Electrolytic nucleation of silver on a glassy carbon electrode

Milchev, A.; Vassileva, Elka

doi:10.1016/s0022-0728(80)80205-1

Cited by 69 publications

(20 citation statements)

References 4 publications

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“…Although N 0 is related to a physical nucleation preferential site, similar parameters as N 0 in Eqs. (25) and (26) can still be defined on the basis of the exclusion zone model discussed here (Eq. (B15)).…”

Section: Resultsmentioning

confidence: 99%

“…The activation energy predicted from classical nucleation theory [24], which equates the Gibbs energy of the critical nucleus to the activation energy for nucleation predicts a linear relation between the logarithm of the nucleation rate and the inverse square of the applied potential. However, atomistic theory predicts a linear relationship between the logarithm of the nucleation rate and the applied potential [25]. The obtained rate constants and number of nuclei (Eq.…”

Section: Discussionmentioning

confidence: 97%

See 1 more Smart Citation

Nucleation at liquid∣liquid interfaces: electrodeposition without electrodes

Johans¹,

Lahtinen²,

Kontturi³

et al. 2000

Journal of Electroanalytical Chemistry

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A model has been developed for diffusion controlled electrodeposition of metallic particles at the interface between two immiscible electrolyte solutions. A rate law was derived for the case where no preferential nucleation sites are present. Palladium particles were deposited at the water 1,2-dichloroethane interface by reduction of aqueous ammonium palladate using butylferrocene in the organic phase as electron donor. Experimental results were in good agreement with the theoretical model derived. The potential dependence of the nucleation rate was found to follow a classical exponential law.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 97%

Nucleation at liquid∣liquid interfaces: electrodeposition without electrodes

Johans¹,

Lahtinen²,

Kontturi³

et al. 2000

Journal of Electroanalytical Chemistry

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“…However, it is readily anticipated that the nucleus saturation density will be determined mainly by the effect of ingestion if I st ¼ AN 0 is very low compared with the growth rate of the nuclei. The nucleus saturation density is an experimentally observable quantity [22][23][24][25][26] so that predictions of theory can be compared directly with the results of visual observation (including techniques such as AFM, STM, . .…”

Section: Nucleation Exclusion Zonesmentioning

confidence: 99%

“…[27,28]). Experimental evidence for the effect of ingestion has been obtained also from studies of the spatial distribution of the nuclei over the electrode surface [2,[14][15][16][17]21,[23][24][25][26]. Ingestion of active sites leads to a decrease of the probability of nucleation in the vicinity of growing nuclei and therefore disrupts the random distribution of nuclei.…”

Section: Nucleation Exclusion Zonesmentioning

confidence: 99%

The potentiostatic transient for 3D nucleation with diffusion-controlled growth: theory and experiment for progressive nucleation

Matthijs

Langerock

Michailova

et al. 2004

Journal of Electroanalytical Chemistry

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The theory of the potentiostatic transient for 3D nucleation with diffusion-controlled growth is discussed. It is shown that the theoretical model of Mirkin and Nilov [J. Electroanal. Chem., 283 (1990) 35] and Heerman and Tarallo [J. Electroanal. Chem., 470 (1999) 70] predicts too high values of the current, which becomes very apparent for high values of the site density and low values of the nucleation rate constant (progressive nucleation). For example, the model then predicts that the current in the limit of long times will be higher than the Cottrell limit by a factor of 4/3 which is physically unacceptable. Therefore, a modification to this model is proposed which is based on a careful analysis of the Kolmogorov-Avrami theorem. The ''extended area'' in the KolmogorovAvrami theorem includes contributions from ''phantom nuclei'' that are born inside already existing zones but do not exist physically. This is necessary to preserve the randomness of the system and allows the correct calculation of the appearance rate of the nuclei and the nucleus saturation density. The ''extended current'', defined in analogy with the ''extended area'', then also attributes current to the phantom nuclei. It follows that the ratio j ex ðtÞ=h ex ðtÞ which appears in the model of Mirkin and Nilov and Heerman and Tarallo does not correspond to the actual number of nuclei formed on the electrode. Therefore, the ''extended quantities'' in this ratio must be replaced with quantities that relate directly to the real number of clusters (this implies what is fairly obvious, that the appearance rate of the clusters must be calculated first). This makes it is possible to derive an equation that predicts correctly the current in the limits of both short and long times which is directly linked to the N a ðtÞ vs. time relation (where N a ðtÞ is the actual number of nuclei on the electrode). Experiments for the nucleation of silver on glassy carbon electrodes, with the simultaneous recording of both jðtÞ vs. time and N a ðtÞ vs. time relations, are described. The experimental results obtained from the transients and the direct visual counting of nuclei are compared with the theoretical predictions.

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“…atoms for the size of the critical nucleus in the intervals 84-96 and 96-106 m V, respectively. (69,(97)(98)(99) The apparent agreement with theory has, however, to be taken with caution. All experiments up to now have been made in a relatively small overpotential interval and no more than one cusp, i.e., two slopes, of the log J / ' 11c curve has been observed.…”

Section: Comparison With Experimenta' Datamentioning

confidence: 99%

Deposition and Dissolution of Metals and Alloys. Part A: Electrocrystallization

Budevski

1983

Comprehensive Treatise of Electrochemistry

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Electrolytic nucleation of silver on a glassy carbon electrode

Cited by 69 publications

References 4 publications

Nucleation at liquid∣liquid interfaces: electrodeposition without electrodes

Nucleation at liquid∣liquid interfaces: electrodeposition without electrodes

The potentiostatic transient for 3D nucleation with diffusion-controlled growth: theory and experiment for progressive nucleation

Deposition and Dissolution of Metals and Alloys. Part A: Electrocrystallization

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