Electrochemical Degradation of Herbicidal and Pure 2,4-Dichlorophenoxy Acetic Acid on Pb/PbO2 Modified Electrodes

Lead/lead oxide Pb/PbO₂ modified electrodes was prepared for electrocatalytic oxidation of agrochemicals including herbicidal 2,4-D (albar super) and pure 2,4-dichlorophenoxy acetic acid. The results of electrocatalytic oxidation process of the agrochemical solutions were expressed in terms of the remaining concentration and COD removal. The different operating conditions of treatment process were investigated including current density, pH, temperature, time of electrolysis, type of conductive electrolyte, and its specific conductance. This electrode gives good results for the removal of agrochemicals and COD. Also, the results showed the best conductive electrolytes is NaCl. This observation was attributed to the small size of Na⁺ and contribution of Cl^? ion in formation of OCl^?.     

Electrocatalytic Oxidation of Organic Pollutants on Boron-Doped Diamond and Ti–Ru Oxide Anodes in Sulfate Medium

Electrochemical oxidation for degradation of industrial dye Methyl Orange in aqueous sulfate solutions with various electrocatalytic materials: boron-doped diamond electrode and electrode based on titanium and ruthenium oxides. The influence exerted by the main working parameters of electrolysis (current density, concentration of Methyl Orange, pH) on the discoloration efficiency and on the chemical oxygen demand (COD) was examined. It was shown that an increase in the current density and a decrease in the pollutant concentration improve the process efficiency. However, this leads to an increase in the specific electric energy consumption per unit mass of COD. It was found that the boron-doped diamond electrode is a more efficient electrocatalytic material, compared with electrode based on titanium and ruthenium oxides. At low concentrations of Methyl Orange (<50 mg L^–1), there exists the possibility in principle of using the electrode based on titanium and ruthenium oxides not only for discoloration, but also for making lower the COD level.     

Electrografting of 4‐tert‐Butylcatechol on GC Electrode. Selective Electrochemical Determination of Homocysteine

A new sensor based on the grafting of 4‐tert‐butylcatechol on the surface of a glassy carbon electrode (GC) was developed for the catalytic oxidation of homocysteine ( Hcy ). The GC‐modified electrode exhibited a reversible redox response at neutral pH. Under the optimum conditions cyclic voltammetric results indicated the excellent electrocatalytic activity of modified electrode toward the oxidation of Hcy at reduced over‐potential about 350 mV. A linear dynamic range of 0.01–3.0 mM and a detection limit of 1.0 µM were obtained for Hcy . The modified electrode was used as an electrochemical sensor for selective determination of Hcy in human blood.     

Preparation,Characterization and Electrocatalytic Studies on Copper Complex Dye Film Modified Electrodes

Copper complex dye (C.I. Direct Blue 200) film modified electrodes have been prepared by multiple scan cyclic voltammetry. The effect of solution pH and nature of electrode material on film formation was investigated. The optimum pH for copper complex film formation on glassy carbon was found to be 1.5. The mechanism of film formation on ITO seems to be similar to that on GC surface but completely different mechanism followed with gold electrode. Cyclic voltammetric features of our modified electrodes are in consistent with a surface‐confined redox process. The voltammetric response of modified electrode was found to be depending on pH of the contacting solution. UV‐visible spectra show that the nature of copper complex dye is identical in both solution phase and after forming film on electrode. The electrocatalytic behavior of copper complex dye film modified electrode towards oxidation of dopamine, ascorbic acid and reduction of SO₅^2? was investigated. The oxidation of dopamine and ascorbic acid occurred at less positive potential on film electrode compared to bare glassy carbon electrode. Feasibility of utilizing our modified electrode in analytical estimation of dopamine, ascorbic acid was also demonstrated.     

Electrocatalytic Oxidation and Flow-Injection Determination of Sulfur-Containing Amino Acids at Graphite Electrodes Modified with a Ruthenium Hexacyanoferrate Film

The electrochemical behavior of sulfur-containing amino acids (cysteine, cystine, and methionine) at graphite electrodes modified with a ruthenium(III) hexacyanoferrate(II) film was studied. Glassy carbon and carbon paste were used as graphite materials. The electrocatalytic oxidation of amino acids at a modified electrode resulted in a decrease in the oxidation potentials of amino acids and an increase in the currents of their oxidation peaks as compared to those observed at an unmodified electrode. The voltammetric characteristics and hydrodynamic conditions for detecting the maximum catalytic current were found. A procedure is proposed for the electrocatalytic determination of cysteine, cystine, and methionine at a carbon-paste electrode modified with an inorganic film of ruthenium(III) hexacyanoferrate(II) under the conditions of flow-injection analysis.     

Application of multivariate optimization method in nanomolar simultaneous determination of morphine and codeine in the presence of uric acid using a glassy carbon electrode modified with a hydroxyapatite-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticle/multiwalled carbon nanotubes composite

The electrochemical oxidation of morphine (MO) and codeine (COD) has been investigated by the application of a novel glassy carbon electrode modified with a hydroxyapatite-Fe₃O₄ nanoparticles/multiwalled carbon nanotubes composite (HA-FeNPs-MWCNTs/GCE). The modified electrode worked as an efficient sensor for simultaneous determination of MO and COD in the presence of uric acid. Response surface methodology was utilized to optimize the voltammetric response of the modified electrode for the determination of MO and COD. The amount of HA-FeNPs in the modifier matrix (%HA-FeNPs), the solution pH and the accumulation time were chosen as the three important operating factors through the experimental design methodology. The central composite design as a response surface approach was applied for obtaining the optimum conditions leading to maximum oxidation peak currents for MO and COD. The differential pulse voltammetry results showed that the obtained anodic peak currents were linearly proportional to concentration in the range of 0.08–32 µM with a detection limit (S/N = 3.0) of 14 nM for MO and in the range of 0.1–28 µM and with a detection limit of 22 nM for COD. The proposed method was successfully applied to determine these compounds in human urine and blood serum samples.     

尿酸和叶酸存在下改性碳纳米管糊电极上多巴胺电催化氧化MohammadMazloum-Ardakani,MahboobeAbolhasani,Bibi-FatemehMirjalili,MohammadAliSheikh-Mohseni,AfsanehDehghani-Firouzabadi,AlirezaKhoshroo简

A chemically modified carbon paste electrode (CPE), consisting of 2,2''-[(1E)-(1,2-phenylenebis(azanylylidene)] bis(methanylylidene)]bis(benzene-1,4-diol) (PBD) and multiwalled carbon nanotubes (CNTs), was used to study the electrocatalytic oxidation of dopamine using cyclic voltammetry, chronoamperometry, and differential pulse voltammetry (DPV). First, the electrochemical behavior of the modified electrode was investigated in buffer solution. Then the diffusion coefficient, electrocatalytic rate constant, and electron-transfer coefficient for dopamine oxidation at the surface of the PBD-modified CNT paste electrode were determined using electrochemical approaches. It was found that under optimum conditions (pH = 7.0), the oxidation of dopamine at the surface of such an electrode occurred at about 200 mV, lower than that of an unmodified CPE. DPV of dopamine at the modified electrode exhibited two linear dynamic ranges, with a detection limit of 1.0 μmol/L. Finally, DPV was used successfully for the simultaneous determination of dopamine, uric acid, and folic acid at the modified electrode, and detection limits of 1.0, 1.2, and 2.7 μmol/L were obtained for dopamine, uric acid, and folic acid, respectively. This method was also used for the determination of dopamine in a pharmaceutical preparation using the standard addition method.     

Voltammetric and potentiometric study of cysteine at cobalt(II) phthalocyanine modified carbon-paste electrode

Cyclic voltammetry and potentiometry were used to investigate the electrochemical behavior of cysteine at a chemically modified electrode prepared by incorporating cobalt(II) phthalocyanine [Co(II)Pc] into carbon paste matrix. The modified electrode showed high electrocatalytic activity toward cysteine; the overpotential for the oxidation of cysteine was decreased by more than 100 mV, and the corresponding peak current increased significantly. The electrocatalytic process was highly dependent on the pH of the supporting electrolyte. The peak currents decreased when the pH was raised to 6 and totally disappeared at pH≥ 7, resulting from the autocatalytic oxidation of cysteine by Co(II)Pc at the electrode surface. Therefore, at pH values of 6 to 8, the modified electrode was used as a potentiometric sensor for quantitative measurement of cysteine in the presence of oxygen in air saturated solutions. In fact, the Co(II)Pc/Co(I)Pc couple acts as a suitable mediator for indirect oxidation of cysteine by dissolved oxygen at approximately neutral pH values. Under the optimized conditions, the potentiometric response of the modified electrode was linear against the concentration of cysteine in the range of 0.6 μM to 2 mM. The limit of detection was found to be 0.5 μM. The potentiometric response time was ≤15 s. The electrode showed long term stability; the standard deviation of the slope obtained after repeated calibration during a period of two months was 2.8% (n = 7). Application of the electrode in a recovery experiment for the determination of cysteine added to a synthetic serum sample is described.     

Electrocatalytic Oxidation of 2‐Thiouracil and 2‐Thiobarbituric Acid at a Carbon‐Paste Electrode Modified with Cobalt Phthalocyanine

Voltammetric behavior of two mercaptopyrimidine derivatives (2‐thiouracil and 2‐thiobarbituric acid) has been studied by cyclic voltammetry at a cobalt phthalocyanine (CoPc)‐modified carbon‐paste electrode. The results of voltammetric determinations showed that the CoPc in the matrix of modified electrode acts as catalyst for electrooxidation of these thiols (RSH), lowering the overpotential of the reaction and significantly increasing the sensitivity for detection of thiols in neutral conditions. The results of voltammetric and polarization measurements in solutions with various pHs were used for prediction of the mechanism of electrocatalytic oxidation at the surface of modified electrode. These results showed that at the modified electrode, electrochemical oxidation of thiolate anion (RS^?) is the rate‐determining step. It was found that the modified electrode exhibits good selectivity for catalytic oxidation of mercaptopyrimidines over other biologically important mercaptans such as cysteine, glutathione and thioglycolic acid. The results demonstrate that the peak current for thiol oxidation has a linear variation with the concentration in the range of 1×10^?2–1×10^?5 M. This system can be used for sensitive and selective voltammetric detection of mercaptopyrimidine derivatives.     

Direct Electrocatalytic Oxidation and Simultaneous Determination of 5‐Methylcytosine and Cytosine at Electrochemically Reduced Graphene Modified Glassy Carbon Electrode

Direct electrocatalytic oxidation and simultaneous determination of 5‐methylcytosine (5‐mC) and cytosine(C) were realized in alkaline solutions by differential pulse voltammetry (DPV) based on an electrochemically reduced graphene oxide (er‐GO) modified glassy carbon electrode (er‐GO/GCE). The as‐prepared er‐GO/GCE exhibited good electrocatalytic activity towards the oxidation of 5‐mC and C. Under optimum conditions, the er‐GO/GCE was applied to the simultaneous determination of 5‐mC and C with a significantly improved peak potential resolution (about 150 mV), and a linear relationship can be obtained in the range of 6–200.0 µmol/L and 8–250.0 µmol/L, respectively. In addition, the proposed method was further successfully applied to the analysis of methylation status in short CpG oligonucleotides with satisfactory results.     

The electrocatalytic examination of cephalosporins at carbon paste electrode modified with CoSalophen

The electrocatalytic oxidation of cephalexin and cefazolin has been studied at a carbon paste electrode modified with cobalt salophen (CoSal) by cyclic voltammetry. The selectivity of the carbon paste modified with CoSal in detecting cephalexin and cefazolin was examined. To suggest the electrocatalytic mechanism for electro-oxidation of cefazolin, the electrochemical behavior of ceftriaxone was investigated which has a thiol group out of the beta lactam ring. The electrocatalytic oxidation of these antibiotics is shown to be irreversible at the CoSal modified electrode. Scan rate dependence of cefazolin, which is a sulfur-containing compound, has been examined. The results indicated that the electrocatalytic oxidation of the compounds is diffusion controlled. The responses of the modified electrode were compared with those of unmodified electrode and it has shown that the modified electrode has better sensitivity than unmodified electrode to the detection of cefazolin. The overall number of electrons contributed to the oxidation of cefazolin is obtained 1 by chronoamperometry; the number of electron involved in the rate-determining step was 1. The results of differential pulse voltammetry (DPV) using the modified electrode with high sensitivity were applied for the determination of cefazolin in human synthetic serum samples. The linear range was obtained from 1 × 10⁻⁵ to 1 × 10⁻³ M for DPV determination of cefazolin in buffered solutions (pH 3.0).     

聚苯胺薄膜修饰电极对抗坏血酸的电催化氧化

本文表明聚苯胺(PAn)薄膜修饰电极对水溶液中的抗坏血酸(AH_2)在较宽的pH范围和较宽的浓度范围内均有良好的电催化氧化作用, 为EC平行催化过程。利用旋转圆盘电极(RDE)进行了催化过程动力学分析, 求出了催化反应动力学参数。在抗坏血酸浓度10~(-2)～10~(-6) mol·L~(-1)范围内, 催化峰电流与AH_2浓度均成良好的线性关系, 且PAn薄膜修饰电极具有很好的稳定性, 有应用分析抗坏血酸的意义。     

Sensitive Voltammetric Determination of Captopril Using a Carbon Paste Electrode Modified with Nano-TiO2/Ferrocene Carboxylic Acid

A carbon paste electrode (CPE) modified with ferrocene carboxylic acid (FcCA) and TiO2 nanoparticles was constructed by incorporating TiO2 nanoparticles and ferrocene carboxylic acid into the carbon paste matrix.The electrochemical behavior of captopril (CAP) at the surface of the modified electrode was investigated using electroanalytical methods.The modified electrode showed excellent electrocatalytic activity for the oxidation of CAP in aqueous solutions at physiological pH values.Cyclic voltammetric curves showed that the oxidation of CAP at the surface of the modified electrode reduced its overpotential by more than 290 mV.The modified electrode was used for detecting captopril using cyclic voltammetry and square wave voltammetry techniques.A calibration curve in the range of 0.03 to 2400μmol/L was obtained that had a detection limit of 0.0096 μmol/L (3σ) under the optimized conditions.The modified electrode was successfully used for the determination of captopril in pharmaceutical and biological samples.     

Electrocatalytic study of an electrode modified with Reactive Blue 4 dye covalently immobilized on amine-functionalized silica

In the present work, we investigated the immobilization and electrochemical behavior of Reactive Blue 4 dye on 3-aminopropyl-functionalized silica. The electrochemical behavior of the modified electrode and the electro-oxidation of dipyrone were studied by cyclic voltammetry. The modified electrode showed a well-defined redox coupling with a formal potential of 0.45 V (vs. saturated calomel reference electrode) assigned to anthraquinone/anthrahydroquinone redox process (pH?=?2). The modified electrode also demonstrated electrocatalytic activity and an increased peak current towards the oxidation of dipyrone at a reduced overall potential. The electrocatalytic process was found to be highly dependent on the pH of the supporting electrolyte. The voltammetric responses for dipyrone were linear in the concentration range of 49.9 to 440 μmol L^?1 at a pH of 2.0 with a detection limit and sensitivity of 22.0 μmol L^?1 and 0.0278 μA mmol L^?1, respectively.     

Simultaneous determination of uric acid, xanthine and hypoxanthine at poly(pyrocatechol violet)/functionalized multi-walled carbon nanotubes composite film modified electrode

A sensitive and selective electrochemical method was developed for simultaneous determination of uric acid (UA), xanthine (XA) and hypoxanthine (HX) based on a poly (pyrocatechol violet)/carboxyl functionalized multi-walled carbon nanotubes composite film modified electrode. The preparation and basic electrochemical performance of the novel composite film modified glassy carbon electrode were investigated in details. The electrochemical behaviors of UA, XA and HX at the modified electrode were studied by cyclic voltammetry. The results showed that this new electrochemical sensor exhibited excellent electrocatalytic activity towards the oxidation of the three analytes. The mechanism of catalysis was discussed. The anodic peaks of the three species were well defined with lowered oxidation potential and enhanced oxidation peak currents, so the modified electrode was used for simultaneous voltammetric measurement of UA, XA and HX by differential pulse voltammetry. Under the optimum conditions, the detection limits were 0.16 μmol L(-1) for UA, 0.05 μmol L(-1) for XA and 0.20 μmol L(-1) for HX, respectively (S/N of 3). The proposed method has been successfully applied to simultaneous determination of UA, XA and HX in human serum samples.     

Electrochemical oxidation technology to treat textile wastewaters

Dye-contaminated wastewater is hardly treated with conventional treatments. Consequently, there is an urgent need to develop powerful oxidation methods to ensure their removal and ensure water quality. In this framework, the scientific community is studying various treatment approaches, and this review aims to present important ideas on the applicability of electrochemical oxidation as an alternative to remove dyes from wastewater through the use of new carbon-based electrodes and dimensional stable anodes (DSAs) as commercial, environmentally friendly, and suitable electrocatalytic materials. In the discussion, the effect of the most important variables in this type of process is analyzed, namely, the type of dye, electrode material, and the different experimental conditions, that is, current density, electrolysis time, removal efficiency, color, or also abatement of the organic matter, such as total organic carbon (TOC) or chemical oxygen demand (COD).     

纳米La(OH)3修饰电极对邻苯二酚和对苯二酚的同时测定

研究了纳米La(OH)3修饰电极的制备及其对邻苯二酚和对苯二酚的电催化作用。讨论了支持电解质种类、酸度等对邻苯二酚和对苯二酚伏安响应的影响,获得了较为优化的实验条件。在0.1mol/LPBS(pH7.0)中,采用示差脉冲伏安测定邻苯二酚和对苯二酚,其浓度与氧化峰电流线性关系良好。共存的多种金属离子、抗坏血酸及等量的苯酚等不干扰测定。该电极用于模拟废水样中邻苯二酚和对苯二酚的测定,结果令人满意。     

Electrocatalytic oxidation of hydrazine at cobalt hexacyanoferrate- modified glassy carbon, Pt and Au electrodes

The electrocatalytic oxidation of hydrazine has been studied on glassy carbon, Pt and Au electrodes modified by cobalt hexacyanoferrate (CoHCF) using cyclic voltammetry and rotating disc techniques. It has been shown that the oxidation of hydrazine to nitrogen occurs at the potential coinciding with that of Co(II) to Co(III) transformation in a CoHCF film, where no oxidation signal is observed at a bare glassy carbon electrode. A Tafel plot, derived from RDE voltammograms, exhibits a slope of 150 mV, indicating a one-electron charge transfer process to be the rate-limiting step. The electrocatalytic efficiency of the modified electrode towards hydrazine oxidation depends on solution pH, and the optimum range was found to be located between pH 5 and pH 7. The kinetic behaviour and location of the electrocatalytic process were examined using the W.J. Albery diagnosis table, and it was concluded that the reaction has either a “surface” or a “layer” reaction mechanism. Pt- and Au-CoHCF-modified electrodes show no significant electrocatalytic activity towards hydrazine oxidation. Received: 25 April 1997 / Accepted: 12 August 1997     

原位电化学还原制备石墨烯修饰玻碳电极及其对亚硝酸根离子的电催化氧化性能

通过原位电化学还原直接制备石墨烯修饰玻碳电极,并用电化学阻抗谱（EIS）和扫描电子显微镜（SEM）对其进行了表征,研究了亚硝酸根离子（NO2-）在石墨烯修饰玻碳电极上的电化学行为.结果表明：石墨烯修饰玻碳电极对NO2-的氧化反应有良好的电催化活性,NO2-的浓度与峰电流呈良好的线性关系,且在pH 7.0的磷酸盐缓冲液（PBS）中其氧化峰电流最高.利用该方法测定了模拟废水中NO2的含量,结果令人满意.     

Voltammetric measurement of trace amount of glutathione using multiwall carbon nanotubes as a sensor and chlorpromazine as a mediator

In this work, we propose chlorpromazine as a new mediator for the rapid, sensitive, and highly selective voltammetric determination of glutathione (GSH) using multiwall carbon nanotubes paste electrode (MWCNTPE). The experimental results showed that the carbon nanotubes paste electrode has a highly electrocatalytic activity for the oxidation of GSH in the presence of chlorpromazine as a mediator. Cyclic voltammetry, double potential step chronoamperometry, and differential pulse voltammetry (DPV) are used to investigate the suitability of chlorpromazine at the surface of MWCNTPE as a mediator for the electrocatalytic oxidation of GSH in aqueous solutions. It is shown that chlorpromazine can catalyze the oxidation of GSH in an aqueous buffer solution to produce a sharp oxidation peak current at about +0.70 versus Ag/AgCl as a reference electrode. Kinetic parameters such as electron transfer coefficient and catalytic reaction rate constant, k/h, are also determined. Using DPV and under the optimum conditions at pH 4.0, the electrocatalytic oxidation peak current of GSH shows a linear dependence on GSH concentration in the GSH concentration range of 0.3 to 18.3 µM. The detection limit (3σ) is determined to be 0.16 µM. The relative standard deviation for 1.5 and 5.0 µM GSH are found to be 3.7% and 2.5%, respectively. The proposed method may, thus, also be used as a novel, selective, simple, and precise method for the voltammetric determination of GSH in such real samples as hemolyzed erythrocyte.