Mária Ujvári

New EQCM, voltammetric and radiotracer evidences proving the role of Cu+ ions in the behavior of the Cu2+–Cu system

Abstract Combined EQCM and voltammetric studies in conjunction with radiotracer adsorption investigations were carried out in order to obtain direct information on the interfacial behavior of the Cu 2+ –Cu system under equilibrium and dynamic conditions with the aim of clarifying the role and participation of Cu + ions formed by the interaction of cupric ions and copper metal. The appearance and accumulation of Cu + ions in the solution phase is clearly demonstrated through radiotracer experiments using labeled Cl − ions. The formation of bulk CuCl phase is preceded by the formation of a CuCl surface layer. Data obtained from combined voltammetric and EQCM studies allow us to separate the potential regimes where the electrosorption, the formation of Cu + or Cu 2+ ions, and dissolution of CuCl are the predominant processes.

On the reduction of ClO4− ions in the course of metal dissolution in HClO4 solutions

The problem of the application of perchloric acid and/or perchlorate supporting electrolyte in electrochemical and corrosion studies is discussed. It is demonstrated that in contrast to the general view in the literature the reduction of perchlorate ions could be an important step in the overall process occurring in the course of spontaneous dissolution of some metals in acid perchlorate medium. It is shown that especially in the case of the dissolution of iron the reduction of ClO4− leading to the formation of Cl− plays a substantial role. Consequently, all interpretations concerning the dissolution of iron in the presence of ClO4− ions should be revisited taking into consideration the possibility of the reduction process.

The problem of the low-frequency dispersion in the case of polymer film electrodes — an experimental impedance study on Au|poly(o-phenylenediamine) electrodes

Abstract Electrochemical impedance spectra are presented for Au|poly( o -phenylenediamine) electrodes in contact with 1 mol dm −3 perchloric acid solution. The roughness of the gold substrate and the film thickness, respectively, were systematically varied. The results obtained affirm that the dispersion of the low-frequency capacitance is connected with the inhomogeneity of the surface film, and the role of the surface roughness of the gold substrate is minor, if any, in the development of the CPE behaviour, which is in contrast to some hypotheses presented recently.

Morphological changes in electrochemically deposited poly(3,4-ethylenedioxythiophene) films during overoxidation

Electrochemical and morphological properties of thin poly(3,4-ethylenedioxy-thiophene) (PEDOT) films deposited on gold were investigated in aqueous sulfuric acid solutions. X-ray diffraction and electron microscopy were used for monitoring the morphological changes and structure evolution caused by overoxidation. The diffraction peaks of PEDOT became sharper and more intensive during the subsequent oxidation cycles. This indicates that besides the degradation of the PEDOT film, its crystallinity was gradually improved with increasing the number of oxidation cycles. These changes may result in the appearance of novel properties that may be advantageous for specific applications.

The electrochemical degradation of poly(3,4-ethylenedioxythiophene) films electrodeposited from aqueous solutions

Abstract In this review, results of recent studies on the electrochemical stability and degradation properties of poly(3,4-ethylenedioxythiophene) films are summarized, with particular emphasis on the structural changes induced by overoxidation and electrochemical degradation. The most important electrodeposition methods for the preparation of PEDOT films in surfactant free aqueous media have also been summarized, and several experimental techniques suitable for monitoring the degradation process have been discussed. Morphological changes in PEDOT films during overoxidation have been analyzed. Overoxidation mechanisms proposed in the literature have been surveyed.

Electrical cross-talk in four-electrode experiments

AbstractThe subject of this paper is electrical cross-talk, an interference between the current/voltage characteristics of the two working electrodes in four-electrode (generator/collector) systems. Cross-talk arises in electrochemical cells of finite resistance due to the superposition of the electrical fields of the working electrodes, and often causes difficulties in the interpretation of measurement results. In this paper, we present an algorithm for modelling simple generation/collection experiments with a rotating ring–disk electrode (RRDE) immersed into a finite resistance solution of a redox couple. We show that based on the analysis of the Kirchhoff (Laplace) matrix of the simulation mesh, the effect of electrical cross-talk may be accounted for in such experiments. The intensity of cross-talk is found to be heavily influenced by the selection of the reference point for potential measurements; in practice, this is the position of the reference electrode or the tip of the Luggin probe. The devised model is validated by means of a simple and demonstrative experiment. Graphical Abstractᅟ

Characterization of the Capacitance of a Rotating Ring–Disk Electrode

The use of rotating ring–disk electrodes as generator-collector systems has so far been limited to the detection of Faradaic currents at the ring. As opposed to other generator-collector configurations, non-Faradaic detection has not yet been carried out with rotating ring–disk electrodes. In this study, a.c. perturbation based detection for measurement of the ring impedance is introduced. By using a conducting polymer-modified disk electrode in combination with a bare gold ring as a model, it is shown that the measured ring capacitance correlates with the polarization of the polymer film, most probably due to counter-ion exchange. A method of calculating the ring capacitance based on a small-signal sinusoid perturbation is described and the most important instrumental limitations are identified.

Electrochemical aspects of the behavior of perchlorate ions in the presence of iron group metals

Abstract The problem of the stability of perchlorate ions in the presence of iron group metals is discussed. It is suggested that electrochemists should consider the reduction process as important evidence that should be taken into account. It has been shown that the mechanical properties of the passive layer on nickel are influenced by the presence of Cl− ions, presumably because chloride ions incorporated in the passive film facilitate the formation of a more ordered structure.

Apparatus and methods for using a rotating ring–disk electrode with potentiodynamic control of both working electrodes

Abstract When studying electrochemical processes, one of the most widely used methods of determining the reaction pathway is an electrochemical assay of products using a rotating ring–disk electrode (RRDE). An RRDE tip consists of two electron conducting parts: a centrally located disk and a ring around it. When brought into contact with an electrolyte solution, the disk and the ring both form electrodes, the potentials of which can be independently controlled by a bi-potentiostat. When the tip is rotated, reactants from the solution arrive at the disk where they undergo an electrode reaction (oxidation or reduction) at a given rate, depending on the rotation speed. The formed products leave the disk surface and due to forced convection make their way towards the ring electrode where they can undergo another electrode reaction and can thus be detected. Normally, one applies potentiostatic control to at least one of the electrodes when carrying out an RRDE experiment; albeit the simultaneous potentiodynamic perturbation of the electrodes offers an increased applicability range. This paper presents the construction of a measuring system capable for the “bi-potentiodynamic” perturbation of two working electrodes, and demonstrates the use of such methods in case of a few chosen example systems.

Experimental methods for the determination of stress changes at electrified solid-liquid interfaces

Abstract In the present study some of the methods developed for the experimental determination of (interfacial or film) stress changes in electrochemical systems containing solid-liquid interfaces are briefly reviewed, as well as the kind and quality of information that can be obtained using these methods are discussed. The “bending beam” (“bending cantilever”, “laser beam deflection”, “wafer curvature”) method and related techniques, the piezoelectric method, the extensometer method, and the method based on the measurement of contact angle are discussed in detail. Special attention has been paid to problems related to the use of optical methods for position sensing.