Theory of the reversible electrode process in case of cyclic voltammetry at finite thickness film electrode

Nazarov, B. F.; Larionova, Ekaterina; Stromberg, A. G.; Антипенко, И. С.

doi:10.1016/j.elecom.2007.04.014

Cited by 10 publications

(6 citation statements)

References 28 publications

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“…Accordingly, the peak intensities increase linearly with the square root of the scan rate, as inferred from the value 0.5 of the log j p versus log σ slope in this region. At lower scan rates, the peak potentials depart from their constant value and shift toward more negative potentials, in agreement with the trend observed experimentally and in previous works on mercury thin films or microelectrodes. , To rationalize this fact, the finite size of the mercury hemisphere has to be taken into account. – At high scan rates, the size of the diffusion layer, both in solution and in the amalgam, is much smaller than the hemisphere radius, and the observed behavior is equivalent to that obtained under semi-infinite diffusion conditions (see, for instance, Figure C). However, the smaller the scan rate, the thicker the diffusion layer becomes, until it greatly exceeds the radius of the mercury hemisphere.…”

Section: Resultssupporting

confidence: 89%

Voltammetry Involving Amalgam Formation and Anodic Stripping in Weakly Supported Media: Theory and Experiment

et al. 2010

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The voltammetric behavior of the Tl(I)/Tl(Hg) redox couple at a small mercury hemisphere (45 µm radius) is theoretically and experimentally investigated in the presence of various concentrations of supporting electrolyte, covering the range between "self-supported" (no electrolyte) to "fully supported" (very large excess of supporting electrolyte). A theoretical model is described, implementing the Nernst-Planck-Poisson equations, to account for both diffusional and migrational contributions to the mass transport, as well as for the potential distribution in solution. The model accurately reproduces the experimental results and then is used to predict the cathodic and anodic peak potentials and intensities for a wide range of supporting conditions, potential sweep rates, and electrode sizes. The influence of diffusion (linear vs spherical, semi-infinite vs finite), electrode size, and potential drop in solution are discussed in light of the theoretical and experimental results.

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Section: Resultssupporting

confidence: 89%

Voltammetry Involving Amalgam Formation and Anodic Stripping in Weakly Supported Media: Theory and Experiment

et al. 2010

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“…A theoretical model was developed to quantitatively assess ion diffusion in a solid-supported liquid membrane by cyclic voltammetry. The model is analogous to that of a thin mercury film electrode. , The diffusion problem based on the model was solved using COMSOL Multiphysics version 3.4 (COMSOL, Inc., Burlington, MA), which applies the finite element method. The simulation accuracy of this software package for two-phase diffusion processes was demonstrated previously. , Calculation of each CV took <10 s on a workstation equipped with a Xeon 3.0 GHz processor unit and 5.0 GB RAM with Linux.…”

Section: Theorymentioning

confidence: 99%

Stripping Analysis of Nanomolar Perchlorate in Drinking Water with a Voltammetric Ion-Selective Electrode Based on Thin-Layer Liquid Membrane

2008

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A highly sensitive analytical method is required for the assessment of nanomolar perchlorate contamination in drinking water as an emerging environmental problem. We developed the novel approach based on a voltammetric ion-selective electrode to enable the electrochemical detection of "redox-inactive" perchlorate at a nanomolar level without its electrolysis. The perchlorate-selective electrode is based on the submicrometer-thick plasticized poly(vinyl chloride) membrane spin-coated on the poly(3-octylthiophene)-modified gold electrode. The liquid membrane serves as the first thin-layer cell for ion-transfer stripping voltammetry to give low detection limits of 0.2-0.5 nM perchlorate in deionized water, commercial bottled water, and tap water under a rotating electrode configuration. The detection limits are not only much lower than the action limit (approximately 246 nM) set by the U.S. Environmental Protection Agency but also are comparable to the detection limits of the most sensitive analytical methods for detecting perchlorate, that is, ion chromatography coupled with a suppressed conductivity detector (0.55 nM) or electrospray ionization mass spectrometry (0.20-0.25 nM). The mass transfer of perchlorate in the thin-layer liquid membrane and aqueous sample as well as its transfer at the interface between the two phases were studied experimentally and theoretically to achieve the low detection limits. The advantages of ion-transfer stripping voltammetry with a thin-layer liquid membrane against traditional ion-selective potentiometry are demonstrated in terms of a detection limit, a response time, and selectivity.

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“…The number of electrons involved in the redox reaction at the CTS/NPC/ITO electrode was ascertained by eq where E p was the peak potential and E p/2 was the half peak potential. The calculated value of n was ∼ 1 (peak III of Figure b was taken as an example to determine n ).…”

Section: Results and Discussionmentioning

confidence: 99%

“…The number of electrons involved in the redox reaction at the CTS/NPC/ITO electrode was ascertained by eq 2 48 n E E 0.0565( )…”

mentioning

confidence: 99%

Carbohydrates-Derived Nitrogen-Doped Hierarchical Porous Carbon for Ultrasensitive Detection of 4-Nitrophenol

Peng

Xia

et al. 2018

ACS Sustainable Chem. Eng.

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A facile, cost-effective approach to obtain sensor electrode materials with excellent electrochemical performance for sensitive and fast detection of 4-nitrophenol (4-NP) is of great importance to the environment and human health. Herein, a smart strategy was proposed for fabrication of nitrogen-doped hierarchical porous carbon (NPC) material with large surface area and unique hierarchical porous structure derived from conveniently available carbohydrates via a facile process. NPC combined with chitosan (CTS) was used to modify an indium-tin oxide (ITO) electrode, referred to as a CTS/NPC/ITO electrode, in which CTS acted as dispersant and immobilization reagent. On the basis of the optimum conditions, 4-NP was successfully deposited on a CTS/NPC/ITO electrode and the cathodic deposit of 4-NP showed reversible characteristics in a potential range between −0.22 and −0.00 V as well as high ionic-electronic conductivity. Moreover, the electrochemical reaction kinetics and mechanism of 4-NP were explored in detail by CVs, FTIR spectra, and LC–MS. The response sensitivities of the electrode for 4-NP were obtained as 4.85 μA μM–1, 2.212 μC μM–1, and 0.118 μA μM–1 (RSD ∼ 5%) while detection limits (S/N = 3) were 27.55, 30.10, and 5.44 μM by applying cyclic voltammetry, chronocoulometry, and differential pulse voltammetry, respectively. The results were presented to demonstrate that the CTS/NPC/ITO electrode had excellent reproducibility, repeatability, good stability, and high selectivity for detecting 4-NP in real water samples.

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Theory of the reversible electrode process in case of cyclic voltammetry at finite thickness film electrode

Cited by 10 publications

References 28 publications

Voltammetry Involving Amalgam Formation and Anodic Stripping in Weakly Supported Media: Theory and Experiment

Voltammetry Involving Amalgam Formation and Anodic Stripping in Weakly Supported Media: Theory and Experiment

Stripping Analysis of Nanomolar Perchlorate in Drinking Water with a Voltammetric Ion-Selective Electrode Based on Thin-Layer Liquid Membrane

Carbohydrates-Derived Nitrogen-Doped Hierarchical Porous Carbon for Ultrasensitive Detection of 4-Nitrophenol

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