Electrochemical behaviour of phenylethanolamine at gold in aqueous solution

The electrooxidation of phenylethanolamine (2-amino-1-phenylethanol) at a gold electrode in alkaline electrolyte has been studied. Measurement of the differential capacitance of the electric double layer versus the electrode potential has shown that the adsorption of phenylethanolamine at the gold-solution interface plays a significant role in the oxidation mechanism. The effect of amine concentration, electrolyte pH and potential scan rate on the electrooxidation is analysed.     

Iodide mediated electrolysis of acidic coke/coal suspension

Hydrogen is among the emerging energy vectors that are being developed to replace nonrenewable hydrocarbon energy sources. The preferred method to produce hydrogen without generating greenhouse gases is the electrolysis of water using renewable energy. The reduction of energy during the water electrolysis process is a desirable goal regardless of the source of electric power. Similar to ferrous/ferric mediation, iodide can be used as a mediator in the electrolysis of an acidic suspension of coke or coal. The iodide ion is oxidized at a far lower anodic potential than the alternative oxygen evolution reaction. This reduces the cell electrolysis voltage and, consequently, reduces electricity use. The iodide consumed at the anode is continuously regenerated by chemical reaction with the coke/coal in suspension.     

Computer simulation of the effective double layer occurring on a catalyst surface under electro-chemical promotion conditions

In this work, the structural and energetic properties of two typical catalytic surfaces, Na/Pt(111) and O/Pt(111), are studied by means of quantum mechanical calculations and Monte Carlo Grand Canonical simulations. The simulations were performed with electrostatic potentials at different truncation schemes. In order to elucidate the modification of catalyst surfaces produced by the backspillover of ionic species onto Pt(111), the electrostatic field at the interface due to the electric double layer was also analyzed.     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.     

Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

Electrochemical perfluorination (ECPF) of n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl and n-decanoyl chlorides was carried out under identical experimental conditions in liquid HF. The product distribution among perfluorinated carboxylic acids, perfluoro ethers, perfluoroalkanes, isomerised and fragmented products containing less number of carbon atoms was identified using ¹⁹F NMR. The selectivity of C₆–C₁₀ perfluoro carboxylic acid varied between 29 and 36%. The alkali insoluble perfluoro cyclic ether and perfluoro alkane fractions increased with increasing chain length. The increase of perfluoroalkane fractions is mainly due to decarboxylation. Cyclic ether fractions also decreased slightly with increase in chain length. Among the cyclic ethers α substituted oxolanes were the predominant products. Six membered cyclic ethers were always found to contain β substitution. The possible pathways for these products are also indicated. An erratum to this article can be found at     

Streaming potential measurements on stainless steels surfaces: evidence of a gel-like layer at the steel/electrolyte interface

Electric charges at the surface of a passive stainless steel are generally considered as concentrated either in the passive film itself, or at the metal/passive film interface, or in the electrical double layer at the film solution interface. Rest potential time dependence after immersion of a passive surface in aqueous electrolytes suggests however that slow processes occur in the onset of the surface charge. Specific experiments, such as streaming potential measurements and electrochemical impedance spectroscopy in a thin electrolyte cell, were carried out for understanding better this phenomenon. An AISI 304 type austenitic stainless steel with polished or bright annealed surface finishes was immersed in NaCl aqueous solutions with various pH and chloride concentrations. The streaming potential time evolution shows two steps: a first rapid one (∼2 min) is attributed to the onset of the surface charge. The second step is much slower (approximately several hours) and possibly due to an interphase layer between the passive film and the solution. Following this idea, the whole kinetics is controlled by cation migration across the interphase when the pH is larger than the isoelectric pH (pH_iep), while chloride ions are incorporated in the interphase when pH < pH_iep. Impedance measurements allow determining both the kinetics of charge transport and the thin cell conductivity. When glass is used as reference material for the cell walls instead of stainless steel, the Nyquist plots show a high-frequency response. For stainless steel cell walls, a low-frequency response is observed, attributed to a slow charge reorganisation inside the interphase layer. The charge distribution at metal/electrolyte interface is discussed in terms of a gel-like layer which possibly takes place at the passive film/electrolyte interface.     

A disposable single-use electrochemical sensor for the detection of uric acid in human whole blood

We report here a non-enzymatic detecting electrode strip for fast monitoring of uric acid in human whole blood. A single-use amperometric uric acid sensor strip, incorporating a three-electrode configuration, has been fabricated on a polypropylene substrate using low cost screen-printing (thick-film) technology. Both the working and counter electrodes were prepared by screen-printing commercial carbon ink. The integration on the same support of pseudo-reference electrode was obtained by screen-printing a commercial silver ink and subsequent electrochemical pretreatment. Simply by placing a 20 μl human whole blood drop on the strip is enough for uric acid analysis by square-wave voltammetry. Real human whole blood samples were analyzed by this method and compared to the phosphotungstic acid clinical test procedure with satisfactory results.     

Electrochemical chlorination of azulene derivatives: Insight into the mechanism of anodic oxidative chlorination

The cyclic voltammetry behavior of a series of five 1-substituted azulenes has been investigated as well as the electrochemical chlorination of these compounds. In the case of azulene compounds containing electron withdrawing groups which have higher oxidation potentials than that of the chloride ion, the electrochemical chlorination led usually to 3-chloro derivatives. The electrochemical chlorination fails for azulenes with lower oxidation potentials. Additionally some polyhalogenated compounds were obtained by controlled potential electrolyses. The paper also discusses the reaction mechanism of the electrochemical halogenation of 1-substituted azulenes.     

Electrochemical noise analysis for estimation of corrosion rate of carbon steel in bicarbonate solution

We have investigated the electrochemical noise behavior of carbon steel in fully deaerated aqueous bicarbonate solutions, and discussed the optimum conditions of the noise analysis for estimating corrosion rate of the steel. Noise of the potential difference and of the short-circuit current between two identical steel coupons were successfully measured. The time-series noise patterns were transformed into frequency domain by fast Fourier transformation, and then their power spectrum densities (PSDs) at a frequency were determined to be compared with the corrosion rate. The PSDs of the potential and of the current varied with changing environmental factors of bicarbonate concentration, pH, and immersion time. The factors also controlled the corrosion rate of the steel. The PSDs were associated with the corrosion rate, and then it was found that the PSDs of the potential and of the current showed linear correlation with the corrosion rate in log-log scale. There was also linear relationship between the corrosion rate and a spectral noise resistance obtained from the PSDs of the potential and the current. The linearities of the three correlations were better at a lower analyzed frequency. Furthermore, the PSDs of the current and the noise resistance indicated more linear correlation with the corrosion rate than that of the potential. As the simplicity of the measurement system is additionally considered, it is concluded that the PSD of the current noise at an analyzed frequency of 3 mHz is the optimum conditions for estimating the corrosion rate from 10⁻² to 10⁰ A m⁻² in this study.     

Electrochemical properties of ultra-long,aligned, carbon nanotube array electrode in organic electrolyte

The electrochemical properties of an electrochemical double-layer capacitor electrode based on an ultra-long (500 μm), aligned, carbon nanotube array (ACNTA) in Et₄NPF₆/propylene carbonate electrolyte are examined. The specific capacitance of the ACNTA electrode in an organic electrolyte is 24.5 F g⁻¹, which is larger than that obtained in an aqueous electrolyte. The results of ac impedance measurements show that the ACNTA electrode gives a high power density and an excellent rate capability in an organic electrolyte. It is shown that the ACNTA electrode has a lower equivalent series resistance and a better rate capability than activated carbon electrode. This is due to the fact that ACNTA possesses a larger pore size and a more a regular pore structure. Both these features are conformed by scanning electron microscopic and nitrogen gas adsorption studies.