.42 V, with a low detection limit of 0.18 μM (S/N = 3). The sensor demonstrated fast responses and good stability.     

Electrocatalytic reduction of oxygen at glassy carbon electrode modified by polypyrrole/anthraquinones composite film in various pH media

The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. The electrochemical behaviour of the modified electrodes was examined in various pH media and both the formal potential of anthraquinones and reduction potential of dioxygen exhibited pH dependence. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O₂ to H₂O₂. pH 6.0 was chosen as the most suitable medium to study the electrocatalysis by comparing the peak potential of oxygen reduction and enhancement in peak current for oxygen reduction. The diffusion coefficient values of AQ at the modified electrodes and the number of electrons involved in AQ reduction were evaluated by chronoamperometric and chronocoulometric techniques, respectively. In addition, hydrodynamic voltammetric studies showed the involvement of two electrons in O₂ reduction. The mass specific activity of AQ used, the diffusion coefficient of oxygen and the heterogeneous rate constants for the oxygen reduction at the surface of modified electrodes were also determined by rotating disk voltammetry.     

Deposition of new thia-containing Schiff-base iron (III) complexes onto carbon nanotube-modified glassy carbon electrodes as a biosensor for electrooxidation and determination of amino acids

Multiwall carbon nanotubes (MWCNTs) were used as an immobilization matrix to incorporate an Fe (III)–Schiff base complex as an electron-transfer mediator onto a glassy carbon electrode surface. First, the preheated glassy carbon was subjected to abrasive immobilization of MWCNTs by gently rubbing the electrode surface on filter paper supporting the carbon nanotubes. Second, the electrode surface was modified by casting 100 μL of an Fe (III)-complex solution (0.01 M in ACN). The cyclic voltammograms of the modified electrode in an aqueous solution displayed a pair of well-defined, stable and nearly reversible reductive oxidation redox systems with surface confined characteristics. Combinations of unique electronic and electrocatalytic properties of MWCNTs and Fe (III)–Schiff base complexes resulted in a remarkable synergistic augmentation of the response. The electrochemical behavior and stability of the modified electrode in aqueous solutions at pH 1–9 were characterized by cyclic voltammetry. The apparent electron transfer rate constant (K_s) and transfer coefficient (a) were determined by cyclic voltammetry and were approximately 7 s⁻¹ and 0.55, respectively. The modified electrodes showed excellent catalytic activity towards the oxidation of amino acids at an unusually positive potential in acidic solution. They also displayed inherent stability at a wide pH range, fast response time, high sensitivity, low detection limit and had a remarkably positive potential oxidation of amino acids that decreased the effect of interferences in analysis. The linear concentration range, limits of detection (LOD), limits of quantization (LOQ) and relative standard deviation of the proposed sensor for the amino acid detection were 1–55,000, 1.10–13.70, 2.79–27.14 and 1.30–5.11, respectively.     

Uniaxially oriented carbon monoliths as supercapacitor electrodes

Cylindrical carbon monoliths of 7 mm in diameter and certain heights (1, 2, 3, 4 and 5 mm) are studied as model electrodes for supercapacitors. The monoliths show a narrow microporous structure with average micropore size of 0.73 nm and specific surface area of 1086 m² g⁻¹. The monoliths show straight walls and channels, both arranged along the cylinder axis. The former account for a remarkable electrical conductivity (6.5 S cm⁻¹ at room temperature). The latter allow a rapid ionic transport between the electrolyte bulk and the carbon walls and account for a high specific capacitance at high current density. The cell capacitance and resistance increase linearly with the monolith height according to C = (1.78 ± 0.06)h and ESR = (0.08 ± 0.01)h + (1.67 ± 0.04), respectively. The contribution of the electrolyte resistance, monolith resistance and monolith/collector resistance to ESR is discussed. The cell response time or constant time increases with the monolith height but according to a power dependence, τ = (4.5 ± 0.2)h^{(1.61 ± 0.03)}. The carbon of the monoliths show in KOH electrolyte a specific capacitance of 150 F g⁻¹ and a capacitance per surface area of 14 μF cm⁻².     

Adsorption of copper and lead species at electrochemically activated glassy carbon electrodes

The adsorption behaviors of Cu²⁺ and Pb²⁺ species at electrochemically activated glassy carbon obtained by different activation methods have been studied. Micropore structures were developed by cyclic polarization while small void space located at the bottom of the large void space was resulted from potentiostatic activation. The adsorption of the adsorbents would depend on the relative sizes of both the adsorbents and the void space created by electrochemical pretreatment. Different quinone derivatives would adsorb to different adsorption sites at the activated electrode, and consequently, affected the uptake of metal ions at the activated electrode incorporated with different quinone derivatives. Electrostatic and hydrophobic interactions between the adsorbents and the graphite oxide film might be involved.     

The electrocatalytic influence of underpotential lead adsorbates on the reduction of oxygen at glassy carbon electrodes in acid solution

The electrochemical reduction of oxygen and hydrogen peroxide has been investigated on a glassy carbon rotating disk electrode in 0.5 M HClO₄ at various concentrations of Pb²⁺. An overall 2-electron reduction of O₂ to H₂O₂ is found on glassy carbon which, in the presence of Pb²⁺, is positively catalyzed. The electrocatalytic effect can be correlated to an underpotential deposition (UPD) of lead at a limited number of active sites on the glassy carbon surface. The hydrogen peroxide reduction is nearly completely inhibited by the UPD of lead. The observed concentration dependence with respect to Pb²⁺ is in accordance with the Nernstian behaviour of the UPD process.     

Electrocatalytic reduction of dioxygen by cobalt porphyrin-modified glassy carbon electrode with single-walled carbon nanotubes and nafion in aqueous solutions

Cobalt porphyrin (CoP)-modified glassy carbon electrode (GCE) with single-walled carbon nanotubes (SWNTs) and Nafion demonstrated a higher electrocatalytic activity for the reduction of dioxygen in 0.1 M H₂SO₄ solution. Cyclic and hydrodynamic voltammetry at the CoP-SWNTs/GCE-modified electrodes in O₂-saturated aqueous solutions was used to study the electrocatalytic pathway. Compared with the CoP/GCE-modified electrodes, the reduction potential of dioxygen at the CoP-SWNTs/GCE-modified electrodes was shifted to the positive direction and the limiting current was greatly increased. Especially, the Co(TMPP)-SWNTs/GCE-modified electrode was catalyzed effectively by the 4e⁻ reduction of dioxygen to water, because hydrodynamic voltammetry revealed the transference of approximately four electrons for dioxygen reduction and the minimal generation of hydrogen peroxide in the process of dioxygen reduction.     

Electrooxidation of DNA at glassy carbon electrodes modified with multiwall carbon nanotubes dispersed in polyethylenimine

This work reports the electrochemical response of the complex between dsDNA and PEI formed in solution and at the surface of glassy carbon electrodes (GCE) modified with a dispersion of multi-walled carbon nanotubes in polyethylenimine (CNT-PEI). Scanning Electron Microscopy and Scanning Electrochemical Microscopy demonstrate that the dispersion covers the whole surface of the electrode although there are areas with higher density of CNT and, consequently, with higher electrochemical reactivity. The adsorption of DNA at GCE/CNT-PEI is fast and it is mainly driven by electrostatic forces. A clear oxidation signal is obtained either for dsDNA or a heterooligonucleotide of 21 bases (oligoY) at potentials smaller than those for the oxidation at bare GCE. The comparison of the behavior of DNA before and after thermal treatment demonstrated that the electrochemical response highly depends on the 3D structure of the nucleic acid.     

Electrocatalytic hydrazine oxidation on quinizarine modified glassy carbon electrode

The electrocatalytic oxidation of hydrazine has been studied on glassy carbon modified by electrodeposition of quinizarine, using cyclic voltammetry and chronoamperometry techniques. It has been shown that the oxidation of hydrazine to nitrogen occurs at a potential where oxidation is not observed at the bare glassy carbon electrode. The apparent charge transfer rate constant and transfer coefficient for electron transfer between the electrode surface and immobilized quinizarine were calculated as 4.44 s⁻¹ and 0.66, respectively. The heterogenous rate constant for oxidation of hydrazine at the quinizarine modified electrode surface was also determined and found to be about 4.83 × 10³ M⁻¹ s⁻¹. The diffusion coefficient of hydrazine was also estimated as 1.1 × 10⁻⁶ cm² s⁻¹ for the experimental conditions, using chronoamperometry.