0000000000328372
AUTHOR
D. Benito
Electrochemical behaviour of Nafion®+cupromeronic phthalocyanine films
Abstract The surface of indium tin oxide (ITO) and graphite+polymer composite electrodes can be modified by Nafion ® films containing a little amount of dispersed electroactive substances, such as phthalocyanines. This procedure allows electroanalytical information on the electroactive deposited substance to be obtained. The preparative methods of these type of modified electrodes are discussed from voltammetric results in this work. The proposed equivalent circuit explains the voltammetric differences between these electrodes. The Nafion ® net acts as a permeable membrane to the hydrogen ions. Besides, the presence of methylviologen within the Nafion ® film makes the electron transport thr…
Study by EQCM on the voltammetric electrogeneration of poly(neutral red). The effect of the pH and the nature of cations and anions on the electrochemistry of the films
Generation of poly(neutral red) films has been studied by means of the simultaneous measurements of current–potential and mass–potential curves during cyclic voltammetry (CV) experiments. It has been proved that the presence of molecular oxygen in the solution increases the amount of polymer deposited on the electrode. Otherwise, using the mass/charge ratio it is possible to obtain quantitative information about the electrodeposition by different procedures. It is observed that this ratio decreases when the amount of polymer electrogenerated increases, except when the polymer is not reduced and oxidised after its electrogeneration. The study of poly(neutral red) by CV and quartz crystal mic…
Electrochemical impedance spectroscopy of conductor-insulator composite electrodes: properties in the blocking and diffusive regimes
Abstract The electrochemical response of graphite + high-density polyethylene composite electrodes as a function of the conductivity load was investigated. Percolation theory was used in order to explain the electrochemical behaviour of this type of composite electrode. In the blocking regime the electrochemical impedance of this electrode material behaved as R 0 + q · ( ω j) − η , where R 0 represents the uncompensated resistance of the cell. Its value depended on the graphite volume proportion ( ν ) with a power law R 0 ∞ ( ν — ν c ) − t with a critical exponent t = 3.2 ± 0.1 which is close to the mean field value, t = 3. With potassium chloride concentrations greater than 0.7 M, the unco…
Prussian blue films deposited on graphite+epoxy composite electrodes: electrochemical detection of the second percolation threshold
Abstract The electrochemical behavior of Prussian blue films galvanostatically electrodeposited on graphite+epoxy-resin composite electrodes was studied. The composite electrodes were prepared with different graphite proportions and their effect on electrochemical reduction of the Prussian blue was analyzed by means of the uncompensated resistance approximation and the electrical percolation theory. The results suggest that the electrode with 60% graphite reaches the second percolation threshold and its internal structure changes from a compact to a porous one. Mechanical tensile tests were performed in order to confirm the critical behavior of this material at the percolation thresholds. T…
Electrochemical behaviour of inorganic redox substances dispersed into Nafion® films
Abstract The voltammetric response of a Nafion ® film deposited on an indium tin oxide (ITO) electrode was studied. It was observed that the response is affected by the thickness of the Nafion ® layer. Also, the voltammograms show differences depending on the concentration and composition of the supporting electrolyte solution. The ITO–Nafion ® system can be stabilised by repetitive cyclic voltammetry, and then the inner hydrogen reduction is not detected by electrochemical impedance spectroscopy. Different substances were dispersed into the Nafion ® matrix in order to study their electrochemical response.
Electrochemical behaviour of poly(neutral red) on an ITO electrode
Abstract The formation of a radical cation, by electrochemical oxidation of the neutral red dye in acidic aqueous solution, is controlled by diffusion towards the electrode surface. This is the initiation step of the electrogeneration, potentiostatic or potentiodynamic, of poly(neutral red) films on an indium–tin oxide (ITO) electrode. The polymeric film is a redox semi-conductor, and shows a microporous membrane-like character. Its electrochemical behaviour depends on the generation process. The hydrogen ions play a double role: first as reactants at electrochemical and acid–base equilibrium, second as counterions of the electrons. The global process of the electron-hopping is limited by t…
An electrochemical impedance and ac-electrogravimetry study of PNR films in aqueous salt media
Electrochemical impedance spectra and ac-eletrogravimetry of poly(neutral red) films are studied in different aqueous media. The dependence of these experimental data on the nature of alkaline cation and monovalent anion present in the solution and on the pH is analysed. During the electrochemical processes, it is observed that all three species—the salt cation, the salt anion and the hydronium ion—participate to balance the electrical charge within the film. It is also possible to conclude that the participation of anions takes place faster than hydronium ions participation. Besides, the relative participation of these species is related to the pH of the solution. Keywords: Poly (neutral r…
Determination of the electroactive area of graphite+polyethylene composite electrodes. Uncompensated resistance effects and convolution analysis of chronoamperograms
In this work, it is shown how the convolution analysis of chronoamperograms permits the observation of the uncompensated resistance and the natural convection effects on the electrochemical response of potassium ferrocyanide. The uncompensated resistance causes the current intensity to follow the Cottrell equation only after a certain critical time. The convolution of chronoamperograms worked out at different integration times shows a maximum when this time is long enough. The classical diffusion equations cannot explain this phenomenon themselves. The development of this maximum associated with the natural convection is discussed. If both these factors, the ohmic drop and the natural conve…
Surface modification of graphite+polymer composite and ITO electrodes by Nafion®+cupromeronic phthalocyanine films
Abstract The surface of indium tin oxide (ITO) and graphite+polymer composite electrodes can be modified by Nafion ® films containing a little amount of dispersed electroactive substances, such as phthalocyanines. This procedure allows the recovery of electroanalytical information on the electroactive deposited substance. The preparation methods for these types of modified electrodes are discussed from the voltammetric results obtained in this work. The Nafion ® net acts as a permeable membrane to the hydrogen ions. Furthermore, the presence of methylviologen within the Nafion ® film makes the electron transport throughout this membrane easy.