Electrocatalysis of the first and second kind: Theoretical and experimental study in conditions of square-wave voltammetry

Mirčeski, Valentin; Bobrowski, Andrzej; Zarębski, Jerzy; Spasovski, Filip

doi:10.1016/j.electacta.2010.07.088

Cited by 23 publications

(16 citation statements)

References 21 publications

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“…where k s is standard rate constant and β is anodic electron transfer coefficient. The modelling of the electrode reaction (1) is well known and described elsewhere , . The solution for the quasireversible electrode reaction at a planar electrode is given in the form of the following recurrent formula [Eq.…”

Section: The Modelmentioning

confidence: 99%

Electrochemical Faradaic Spectroscopy

2017

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For the purpose of simplification of the electrochemical study under conditions of square-wave voltammetry (SWV), a simplified form of potential modulation is proposed by replacing the staircase potential ramp with a constant potential. The resulting potential modulation, which could be considered as a pulse form of a chronoamperometric experiment (i. e., square-wave chronoamperometry), is provisionally termed as electrochemical faradaic spectroscopy, considering the fact that the main tool in the kinetic analysis is the frequency of the potential pulses applied. The proposed technique is illustrated with theoretical analysis of a simple, kinetically controlled electrode reaction of a dissolved redox couple and experimentally verified with the Eu 3 + (aq)/Eu 2 + (aq) redox couple at a mercury electrode. The square-wave chronoamperometry exhibits unique features of the response absent in both conventional SWV and chronoamperometry, widening the range of accessible electrode kinetics.

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Section: The Modelmentioning

confidence: 99%

Electrochemical Faradaic Spectroscopy

2017

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“…In addition to the theory of catalytic mechanisms, Mirceski et al [40] performed a comparative analysis of the electrocatalytic mechanisms of the first and second kind at a planar electrode, considering quasireversible electrode reactions. The catalytic mechanism of the first kind is represented by a simple regenerative EC' reaction scheme, whereas the electrocatalysis of the second kind assumes first formation of an electroactive complex YS between the catalyst Y and the electroinactive substrate S, followed by an irreversible electrochemical reaction of YS that yields the catalyst Y and the final electroinactive product P.…”

Section: Electrode Mechanisms Studied With Swvmentioning

confidence: 99%

“…In the reviewed period significant contributions in the theory of SWV have been done by the research groups of Lovric [18][19][20][22][23][24][25][26][27][28][29], Molina [17,[30][31][32][33][34][35], Compton [36][37][38][39], Mirceski [40][41][42][43], Gulaboski [44][45][46][47], and others [48][49][50]. The theory refers to a variety of electrode mechanisms including dissolved or immobilized redox couples at macroscopic planar or microelectrodes, as well as processes undergoing in a restricted diffusion space.…”

Section: Electrode Mechanisms Studied With Swvmentioning

confidence: 99%

Square‐Wave Voltammetry: A Review on the Recent Progress

et al. 2013

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A review on the recent progress of square-wave voltammetry is presented, covering the period of the last five years. The review addresses the new theoretical development of the technique as well as its application for mechanistic purposes, electrode kinetic measurements, biochemical and analytical applications. Besides, a few novel methodological modifications are proposed that might expand the scope and application of the technique.

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“…(2)) is assumed to be electrochemically quasireversible, whereas the coupled chemical reaction (eq. (3)) is chemically irreversible, associated with a pseudo-first order rate constant k c (s À1 ) [33]. As previously known, the voltammetric properties of the EC' mechanism under conventional SWV are controlled by the electrode kinetic parameter k and the catalytic parameter g = k c /f.…”

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confidence: 86%

Characterizing electrode reactions by multisampling the current in square-wave voltammetry

Mirčeski

Guziejewski

Bozem

et al. 2016

Electrochimica Acta

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A B S T R A C TA novel and simple methodology for characterization of electrode processes by square-wave voltammetry (SWV), considered as a complex repetitive double-step chronoamperometric experiment, is proposed. Specifically, the sampling of the current at the very end of each potential pulse, as common in conventional SWV, is replaced with a multisampling protocol during each potential pulse, resulting in generation of a series of corresponding multisampled SW voltammograms constructed out of a single measurement. The evolution of such voltammograms reflects the chronoamperometric properties of the current in the course of each potential pulse, thus being specific to electrode mechanism and electrode kinetics. The proposed methodology could serve as a basis for modification of common SWV mode in commercially available instrumentation for the purpose of an advanced characterization of electrode processes. The methodology is theoretically illustrated by the analysis of three kinetically controlled common electrode mechanisms, such as the electrode reaction of a solution resident and surface confined redox couples, as well as the regenerative catalytic electrode mechanism (EC'), while the experimental verification is done with the electrode reaction of Eu 3+ /Eu 2+ and azobenzene/ hydrazobenzene redox couples.

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Electrocatalysis of the first and second kind: Theoretical and experimental study in conditions of square-wave voltammetry

Cited by 23 publications

References 21 publications

Electrochemical Faradaic Spectroscopy

Electrochemical Faradaic Spectroscopy

Square‐Wave Voltammetry: A Review on the Recent Progress

Characterizing electrode reactions by multisampling the current in square-wave voltammetry

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