Diagnostic Criteria for the Characterization of Electrode Reactions with Chemically Coupled Reactions Preceding the Electron Transfer by Cyclic Square Wave Voltammetry

Helfrick, John C.; Mann, Megan A.; Bottomley, Lawrence A.

doi:10.1002/cphc.201501030

Cited by 10 publications

(14 citation statements)

References 36 publications

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“…In a quest for further methodological development, several modifications have been recently proposed, including multisampling SWV and square-wave chronoamperometry (or electrochemical faradaic spectroscopy) . Here also belongs a cyclic variant of SWV, known for a while as cyclic square-wave voltammetry − and SWV in a reverse mode. , Unique features of the technique for electrokinetic measurements are represented by a series of kinetic methods developed under conditions of constant scan rate. − …”

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confidence: 99%

“…Hence, the technique is seriously limited when slow, quasireversible processes are considered. The latter drawback is partly overcome with cyclic square-wave voltammetry ,, or SWV applied in a reverse mode; , unfortunately, the two variants are more complex than conventional SWV and interpretation and understanding of the voltammetric experiment could be even more difficult.…”

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Differential Square-Wave Voltammetry

et al. 2019

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A new voltammetric technique designed as a hybrid between differential pulse and square-wave voltammetry is proposed for the purpose of unifying the advantages of both techniques, i.e., the ability to provide mechanistic information, studying electrode kinetics of both sluggish and very fast electrode reactions, and the ability to suppress effectively residual background current. Voltammetric modulation of the hybrid technique consists of a staircase potential combined with square-wave potential modulation superimposed at the end of each potential step. By measuring the current at the end of each potential step and pulse, differential forward and backward voltammetric components can be composed, which is a unique ability of the hybrid technique. In addition, by analogy to square-wave voltammetry, a net differential component can be contracted with improved analytical performances compared to square-wave voltammetry. The proposed technique opens a new avenue for an advanced analysis of electrochemical processes and analytical application.

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Differential Square-Wave Voltammetry

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“…The scheme of derivative voltammetric (DV) approach is simpler, more straight-forward and faster compared with other methods of studying electrode reaction mechanisms, namely, CV [1,[38][39][40][41] and CSWV [66][67][68][69][70]. The present DV only requires, in general, a single scan for a system under investigation: few experimental variables need to be changed although some experimental variables (such as duration of the pulse) can be optimized at an initial stage of measurement.…”

Section: Advantages Of Derivative Voltammetric Methodsmentioning

confidence: 99%

“…Cyclic square-wave voltammetry (CSWV), which is an extension of SWV [62][63][64][65], has been adopted by Bottomley group [66][67][68][69][70]. Like pulse voltammetric techniques, SWV is effective in removing the interference from the capacitive current that is inherent in cyclic voltammetry(CV).…”

Section: Other Approaches For Diagnostic Criteria With Cyclic Square-wave Voltammetry (Cswv)mentioning

confidence: 99%

“…SWV, like DPV, is a pseudoderivative technique in which a derivative-shaped peak is obtained from the current with electronic control of input of square-wave potentials and current sampling times [62]. Diagnostic criteria as a tool for studying electrode mechanisms based on CSWV scheme have been investigated by the group for reversible [66] and quasireversible [67] processes, EC type [68], ECE type [69], CE type [70] mechanisms, and other non-unity stoichiometric cases [71]. Basically, the impact of experimental SW parameters -such as pulse heights (or amplitude), step heights (or potential increments), switching potentials, and periodon the peak-currents, peakpotentials and separations, peak-widths were examined.…”

Section: Other Approaches For Diagnostic Criteria With Cyclic Square-wave Voltammetry (Cswv)mentioning

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Advances in Derivative Voltammetry - A Search for Diagnostic Criteria of Several Electrochemical Reaction Mechanisms

Kim¹

2021

Analytical Chemistry - Advancement, Perspectives and Applications

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New methods for analysis of current-potential curves in terms of their derivatives are presented for studying various types of electrode processes – such as simple electron transfer reactions (reversible, quasi-reversible, and irreversible electron transfer) as well as chemically coupled electron transfer reactions along with a diagnostic scheme for differentiating these various types of electrochemical reaction mechanisms. Expressions for first- and higher order derivatives are derived from theoretical analytical solutions for currents for the different types of electrode mechanisms. The derivative curves are analyzed in terms of various parameters which characterize peak shape or peak symmetry with an emphasis on the second derivatives with well-defined anodic and cathodic peaks. Second derivatives can yield, in a simpler manner, the symmetry ratios; i.e., a ratio of anodic to cathodic peak-currents (ipa/ipc), and a ratio of anodic to cathodic peak-widths (Wpa/wpc) and a ratio of anodic to cathodic peak potential differences (ΔEpa/ΔEpc) or a peak separation (Epa-Epc) are evaluated, and these ratio can be related to kinetic parameters associated with a particular types of electrode mechanisms. Peaks are found to be symmetrical for a simple reversible electron transfer process (Er). However, peaks become asymmetrical when the electron transfer become slower (namely, irreversible, Eirr) or e− transfer reaction is coupled with homogeneous chemical reactions such as a prior reaction (CEr) or a follower-up reaction (ECr). From measured values of such symmetry ratios above, one can gain insight to the nature of the electrochemical systems enabling us to determine various kinetic parameters associated with a system. A diagnostic criteria for assigning an electrode mechanism is devised based on the values of asymmetry parameters measured, which are unity for a simple reversible electron transfer process.

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Mechanistic insights into homogeneous electrocatalytic reaction for energy storage using finite element simulation

Song

Yin

2022

Chinese Journal of Chemical Engineering

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Diagnostic Criteria for the Characterization of Electrode Reactions with Chemically Coupled Reactions Preceding the Electron Transfer by Cyclic Square Wave Voltammetry

Cited by 10 publications

References 36 publications

Differential Square-Wave Voltammetry

Differential Square-Wave Voltammetry

Advances in Derivative Voltammetry - A Search for Diagnostic Criteria of Several Electrochemical Reaction Mechanisms

Mechanistic insights into homogeneous electrocatalytic reaction for energy storage using finite element simulation

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