Electrochemical nucleation on microelectrodes. Theory and experiment for diffusion-controlled growth

Heerman, L.; Tarallo, Anthony

doi:10.1016/s0022-0728(98)00101-6

Cited by 67 publications

(38 citation statements)

References 27 publications

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“…In coordinates vs. logt, potentiostatic curves were characterized each by two linear portions: 0.5-0.6, then 0.03-0.10. Initial portions of current transients were approximated by a linear dependence of I c on t 1/2 , which is characteristic of instantaneous diffusion-controlled nucleation [13][14][15] or diffusion-controlled growth of nuclei on microelectrodes [16,17]: I(t) = zFDck(πDt) 1/2 , where c is the bulk concentration of electrochemically active species, D is the diffusion coefficient, F is Faraday's constant, z is the number of electrons that take part in an analysis of redox process, and k is a dimensionless constant that depends on the experimental conditions.…”

Section: Resultsmentioning

confidence: 99%

Effect of the Electrode Material on the Reduction of La3+ and Ce3+ in Fluoride-Conducting Solid Electrolytes

et al. 2005

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The reduction of immobile cations La 3+ and Ce 3+ in fluoride-conducting solid electrolytes (FSE) LaF 3 ( Eu 2+ 0.8 mol %), LaF 3 ( Sr 2+ 5 mol %), and CeF 3 ( Sr 2+ 5 mol %) in contact with Ag, Bi, Si, La, Ce, and Sm working electrodes is studied by chronoamperometry and voltammetry with linear potential scan. Discovered is linear dependence of initial segments of potentiostatic transients of cathodic current on t 1/2 at FSE interfaces with Ag, Bi, La, Ce, and Sm. The dependence is due to diffusion-controlled instantaneous nucleation of Ln and Ce. The La 3+ and Ce 3+ reduction at the FSE/Ag interface is reversible in a narrow region. The reduction and oxidation of La 3+ and Ce 3+ (cations of the FSE rigid lattice) at the FSE/Me (Me = La, Ce and Sm, Bi, Si) interface is irreversible and involves a chemical reaction.

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Section: Resultsmentioning

confidence: 99%

Effect of the Electrode Material on the Reduction of La3+ and Ce3+ in Fluoride-Conducting Solid Electrolytes

et al. 2005

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“…Each of the transients in Figure 5a exhibits an increase in current density up to a maximum followed by a decay that converges to the limiting current, which corresponds to linear diffusion of the electroactive ions to a planar electrode. This behavior can be described by the theoretical model proposed by Tarallo et al [29][30][31] for diffusioncontrolled crystal nucleation and growth in three dimensions (3D )dc ) [32]: Table 2. Charge values associated with the reduction processes, Q PI'c , Q PII'c , total cathodic charge (Qc) and total anodic charge (Qa), obtained from the voltammograms recorded at different concentrations of BDA (Figure 3) [BA]/gl )1 Q I'c /l C cm )2 Q II'c /l C cm )2 Q c (Q I'c + Q II'c )/l C cm )2 Q a /l C cm )2 where…”

Section: Chronoamperometric Studymentioning

confidence: 96%

Electrochemical and AFM study of Zn electrodeposition in the presence of benzylideneacetone in a chloride-based acidic bath

et al. 2005

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The influence of benzylideneacetone (BDA) on the mechanism of zinc deposition and nucleation was studied by voltammetry, chronoamperometry and atomic force microscopy (AFM). The addition of BDA to the electrolyte solution partially inhibited (97%) the reduction of zinc at the potential E ¼ )1.15 vs SCE/V, giving rise to an increase in the overpotential for the discharge of the metal ion. This leads to the existence of two reduction processes with different energies that involve the same species, ZnCl 2À 4 . Analysis of chronoamperograms obtained in the absence and presence of BDA indicates that distinct nucleation mechanisms are involved during the initial stages of Zn deposition. In the absence of BDA, the transients are consistent with the model of 3D diffusion-controlled nucleation. In the presence of BDA, the transients exhibit a more complex form involving two growth processes. The first process, which occurs at short times, is explained in terms of a combination of three simultaneous nucleation processes: 2D progressive, 2D instantaneous, and 3D progressive nucleation, each limited by the incorporation of adatoms. The second process, which occurs at longer times, involves the three processes that occur at short times in conjunction with a principal contribution from a diffusion-controlled 3D nucleation mechanism. AFM imaging shows that the morphology of the deposited zinc depends on the applied electrode potential.

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“…Here I will mention only the pioneering work of Erdey-Gruz and Volmer [31], who were the first to notice that nuclei of the new phase were formed on some preferred sites on the electrode surface, the work of Fleischmann and Thirsk [32], who considered the case of equally active sites and the works of Kaischev and Mutaftschiev [33], Markov et al [34][35][36] and Fletcher et al [37][38][39][40][41][42], who examined the nucleus formation on active sites with different activities with respect to the process of nucleus formation. Attention should be paid also to the works of Sharifker and Mostany [43], Sluyters-Rehbach et al [44,45], Mirkin and Nilov [46], Heerman and Tarallo [47][48][49][50] and Danilov et al [51][52][53], who contributed essentially to this very important subject, too (see also Ref. [30] and the references cited therein).…”

Section: Non-stationary Nucleation Kineticsmentioning

confidence: 99%

Nucleation phenomena in electrochemical systems: kinetic models

Milchev

2016

ChemTexts

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The classical thermodynamics allow deriving theoretical expressions for the nucleation work and for the size of the critical nuclei in a supersaturated system. However, information on the rate of nucleus formation should be determined by means of kinetic considerations. This article sheds light on the nucleation kinetics in electrochemical systems at a constant thermodynamic supersaturation Dl. Theoretical expressions are derived for the stationary and non-stationary nucleation rate.

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Electrochemical nucleation on microelectrodes. Theory and experiment for diffusion-controlled growth

Cited by 67 publications

References 27 publications

Effect of the Electrode Material on the Reduction of La3+ and Ce3+ in Fluoride-Conducting Solid Electrolytes

Effect of the Electrode Material on the Reduction of La3+ and Ce3+ in Fluoride-Conducting Solid Electrolytes

Electrochemical and AFM study of Zn electrodeposition in the presence of benzylideneacetone in a chloride-based acidic bath

Nucleation phenomena in electrochemical systems: kinetic models

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