Theory of square-wave catalytic adsorptive stripping voltammetry. How to obtain mechanistic information from experimental data

Vettorelo, Sabrina N.; Garay, Fernando

doi:10.1016/j.jelechem.2018.08.024

Cited by 7 publications

(5 citation statements)

References 27 publications

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“…All other simulation parameters are same as in Fig. 1 elaborated due to mutual interplay between different kinetic parameters [40,[47][48][49][50][51][52][53][54].…”

Section: Discussionmentioning

confidence: 99%

Square-wave protein-film voltammetry: new insights in the enzymatic electrode processes coupled with chemical reactions

Gulaboski

Mirčeski

Lovrić³

2019

J Solid State Electrochem

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Redox mechanisms in which the redox transformation is coupled to other chemical reactions are of significant interest since they are regarded as relevant models for many physiological systems. Protein-film voltammetry, based on surface confined electrochemical processes, is a methodology of exceptional importance, which is designed to provide information on enzyme redox chemistry. In this work, we address some theoretical aspects of surface confined electrode mechanisms under conditions of square-wave voltammetry (SWV). Attention is paid to a collection of specific voltammetric features of a surface electrode reaction coupled with a follow-up (EC rev), preceding (C rev E) and regenerative (EC') chemical reaction. While presenting a collection of numerically calculated square-wave voltammograms, several intriguing and simple features enabling kinetic characterization of studied mechanisms in time-independent experiments (i.e., voltammetric experiments at a constant scan rate) are addressed. The aim of the work is to help in designing a suitable experimental setup for studying surface electrode processes, as well as to provide a means for determination of kinetic and/or thermodynamic parameters of both electrode and chemical steps.

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“…All other simulation parameters are same as in Fig. 1 elaborated due to mutual interplay between different kinetic parameters [40,[47][48][49][50][51][52][53][54].…”

Section: Discussionmentioning

confidence: 99%

Square-wave protein-film voltammetry: new insights in the enzymatic electrode processes coupled with chemical reactions

Gulaboski

Mirčeski

Lovrić³

2019

J Solid State Electrochem

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“…Square-wave voltammetry (SWV), as a special form of the popular differential pulse voltammetry, , is one of the most advanced members in the family of pulse voltammetric techniques, − being primarily designed to provide high sensitivity and speed of the analytical measurement. , The popularity of the technique has been permanently progressing since the seminal work of Ramaley and Krause, contributions of Osteryoungs and O’Dea, Lovric et al., − and others. − Methodological development and application of the technique have been reviewed recently. , In the past 2 decades the application for studying mechanism − and kinetics , of electrochemical processes has been progressively increasing revealing the versatility and sophistication of the technique.…”

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confidence: 99%

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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“…Two factors with detrimental effect on signal stability should be mentioned: the peak widening and the background current, both increasing with the square wave frequency. The first one is caused by the increase in potential separation between the forward and backward components of the square‐wave modulation in irreversible or quasireversible systems , whereas the second one by the increase of the capacitive current with scan speed. As a result, a frequency of 10 Hz ensured the best compromise between sensitivity and signal stability (i. e. the best S/N ratio), as already reported in our previous work .…”

Section: Figurementioning

confidence: 99%

“…The limit of linearity (LOL) was also evaluated by subsequent additions of iron standard solution up to the loss of linearity in the calibration curve. For the characterization of the adsorption and electrochemical behavior see .…”

Section: Figurementioning

confidence: 99%

Fostering and Understanding Iron Detection at the Ultratrace Level by Adsorptive Stripping Voltammetry with Catalytic Enhancement

Sanvito

Monticelli

2019

Electroanalysis

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Iron detection at the ultratrace level in seawater is at the forefront in chemical oceanography research and analytical methodologies for its determination are actively sought. Voltammetric methods and specifically cathodic stripping voltammetry (CSV) with catalytic enhancement, are particularly fit for this purpose as they avoid any separation and pretreatment step, showing high sensitivity and robustness towards the saline matrix. Here we introduce a simplification in the instrumentation for iron detection by CSV using 2,3‐dihydroxynaphthalene (DHN) as the ligand, atmospheric oxygen as the catalytic enhancer and a small 0.5 mL cell. The simplification involves the use of a standard, non‐specialized voltammetric cup as a holder for the small cell and the introduction of a simple silver wire as a pseudoreference electrode. The latter reduces the risk of sample contamination and is perfectly suited for employment with the small, 0.5 mL volume cell. Extensive optimization was performed in both ultrapure and seawater: a square wave frequency of 10 Hz was adopted, whereas the ligand concentration did not significantly influence the limit of detection (around 10 and 40 pM for ultrapure and seawater, respectively). The latter difference in signal to noise ratio was explained by the kinetics of iron complex reduction. The method was successfully validated by the analysis of a seawater sample with consensus value.

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Theory of square-wave catalytic adsorptive stripping voltammetry. How to obtain mechanistic information from experimental data

Cited by 7 publications

References 27 publications

Square-wave protein-film voltammetry: new insights in the enzymatic electrode processes coupled with chemical reactions

Square-wave protein-film voltammetry: new insights in the enzymatic electrode processes coupled with chemical reactions

Differential Square-Wave Voltammetry

Fostering and Understanding Iron Detection at the Ultratrace Level by Adsorptive Stripping Voltammetry with Catalytic Enhancement

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