Study on the oxidation of C4-phenolic-1,4-dihydropyridines and its reactivity towards superoxide radical anion in dimethylsulfoxide

Electrochemical characterization on glassy carbon electrode (GCE) and reactivity with superoxide radical anion in aprotic medium of three new synthesized C4-phenolic-1, 4-dihydropyridines is reported.Voltammetry, coulometry, controlled-potential electrolysis (CPE), UV-vis spectroscopy, ¹H NMR techniques were employed for the characterization of title compounds.The oxidation mechanism involves initially an oxidation process on the phenol moiety with the formation of the corresponding quinone followed by a second one affecting the dihydropyridine ring to give the pyridine derivative. Both processes appeared irreversible in character.Cyclic voltammetry was used to generate O₂⁻ by reduction on GCE of molecular oxygen in DMSO. The reactivity of DHPs towards O₂⁻ was directly measured by the anodic current decay of the radical in the presence of increasing concentration of tested 1,4-dihydropyridines and compared with the reaction of the reference antioxidant, Trolox. The linear correlations obtained between the anodic current of O₂⁻ and compound concentrations in the range between 0.01 mM and 1.00 mM allowed the determination of both the DHP antioxidant index (AI) and the concentrations needed to consume 50% of O₂⁻. Synthesized C4-phenolic 1,4-dihydropyridines exhibited significant scavenging capacity towards superoxide radical anion higher than Trolox and tested commercial 1,4-dihydropyridines.     

Electrografting of the cyanomethyl radical onto carbon and metal surfaces

Nanometer layers are grafted on the surface of carbon or metallic electrodes by electrochemical reduction of iodo or bromoacetonitrile in acetonitrile. The structure of these layers, (carbon or metal)–[CH₂–CH(NH₂)–]_n, is determined by electrochemistry, ellipsometry and IRRAS. The bond between the surface and the organic layer is evidenced by ToF-SIMS. A mechanism is proposed to account for the formation of the layers: the grafting is assigned to the reaction of the cyanomethyl radical, CH₂CN, with the electrode surface and the latter is partly reduced to the cyanomethyl anion ⁻CH₂CN that attacks the first grafted –CH₂CN group, leading to the growth of the layer. It is also possible to produce the same radical by oxidation of the ⁻CH₂CN anion -obtained by deprotonation of acetonitrile-, but in this case only traces of grafting are detected on the electrode as the radical is trapped by the large excess of anions.     

Electrooxidation of alcohols at a nickel oxide/multi-walled carbon nanotube-modified glassy carbon electrode

Electrocatalytic oxidation of methanol and some other primary alcohols on a glassy carbon electrode modified with multi-walled carbon nanotubes and nano-sized nickel oxide (GCE/MWNT/NiO) was investigated by cyclic voltammetry and chronoamperometry in alkaline medium. The results were compared with those obtained on a nickel oxide-modified glassy carbon electrode (GCE/NiO). Both the electrodes were conditioned by potential cycling in the range of 0.1–0.6 V versus Ag/AgCl in a 0.10 M NaOH solution. The effects of various parameters such as scan rate, alcohol concentration, thickness of NiO film, and real surface area of the modified electrodes were also investigated and compared. It was found that the GCE/MWNT/NiO-modified electrode possesses an improved electrochemical behavior over the GC/NiO-modified electrode for methanol oxidation.     

The preparation of PbO2 coatings on reticulated vitreous carbon for the electro-oxidation of organic pollutants

The preparation of PbO₂ coatings on reticulated vitreous carbon (RVC) has been carried out at constant current from electrolytic baths containing aqueous Pb(II) and methanesulfonic acid (MSA, CH₃SO₃H). The morphological and structural analysis of the RVC/PbO₂ deposits carried out by scanning electron microscopy (SEM) and X-ray diffraction revealed that a thick (100 μm), homogeneous, nanostructured β-PbO₂ film can be successfully formed. As a result, three-dimensional β-PbO₂ structures were obtained, being particularly interesting for their use as anodes in wastewater treatment. The high oxidation ability of these anodes has been verified by the electro-oxidation of Methyl Orange aqueous solutions. Quick decolourisation was achieved, with total colour removal in less than 60 min at 600 mA due to the production of large amounts of reactive OH radicals from the oxidation of water at high anodic potentials. The progressive mineralisation of the solutions was also ascertained from the total organic carbon (TOC) removal, which was much quicker at a higher applied current. All the coated RVC electrodes exhibited excellent long-term stability and remained unaltered after prolonged electrolyses. In addition, novel PbO₂ composite coatings were prepared in the presence of hydrothermally synthesized titanate nanotubes (TiNT). The SEM images showed the presence of TiNT agglomerates along the PbO₂ surface, which led to higher anodic current in the cyclic voltammetries carried out with Methyl Orange solutions. It is suggested that TiNT favour the adsorption of the organic molecules, facilitating the contact with the OH radicals and thus accelerating the electro-oxidation process. This was confirmed by the faster TOC removal compared to that yielded by the RVC/PbO₂, being 45% instead of 24% at 120 min.     

Poly(methylene blue) doped silica nanocomposites with crosslinked cage structure: Electropolymerization, characterization and catalytic activity for reduction of dissolved oxygen

The poly(methylene blue) (PMB) modified glassy carbon electrode (GCE) exhibiting different electrochemical behavior was prepared via two methods, respectively. The PMB polymer, derived from the two-step electropolymerization, suffered structure conversion between Poly(leuco-MB) and Poly(MB) during cyclic voltammetric measurement and exhibited electrocatalytic activity for reduction of dissolved oxygen (DO). The monodispersed hollow methylene blue doped SiO₂ nanoparticles were synthesized in the W/O microemulsion. A new material, PMB doped SiO₂ nanocomposites, presenting monolayer sheets with crosslinked cage structure, were electrochemically polymerized on GCE surface. Compared with PMB film, the nanocomposite material provided a significantly improved sensitivity for reduction of DO and an excellent ability to resist interference from macromolecule contaminants. The detection of DO was performed using the nanocomposite material modified electrode. The calibration curve was linear over a DO concentration range of 0.112–5.78 mg L⁻¹ with a correlation coefficient of 0.998 and a detection limit (3σ) of 0.037 mg L⁻¹.     

Electrochemical studies of kerosene-pyrolysedcarbon films

Polycrystalline thin films of conducting carbon are deposited on alumina substrates by the pyrolysis of kerosene vapour at 1000C for 2h in argon atmosphere. Preliminary structural analysis is done by XRD, laser-Raman, FTIR and SEM studies. The electrochemical behaviour of as-grown conducting carbon films was investigated in various electrolytes at different pH and the performance was compared with that of platinum and glassy electrodes. The electrochemical window of the kerosene carbon electrode in 100mm H2SO4 was found to be 2.91V which is greater than that of glassy carbon (2.79V) and platinum (2.02V). Cyclic voltammetry reveals that Pt electrode has almost an equal tendency towards hydrogen and oxygen evolution, whereas glassy carbon favours hydrogen evolution and kerosene carbon favours oxygen evolution. It is suggested that the kerosene carbon electrode can be used as an oxygen electrode more efficiently. Unlike diamond films or glassy electrodes, kerosene carbon thin films are of low cost and good stability; they are also easy to grow on various ceramic substrates of any size. Moreover, these electrodes are very economical and promising for application in chlor-alkali industry.     

Microwave activation of electrochemical processes: High temperature phenol and triclosan electro-oxidation at carbon and diamond electrodes

The electrochemical oxidation of phenolic compounds in aqueous media is known to be affected by the formation of electro-polymerized organic layers which lead to partial or complete electrode blocking. In this study the effect of high intensity microwave radiation applied locally at the electrode surface is investigated for the oxidation of phenol and triclosan in alkaline solution at a 500 μm diameter glassy carbon or at a 500 μm × 500 μm boron-doped diamond electrode. The temperature at the electrode surface and mass transport enhancement are determined by calibration with the Fe(CN)₆^3−/4− redox system in aqueous 0.3 M NaOH and 0.2 NaCl (pH 12) solution. The calibration shows that strong thermal and mass transport effects occur at both glassy carbon and boron-doped diamond electrodes. The average electrode temperature reaches up to 390 K and mass transport enhancements of more than 20-fold are possible. For the phenol electro-oxidation at glassy carbon electrodes and at a concentration below 2 mM a multi-electron oxidation (ca. 4 electrons) occurs in the presence of microwave radiation. For the electro-oxidation of the more hydrophobic triclosan only the one-electron oxidation occurs. Although currents are enhanced in presence of microwave radiation, rapid blocking of the electrode surface in particular at high phenol concentrations still occurs.     

Correlation of cyclic voltammetry behaviour and photooxidative properties of indoprofen and its photoproducts

The electrochemical behaviour of indoprofen (INP) and its photoproducts was investigated in acetonitrile containing tetrabutylammonium hexafluorophosphate at a Pt or Cv ultramicro-electrodes. These photosensitizers (PS) undergo irreversible oxidation yielding at first a radical cation PS⁺ and more or less reversible reductions through monoelectronic exchange involving a radical anion PS⁻. By varying the potential scan speed, the stabilities of the radical anions were evaluated. The determination of the redox potential and Rehm-Weller's equation shows the high exergonicity of the oxidative photodamagings whatever is the compound PS. The difference in DNA photosensitizing properties could rather be related to a kinetic control and then to the relative stabilities of the radical anions PS⁻. Cyclic voltammetry was found powerful in order to get a new insight in the photosensitizing properties of drugs.     

Electron transfer to sulfides:: Heterogeneous kinetics, CS bond cleavage, and self-protonation

The problem of characterizing the steps associated with the dissociative reduction of sulfides has been addressed. The electrochemical reduction of diphenylmethyl para-methoxyphenyl sulfide in N,N-dimethylformamide, on both glassy carbon and mercury electrodes, was chosen as a test system. The electrode process involves the slow heterogeneous outer-sphere electron transfer to the sulfide, the fast cleavage of the CS bond, the reduction of the ensuing carbon radical, and the self-protonation triggered by the generation of the strong base Ph₂CH⁻. The latter reaction is rather slow, in agreement with the large intrinsic barriers characterizing proton transfers between CH-acids and carbon bases. The dissociative reduction was studied in the presence of an exogenous acid. The results, obtained by convolution analysis, point to a stepwise DET mechanism in which the ET step is accompanied by rather large reorganization energy. Similar results were obtained on both electrode materials. Analysis of the heterogeneous electron transfer and associated CS bond cleavage indicate that the reduction of this and other sulfides lies between the stepwise dissociative electron transfers leading to the formation of stiff π^* radical anions and those going through the intermediacy of loose σ^* radical anions.     

Anodic oxidation of chlorophenols in micelles and microemulsions on glassy carbon electrode: the medium effect on electroanalysis and electrochemical detoxification

The voltammetric behavior of 2, 4-dichlorophenol (DCP), 2, 4, 6-trichlorophenol (TCP) and pentachlorophenol (PCP) in aqueous sodium hydroxide (NaOH), aqueous NaOH–sodium dodecylsulphate (SDS) micellar solution and SDS/n-hexane/n-butanol/water microemulsion on glassy carbon electrode (GC) is reported. In aqueous alkaline medium, the electrode fouling is significant. Among the three media, the electrode fouling is the minimum in aqueous microemulsion. The fouling effect also depends on the nature of the phenolic compound. DCP exhibits the maximum fouling effect, and PCP exhibits the minimum fouling effect. During oxidation of the TCP in the microemulsion, quinone–hydroquinone-like redox couples were formed on the electrode surface. Reproducible voltammetric responses without electrode fouling could be obtained for all the three phenolic compounds up to 20 mM concentrations in microemulsion. In the galvanostatic oxidation in NaOH media, DCP and TCP led to formation of polymeric films on the glassy carbon surface. The Average molecular weight of the polymer obtained is in the range of 7,500–9,500. Even 2.5% by weight of chlorophenols could be oxidized under galvanostatic conditions in microemulsions without significant fouling.     

Mechanism of heterogeneous catalytic ozonation of nitrobenzene in aqueous solution with modified ceramic honeycomb

The degradation efficiencies of nitrobenzene in aqueous solution were investigated by semi-continuous experiments in the processes of ozone alone, ozone/ceramic honeycomb (CH) and ozone/modified ceramic honeycomb (MCH). MCH with 1.0% Mn and 0.5% Cu had more pronounced catalytic ability than CH to accelerate the degradation of nitrobenzene, to increase the utilization efficiency of ozone, to improve the concentrations of hydrogen peroxide (H₂O₂) formation and hydroxyl radical (OH) initiation, and to enhance the removal efficiency of TOC. The modification process of CH with the metals enhanced the density of surface hydroxyl groups, which determines the initiation of OH from ozone decomposition and the generation of intermediate species on heterogeneous catalytic surface, yielding the acceleration of the degradation of nitrobenzene in aqueous solution. Possible reaction mechanism of ozone with heterogeneous catalytic surface in aqueous solution was proposed, and the formation mechanism of H₂O₂ and OH was also discussed according to the combined reactions in heterogeneous and homogeneous catalytic systems.     

Solar photoassisted anodic oxidation of carboxylic acids in presence of Fe using a boron-doped diamond electrode

This paper reports a comparative study on the anodic oxidation of 2.5 l of 50 mg l⁻¹ TOC of formic, oxalic, acetic, pyruvic or maleic acid in 0.1 M Na₂SO₄ solutions of pH 3.0 with and without 1.0 mM Fe³⁺ as catalyst in the dark or under solar irradiation. Experiments have been performed with a batch recirculation flow plant containing a one-compartment filter-press electrolytic reactor equipped with a 20 cm² boron-doped diamond (BDD) anode and a 20 cm² stainless steel cathode, and coupled to a solar photoreactor. This system gradually accumulates H₂O₂ from dimerization of hydroxyl radical (OH) formed at the anode surface from water oxidation. Carboxylic acids in direct anodic oxidation are mainly oxidized by direct charge transfer and/or OH produced on BDD, while their Fe(III) complexes formed in presence of Fe³⁺ can also react with OH produced from Fenton reaction between regenerated Fe²⁺ with electrosynthesized H₂O₂ and/or photo-Fenton reaction. Fast photolysis of Fe(III)-oxalate and Fe(III)-pyruvate complexes under the action of sunlight also takes place. Chemical and photochemical trials of the same solutions have been made to better clarify the role of the different catalysts. Solar photoassisted anodic oxidation in presence of Fe³⁺ strongly accelerates the removal of all carboxylic acids in comparison with direct anodic oxidation, except for acetic acid that is removed at similar rate in both cases. This novel electrochemical advanced oxidation process allows more rapid mineralization of formic, oxalic and maleic acids, without any significant effect on the conversion of acetic acid into CO₂. The synergistic action of Fe³⁺ and sunlight in anodic oxidation can then be useful for wastewater remediation when oxalic and formic acids are formed as ultimate carboxylic acids of organic pollutants, but its performance is expected to strongly decay in the case of generation of persistent acetic acid during the degradation process.     

Hydroxyl radical-related electrogenerated chemiluminescence reaction for a ruthenium tris(2,2′)bipyridyl/co-reactants system at boron-doped diamond electrodes

An electrogenerated chemiluminescence (ECL) reaction of the Ru(bpy)₃²⁺ (2,2′-bipyridyl, bpy)/co-reactant system in the extremely high-potential region (over 2.6 V versus Ag/AgCl) was probed using a boron-doped diamond (BDD) electrode. At the BDD electrode, three ECL waves (1.25, 2.30 and 3.72 V) were observed in cyclic voltammograms for 20 mM ascorbic acid (AA). For the ECL peaks observed at 1.25 V corresponding to the oxidation potential for Ru(bpy)₃²⁺ (1.15 V), the light intensities and current densities were found to depend on the square root of the AA concentration. This suggests that AA oxidation, followed by the formation of the reducing radical that is necessary for generating the excited state of Ru(bpy)₃^2+* occurred through homogeneous electron-transfer between Ru(bpy)₃³⁺ and the AA species. However, for the ECL peaks at 2.30 V, the current densities and light intensities linearly increased with increasing AA concentration, suggesting that the reducing radical was formed through the direct oxidation at the electrode surface. The ECL reaction at 3.72 V was observed only at the BDD electrode and not at other electrodes. The onset potentials for the light intensity were approximately 2.6 V, independently of the type of the co-reactants (e.g. 2-propanol and AA). The peak potentials exhibited linear relation with the co-reactant concentration. In the analysis of the ECL intensity for various co-reactants (alcohols) that show different reactivity for the hydrogen abstraction reaction, the order of the light intensities at the peaks for alcohols was found to be consistent with that for the rate constants of the hydrogen abstraction reaction. These results indicate that the co-reactant radical was formed through the hydrogen abstraction reaction with the hydroxyl radical (HO) generated during the oxygen evolution reaction.     

玻碳电极上碘仿电解合成的机理

本文采用循环伏安法研究了在Na2CO3溶液介质中KI在金电极和玻碳电极上的电化学行为.在0.2V～1.2V电位范围内玻碳电极上仅发生I-被氧化为I2的反应,而在金电极上除了I-被氧化为I2外,还发生生成IO3-的氧化反应.同时通过不同电位扫描速度下的循环伏安行为分析发现电极过程为传质控制步骤.     

Platinum catalysed decomposition of hydrogen peroxide in aqueous-phase pulsed corona electrical discharge

Electrical discharges in water produced by a pulsed high voltage power supply generate chemically active species (OH, H₂, O₂, H₂O₂, HO₂ and O) that are capable of degrading various hazardous chemicals. Previous experimental studies showed that platinum high voltage electrodes in a pulsed corona electrical discharge lead to significantly higher pollutant removal in comparison to that with other electrode materials. In the present work it was observed that when nickel–chromium was used as a high voltage electrode, the pulsed corona electrical discharge in water produces hydrogen peroxide at a constant rate regardless of the initial pH of the solution. Replacement of the nickel–chromium electrode with a platinum high voltage electrode leads to the decomposition of hydrogen peroxide where the rate of decomposition increases with increasing pH. An Eley-Rideal mechanism describing heterogeneous catalytic hydrogen peroxide decomposition is proposed. It is assumed that the decomposition occurs on the surface of the platinum particles ejected from the platinum high voltage electrode. Combination of the experimental measurements and a mathematical model describing the platinum catalysed hydrogen decomposition suggests that the pH dependent hydrogen peroxide decomposition is caused by the adsorption of molecular hydrogen produced by the discharge and hydroxyl ions on the platinum surface. The influence of gases bubbled into the reactor (argon, oxygen and hydrogen) on the hydrogen peroxide decomposition was also tested by both experiments and the model. Finally, the model was utilized to predict molecular hydrogen and oxygen concentrations at three pH values when either nickel–chromium or platinum high voltage electrodes are used.     

The underlying electrode causes the reported ‘electro-catalysis’ observed at C60-modified glassy carbon electrodes in the case of N-(4-hydroxyphenyl)ethanamide and salbutamol

The reported ‘electro-catalysis’ of C₆₀-film-modified electrodes for the electrochemical oxidation of N-(4-hydroxyphenyl)ethanamide and salbutamol has been explored at boron-doped diamond and glassy carbon electrodes. Using both C₆₀-film-modified boron-doped diamond and glassy carbon as underlying electrode substrates no electro-catalytic response is observed using the target analytes but rather the C₆₀ serves to block the electrode surface.A common experimental protocol used by researchers in this field is to electrochemically pre-treat the C₆₀-film-modified electrode. The response of employing this electrochemical pre-treatment at both bare glassy carbon and boron-doped diamond electrodes using the target analytes reveals that no effect on the electrochemical responses obtained at the boron-doped diamond electrode whereas a slight but significant effect occurs on glassy carbon which is attributed to the likely introduction of surface oxygenated species.Consequently the previously reported ‘electro-catalysis’ using C₆₀-film-modified electrode is not due to C₆₀ itself being catalytic, but rather that substrate activation through electrode pre-treatment is responsible for the observed ‘electro-catalysis’ likely through the introduction of surface oxygenated species.This work clearly shows that substrate activation is an important parameter which researchers studying C₆₀-film-modified electrodes, especially in electro-analysis needs to be considered.     

Direct hydro-alcohol thermal synthesis of special core–shell structured Fe-doped titania microspheres with extended visible light response and enhanced photoactivity

The influence of ultrasound at 24 kHz on the heterogeneous aqueous oxidation of phenol over RuI₃ with hydrogen peroxide (H₂O₂) was studied isothermally at 298 K. Effect of ultrasound irradiation on catalytic properties and performance of RuI₃ has been studied in details by means of scanning electron microscopy (SEM), X-ray powder diffraction (XRD), dispersion analyzer and a surface analyzer. Turn over frequency of the catalyst was also calculated. In this work, experimental design methodology was applied to optimize the degradation of phenol in aqueous solution, while minimizing an excessive consumption of chemical reagents. The independent variables considered were the catalyst load and oxidant concentration. The multivariate experimental design allowed the development of empiric non-linear quadratic models for total organic carbon (TOC) removal after 120 and 240 min of the reaction, and the time needed for total hydrogen peroxide consumption, which were adequate to predict responses in all of the range of experimental conditions used. Ruthenium leaching was not detected from samples studied at different stages of the reaction, indicating stability of the chosen catalyst. A reaction scheme involving radical species (OH, HO₂) was proposed to explain phenol conversion. Ultrasound-assisted catalytic oxidation demonstrated nearly two-fold increase in phenol conversion (up to 70%), contrary to 31% obtained during silent process. High catalytic activity of RuI₃ associated with isothermal reaction conditions at circum neutral pH was capable to extend the applicability of such catalyst in ultrasound-assisted oxidation processes.     

Anodic electrodeposition of cobalt oxides from an alkaline bath containing Co-gluconate complexes on glassy carbon. An electroanalytical investigation

In this study an electrodeposition procedure of cobalt oxides operating under anodic condition and directly from 0.5 M NaOH solutions containing 12 mM gluconate and 12 mM CoCl₂ was defined for the modification of glassy carbon surface electrode. Different experimental approaches based on cyclic voltammetry, steady-state potentiostatic technique, chronoamperometry and scanning electron microscopy were used to characterize the deposited cobalt oxide films and to evaluate the kinetics and mechanism of electrodeposition. Some aliphatic aldehydes were tested as compound model in order to evaluate the electroanalytical properties of the electrodeposited cobalt film as active redox material for amperometric applications in strong alkaline aqueous solutions. Interesting results in terms of surface electrode modification “in situ” of glassy carbon substrate with cobalt oxides were obtained and critically discussed.     

A novel alkaline air electrode based on a combined use of cobalt hexadecafluoro-phthalocyanine and manganese oxide

Electrocatalytic reduction of O₂ with dual catalysts of cobalt 1, 2, 3, 4, 8, 9, 10, 11, 15, 16, 17, 18, 22, 23, 24, 25-hexadecafluoro-29 H, 31H-phthalocyanine (CoPcF₁₆) and MnOOH was studied in alkaline media with cyclic and rotating ring-disk electrode (RRDE) voltammetry. Cyclic voltammetric results show that CoPcF₁₆ possesses a good catalytic activity for redox-catalyzing an apparent two-electron reduction of O₂ with superoxide (O₂⁻) as an intermediate. The combined use of CoPcF₁₆ with MnOOH which shows a bifunctional catalytic activity toward the sequential disproportionations of the reduction intermediate and product, i.e. O₂⁻ and peroxide (HO₂⁻), eventually enables an apparent four-electron reduction of O₂ to be achieved at a positively-shifted potential in alkaline media. The possibility of utilizing the dual catalysts for the development of practical alkaline air electrodes was further explored by confining the catalysts in active carbon (AC) and carbon black (CB) matrices that are generally used as the substrate for constructing air electrodes. The RRDE voltammetric results suggest that an apparent four-electron reduction of O₂ reduction can be obtained at the as-prepared carbon-based air electrode at a potential close to that at the Pt-based air electrode, and that the as-prepared electrode shows a high tolerance against methanol and glucose crossover.     

Drinking water disinfection by hemin-modified graphite felt and electrogenerated reactive oxygen species

The electrochemical inactivation of microorganisms by a hemin/graphite felt (GF) composite electrode was investigated, and Escherichia coli was treated as the testing species. The composite electrode was constructed by chemically bonding hemin molecules onto an amino-mineralized GF (AGF) surface. Then, the electrode was characterized systematically by electrochemical methods, and the kinetic parameters of the modified electrode were investigated. The hemin molecules on the surface of the composite electrode have high activity for the reduction of O₂. When the composite electrode was applied with negative potentials, the dissolved oxygen was electrochemically reduced to reactive oxygen species (ROS, such as H₂O₂ and OH) at the cathode surface. The ROS can cause biological damage and can eventually result in the death of bacteria. A sterilizing rate up to 99.9% could be obtained after 60 min of inactivation. Thus, this composite electrode could be applied to disinfect drinking water efficiently at a low potential (−0.6 V vs. SCE) without any addition of chloride.