Effect of concentration and temperature on electrochemical oscillations during sulfide oxidation on Ti/Ta2O5-IrO2 electrodes

The impact of current density, concentration, and temperature on the potential oscillations observed during the anodic oxidation of sulfide on Ti/Ta₂O₅-IrO₂ oxide electrodes is investigated. Electrochemical methods including: cyclic voltammetry, linear voltammetry, linear galvanic voltammetry, galvanostatic technique and electrochemical impedance spectroscopy are used in this study. The observed potential oscillations are caused by the periodic formation/removal of sulfur from the electrode surface. Increasing current density has the effect of increasing the frequency of oscillations as well as increasing the onset potential. Both increasing concentration and temperature gave rise to significant increases in current density prior to the onset of potential oscillations. The activation energy for electrochemical oxidation of sulfide was estimated from the temperature studies. Lifetime experiments were also conducted and demonstrated that potential oscillations have a detrimental impact on the electrode lifetime.     

Electrooxidation and inhibition of the antibacterial activity of oxytetracycline hydrochloride using a RuO<Subscript>2</Subscript> electrode

This work reports on the electrochemical oxidation of oxytetracycline hydrochloride (OTCH) [(4S,4aS,5aS,6S,12aS)-4-dimethylamino-1,4,4a,5, 5a,6,11,12a-octahydro-3,6,10,12,12a-hexahydroxy-6-methyl-1,11-dioxonaphthacene-2-carboxamide] on a RuO₂ electrode (DSA^®) by cyclic voltammetry and electrolysis. The electrocatalytic efficiency of the electrode material was investigated as a function of different aqueous buffer solutions with pH values of 2.10 and 5.45 as supporting electrolytes. Spectrophotometric studies have shown that OTCH is stable in such solutions. The electrochemical degradation of OTCH is pseudo-first order at both pH values investigated with rate constants, k, of 9.9 × 10^?5 s^?1 (pH 2.10) and 1.9 × 10^?4 s^?1 (pH 5.45) at 21 ± 1 °C. Microbiological studies with Staphylococcus aureus ATCC 29213 have shown that OTCH lost antibacterial activity after 120 min of electrolysis at 50 mA cm^?2.     

Electrooxidation of glyphosate herbicide at different DSA compositions: pH, concentration and supporting electrolyte effect

This paper has investigated the electrochemical oxidation of glyphosate herbicide (GH) on RuO₂ and IrO₂ dimensionally stable anode (DSA^®) electrodes. Electrolysis was achieved under galvanostatic control as a function of pH, GH concentration, supporting electrolyte, and current density. The influence of the oxide composition on GH degradation seems to be significant in the absence of chloride; Ti/Ir_0.30Sn_0.70O₂ is the best electrode material to oxidize GH. GH oxidation is favored at low pH values. The use of chloride medium increases the oxidizing power and the influence of the oxide composition is meaningless. At 30 mA cm⁻² and 4 h of electrolysis, complete GH removal from the electrolyzed solution has been obtained. In chloride medium, application of 50 mA cm⁻² leads to virtually total mineralization (release of phosphate ions = 91%) for all the evaluated oxide materials.     

Investigation of formic acid oxidation on Ti/IrO2 electrodes

A model has been proposed according to which the voltammetric charge involved in the Ti/IrO₂ electrodes is due to two contributions: a faradaic contribution due to surface redox activities at the IrO₂ coating and a non-faradaic contribution due to the charging of electrical double layer (). The later has been proposed as a tool for the estimation of the relative surface area of the Ti/IrO₂ electrodes.Differential electrochemical mass spectrometry (DEMS) measurements using H₂¹⁸O has demonstrated that we are dealing with an active electrode in which the surface redox couple IrO₃/IrO₂ acts as mediator in the oxidation of formic acid (FA).From the voltammetric measurements using different IrO₂ loading and FA concentrations, the kinetic parameters of FA oxidation via the surface redox couple IrO₃/IrO₂ have been determined.Finally a model has been proposed considering that FA oxidation at Ti/IrO₂ anodes is controlled by mass transfer. The good agreement between the experimental results and the model indicates that the surface reaction between FA and the electrogenerated IrO₃ is a fast reaction.     

Electrocatalytic oxidation of acetaldehyde on Pt alloy electrodes

Reaction intermediates occurring during the oxidation of acetaldehyde were investigated by in situ infrared reflectance spectroscopy (SPAIRS and SNIFTIRS techniques). These measurements, showing that acetaldehyde was transformed into CO and CO₂ successively, allowed us to choose a suitable potential program to oxidize electrocatalytically the reactant on binary and ternary platinum alloy electrodes with two compositions (Pt/Os and Pt/Ru/Os). IR results were useful to set a potential pulse program which allowed to adsorb dissociatively the organic compound. The analysis of the electrolysis products was performed by high performance liquid chromatography (HPLC). Acetic acid, formic acid and carbon dioxide were determined as the main oxidation products of acetaldehyde.     

Preparation of Ir0.3Sn(0.7-x)Ti x O2 Electrodes by the Polymeric Precursor Method: Characterization and Lifetime Study

Thin film electrodes of nominal composition Ir_0.3Sn_(0.7-x)Ti _x O₂ (0 ≤ x ≤ 0.7) were prepared by decomposition of polymeric precursors. The solutions used to prepare the electrodes were obtained by mixing of the precursor salts with a mixture of ethylene glicol and citric acid. The films were burned at 400 °C and characterized by X-ray diffraction, scanning electronic microscopy, energy dispersive X-ray spectroscopy and cyclic voltammetry. The electrodes were submitted to high anodic current density in order to evaluate their lifetime in perchloric acid solution. Results show that the electrodes present compositions similar to that of the precursor solutions, suggesting that there is no loss of tin during the calcination step. The electrodes had large surface area and higher lifetime in comparison with electrodes of similar composition prepared by other methods. The possible mechanisms involved in deactivation of the electrodes are discussed.     

Electrochemical and morphological properties of Ti/Ru0.3Pb(0.7−x)TixO2-coated electrodes

In this work, a ternary coating with the nominal composition Ti/Ru_0.3Pb_(0.7−x)Ti_xO₂ (0≤x≤0.7) deposited on Ti has been prepared through thermal decomposition of ruthenium, titanium and lead inorganic salts dissolved in isopropanol. To find out coatings with reasonable service life for application in electrolysis devices, changes in the firing temperature, heating time and supporting electrolyte have been investigated. Surface morphology and microstructure have been investigated by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). SEM data show that the mud-crack structure is progressively lost with the substitution of titanium by lead oxides. EDS results suggest that lead segregates, forming islands with a high content of Pb. Changes in crystallinity have been obtained with an increase in the lead content. Electrochemical analyses have been carried out in acid medium (HClO₄ 1.0 mol dm⁻³ and H₂SO₄ 0.5 mol dm⁻³). Cyclic voltammetric data and quasi-steady-state polarization curves have been recorded and accelerated life tests have been performed with an anodic current of 400 mA cm⁻². High coating stability has been obtained with the electrode fired at 550 °C. Replacing Ti with Pb extends the service life and improves the catalytic activity for oxygen evolution reaction (OER).     

Preparation of micro-dot electrodes of LiCoO2 and Li4Ti5O12 for lithium micro-batteries

Fabrications of micro-dot electrodes of LiCoO₂ and Li₄Ti₅O₁₂ on Au substrates were demonstrated using a sol-gel process combined with a micro-injection technology. A typical size of prepared dots was about 100 μm in diameter, and the dot population on the substrate was 2400 dots cm⁻². The prepared LiCoO₂ and Li₄Ti₅O₁₂ micro-dot electrodes were characterized with scanning electron microscopy, X-ray diffraction, micro-Raman spectroscopy, and cyclic voltammetry. The prepared LiCoO₂ and Li₄Ti₅O₁₂ micro-dot electrodes were evaluated in an organic electrolyte as cathode and anode for lithium micro-battery, respectively. The LiCoO₂ micro-dot electrode exhibited reversible electrochemical behavior in a potential range from 3.8 to 4.2 V versus Li/Li⁺, and the Li₄Ti₅O₁₂ micro-dot electrode showed sharp redox peaks at 1.5 V.     

A comparative study of commercial and laboratory-made Ti/Ru0.3Ti0.7O2 DSA electrodes: “In situ” and “ex situ” surface characterisation and organic oxidation activity

This paper presents the study of two dimensionally stable anodes (DSA^®) of nominal composition Ti/Ru_0.3Ti_0.7O₂, one obtained commercially and the other prepared in the laboratory. The materials were studied by ex situ (scanning electron microscopy (SEM)) and by in situ techniques (cyclic voltammetry, determination of the morphology factor (φ_morph) and electrochemical impedance spectroscopy (EIS)). The results obtained indicate that both electrodes present similar morphology and voltammetric profiles, with the main difference between the two materials studied being the internal electrode area, with the commercial electrode being demonstrated to possess the greater. The EIS study demonstrates that the differences in the equivalent circuit fitting parameters can be related to the different surface characteristics of the electrodes. However, the abnormal dependence of the solution ohmic resistance on the potential demonstrates that the model should be refined to be adequately applied to commercial electrodes. A study of the activity for organic oxidation was also performed, with the aim of verifying the effect of chain length on the rate of oxidation of different aldehydes (formaldehyde, acetaldehyde, propionaldehyde and n-butyraldehyde). It can be observed that the rate of carboxylic formation can be related to the working electrode potential during electrolysis, with higher potentials (commercial electrode) seeming to favour the more rapid formation of the carboxylic acid.     

Amorphous Ru1−yCryO2 loaded on TiO2 nanotubes for electrochemical capacitors

Amorphous Ru_1−yCr_yO₂/TiO₂ nanotube composites were synthesized by loading different amount of Ru_1−yCr_yO₂ on TiO₂ nanotubes via a reduction reaction of K₂Cr₂O₇ with RuCl₃·nH₂O at pH 8, followed by drying in air at 150 °C. Cyclic voltammetry and galvanostatic charge/discharge tests were applied to investigate the performance of the Ru_1−yCr_yO₂/TiO₂ nanotube composite electrodes. For comparison, the performance of amorphous Ru_1−yCr_yO₂ was also studied. The results demonstrated that the three dimensional nanotube network of TiO₂ offered a solid support structure for active materials Ru_1−yCr_yO₂, allowed the active material to be readily available for electrochemical reactions, and increased the utilization of active materials. A maximum specific capacitance 1272.5 F/g was obtained with the proper amount of Ru_1−yCr_yO₂ loaded on the TiO₂ nanotubes.     

Estimation of the effectiveness factor of an outer-sphere redox couple (Fe3+/Fe2+) using rotating disk Ti/IrO2 electrodes of different loading

The effectiveness factor; E _f , defined as the fraction of the surface that participates effectively in a given reaction, is an important parameter when operating three-dimensional (3D) electrodes. The rotating disk electrode (RDE) technique with the Fe³⁺/Fe²⁺ redox couple as a probe reaction has been used for the evaluation of the effectiveness factor of 3D Ti/IrO₂ electrodes with different IrO₂ loading. For this purpose, steady-state polarization measurements using Ti/IrO₂ rotating disk electrodes in 0.5 M Fe³⁺/Fe²⁺ in 1 M HCl were carried out under well-defined hydrodynamic conditions. The low-field approximation relation has been used for the estimation of the exchange current densities j ₀, of the Fe³⁺/Fe²⁺ redox couple. It was found for this redox couple that the effectiveness factor is very low (<2%) and essentially the 2D electrode surface area works effectively in the steady-state polarization measurements.     

Parallel oxygen and chlorine evolution on Ru1−xNixO2−y nanostructured electrodes

Nanocrystalline materials with chemical composition corresponding to formula Ru_1−xNi_xO_2−y (0.02 < x < 0.30) were prepared by sol-gel approach. Substitution of Ru by Ni has a minor effect on the structural characteristics extractable from X-ray diffraction patterns. The electrocatalytic behavior of Ru_1−xNi_xO_2−y with respect to parallel oxygen (oxygen evolution reaction, OER) and chlorine (chlorine evolution reaction, CER) evolution in acidic media was studied by voltammetry combined with differential electrochemical mass spectrometry (DEMS). The DEMS data indicate a significant decrease of the over-voltage for chlorine evolution with respect to that of pure RuO₂. The oxygen evolution is slightly hindered. The increasing Ni content affects the electrode material activity and selectivity. The overall material's activity increases with increasing Ni content. The activity of the Ru-Ni-O oxides towards Cl₂ evolution shows a distinguished maximum for material containing 10% of Ni. Further increase of Ni content results in suppression of Cl₂ evolution in favor of O₂ evolution. A model reflecting the cation-cation interactions resulting from Ni-doping is proposed to explain the observed trends in electrocatalytic behavior.     

Electro-oxidation of coal on NiO and/or Co3O4 modified TiO2/Pt electrodes

A TiO₂/Pt based electrode exhibited better activity for the oxidation of coal in a basic system compared to Ti/Pt, TiO₂–Cu/Pt and pure metal electrodes. The surface morphologies and composition of the electrodes were studied by SEM and XRD, respectively. Linear sweep voltammetry was employed to investigate the catalytic effects of electrodes, and the product of coal oxidization was determined by a gas collection test. The TiO₂/Pt electrodes that were modified with NiO and/or Co₃O₄ exhibited higher average currents and a lower decrease in mass during electrolysis compared to the other electrodes; this finding indicated that NiO and Co₃O₄ play important roles as catalysts.     

Effect of calcination temperature on electrocatalytic activities of Ti/IrO2 electrodes in methanol aqueous solutions

The electrochemical activity of thermo-decomposed Ti/IrO₂ electrodes in aqueous solution containing methanol compound has been studied, emphasizing on the influence of calcination temperature. Scanning electron microscopy (SEM) images showed that the typical cracked morphology of oxide coatings disappears gradually as the preparation temperature increases, leading to the decrease in the amount of electrochemically active sites as measured by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in organics-free aqueous solution. With the exception of samples prepared at high temperatures (e.g. 600 °C), same change tendency of electro-activity with temperature was also found in methanol aqueous solutions, in which activity was observed to decrease as compared with that in blank solution. Three possible explanations for this phenomenon (i.e. active dissolution of oxide coatings, organics adsorption and dimerization/polymerization on electrode surface, respectively) were discussed, where the former two were believed to be more reasonable considering the CH₃OH small molecular chosen in this system. However, none of these three mechanisms could explain the abnormal activation behavior observed at electrodes prepared at 600 °C in CH₃OH solution. XRD pattern showed the fact that when sintering temperature went up to 600 °C IrO₂ would decompose into metallic iridium component. The existence of metallic iridium might facilitate the organics oxidation as stated in previous literatures, which leads to the exceptional activation of oxide surface by methanol component. A simple reaction mechanism for electrodes in methanol aqueous solutions was proposed and used to interpret the negative shift in startness potential of the oxygen evolution reaction (OER). Organics oxidation seems to facilitate the OER and vice versa. The latter statement has been reported by other workers.     

Stable Ti/RuO2-Sb2O5-SnO2 electrodes for O2 evolution

RuO₂-based electrodes are generally known to be unstable for O₂ evolution. In this paper, a stable type of RuO₂-based electrode, Ti/RuO₂-Sb₂O₅-SnO₂, is demonstrated for O₂ evolution. In the ternary oxide coating, RuO₂ serves as the catalyst, SnO₂ as the dispersing agent, and Sb₂O₅ as the dopant. The accelerated life test showed that the Ti/RuO₂-Sb₂O₅-SnO₂ electrode containing 12.2 molar percent of RuO₂ nominally in the coating had a service life of 307 h in 3 M H₂SO₄ solution under a current density of 0.5 A cm⁻² at 25 °C, which is more than 15 times longer than other types of RuO₂-based electrodes. Instrumental analysis indicated that RuO₂-Sb₂O₅-SnO₂ was a solid solution with a compact structure, which contributed to the stable nature of the electrode.     

A comparative study on IrO2-Ta2O5 coated titanium electrodes prepared with different methods

The electrodes of IrO₂-Ta₂O₅ coated titanium were prepared using conventionally thermal decomposition procedure and polymer sol-gel (Pechini) method, respectively. The microstructure and electrochemical properties of the electrodes were studied with scanning electron microscope (SEM), energy dispersive X-ray (EDX), atomic force microscope (AFM), potentiodynamic polarization, cyclic voltammetry, electrochemical impedance spectroscopy and accelerated life test. As compared with the electrode formed using the traditional method of thermal decomposition, the oxide electrode prepared by Pechini method presents morphology of higher nano-scale roughness and more uniform surface composition with little precipitates. It also has larger electrochemically active surface area, better electrocatalytic activity for oxygen evolution and higher stability.     

Effect of La-doping on the properties of CaCu3Ti4O12 dielectric ceramics

Nano-size Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ (χ = 0.00, 0.05, 0.10, 0.15 and 0.20) precursor powders were prepared via the sol–gel method and the citrate auto-ignition route and then processed into micro-crystal Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ ceramics under heat treatment. Characterization of the as-obtained ceramics with XRD and SEM showed an average grain sizes of ∼1–2 μm, indicating La³⁺ amount to have little impact on grain size. The room-temperature dielectric constant of the Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ ceramics sintered at 1000 °C was of the order of 10³–10⁴ despite the variation of χ values. Compared with CaCu₃Ti₄O₁₂, La³⁺-doped CaCu₃Ti₄O₁₂ showed a flatter dielectric constant curve related to frequency. It was found that the loss tangent of the Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ ceramics was less than 0.20 in ∼600–10⁵ Hz region, which rapidly decreased to a minimum value of 0.03 by La³⁺doping with χ = 0.05. Our measurement of the ceramics conductivities (σ) also indicated that the appropriate introduction of La³⁺ into CaCu₃Ti₄O₁₂ would distinctly result in its dielectric properties.     

Kinetic study of formic acid oxidation on Ti/IrO2 electrodes prepared using the spin coating deposition technique

In the first part of this paper, IrO₂ electrodes produced by thermal decomposition of H₂IrCl₆ precursor were manufactured using the spin coating deposition technique, where centrifugal forces spread the precursor solution with simultaneous evaporation of the solvent on the rotating Ti substrate. It was found using this technique, that it is possible to obtain thin and uniform IrO₂ coatings with controlled loadings. The influence of the concentration of iridium salt in the precursor solution (c₀) as well as the influence of the rotation speed at which the substrate spins (ω) on the IrO₂ loading have been studied using voltammetric charge measurements. From these results, a simple relation has been proposed for the estimation of the IrO₂ loading for a given c₀ and ω.In the second part of this paper and from measurements performed using different IrO₂ loadings and formic acid concentrations, the kinetic parameters of the oxidation of formic acid have been quantitatively determined using a model that involves the redox couple IrO₃/IrO₂ as mediator of this reaction. Furthermore, using the kinetic parameters obtained together with the Nernst equation and the I-V curves of the supporting electrolyte (1 M HClO₄), theoretical I-V curves could be constructed for different concentrations of formic acid and different IrO₂ loadings.     

LixNi0.7Co0.3O2 electrode material: Structural, physical and electrochemical investigations

The layered LiNi_0.7Co_0.3O₂ cathode material was synthesized by the combustion method using sucrose as fuel at 800 °C for 1 h, which leads to homogeneous size distribution with sub-micron particle size. The characterization of this material was realized using X-ray diffraction, scanning electron microscopy and completed by magnetic measurements. The Rietveld refinement shows the presence of 2.6% extra nickel in the interslab space. The presence of nickel ions in the lithium layers was confirmed by magnetization measurements. The 90° Ni-O-Ni ferromagnetic coupling is the main magnetic interactions. Lithium extraction from this phase occurs without major structural modifications. Cycling tests have shown a very good cycling stability at various current rates. Furthermore, this material delivers high reversible capacity of about 150 mAh/g in the 2.8-4.4 V range at the C/20.     

Direct formation of H2O2 from H2 and O2 and decomposition/hydrogenation of H2O2 in aqueous acidic reaction medium over halide-containing Pd/SiO2 catalytic system

Formation of H₂O₂ from H₂ and O₂ and decomposition/hydrogenation of H₂O₂ have been studied in aqueous acidic medium over Pd/SiO₂ catalyst in presence of different halide ions (viz. F⁻, Cl⁻ and Br⁻). The halide ions were introduced in the catalytic system via incorporating them in the catalyst or by adding into the reaction medium. The nature of the halide ions present in the catalytic system showed profound influence on the H₂O₂ formation selectivity in the H₂ to H₂O₂ oxidation over the catalyst. The H₂O₂ destruction via catalytic decomposition and by hydrogenation (in presence of hydrogen) was also found to be strongly dependent upon the nature of the halide ions present in the catalytic system. Among the different halides, Br⁻ was found to selectivity promote the conversion of H₂ to H₂O₂ by significantly reducing the H₂O₂ decomposition and hydrogenation over the catalyst. The other halides, on the other hand, showed a negative influence on the H₂O₂ formation by promoting the H₂ combustion to water and/or by increasing the rate of decomposition/hydrogenation of H₂O₂ over the catalyst. An optimum concentration of Br⁻ ions in the reaction medium or in the catalyst was found to be crucial for obtaining the higher H₂O₂ yield in the direct synthesis.