Electrolytic nucleation of silver on a glassy carbon electrode

Milchev, A.; Vassileva, Elka; Kertov, V.

doi:10.1016/s0022-0728(80)80204-x

Cited by 110 publications

(42 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The counter electrode was a pure silver foil and the reference electrode was a pure silver wire positioned via a Luggin-capillary close to the working electrode. All experiments were performed at the same overpotential, g ¼ À0:112 V. After each experiment the silver clusters were dissolved in nitric acid to maintain a constant surface state of the electrode (it has been shown previously that anodic dissolution leads to an increased activity of the electrode [23]). The electrochemical cell included an optically flat window for the in situ microscopic observation and counting of the growing clusters.…”

Section: Methodsmentioning

confidence: 99%

“…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%

See 2 more Smart Citations

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

View full text Add to dashboard Cite

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.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Nucleation Exclusion Zonesmentioning

confidence: 99%

Section: Nucleation Exclusion Zonesmentioning

confidence: 99%

See 1 more Smart Citation

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

View full text Add to dashboard Cite

show abstract

“…Such a dependence of N c on the applied overpotential is not unexpected, and has been observed before in different systems. [55][56] Interestingly, using a different approach based on the presumption that N o is a potential-independent parameter, Kolb et al 47 also found that N c is 2. . Kinetic characteristics of the copper UPD process onto the copper-free Au(111) electrode surface were observed when the electrode potential was switched from potential A to potential C (see Figure 1).…”

Section: Copper Deposition Onto the Au(111) Electrode Surface Previomentioning

confidence: 99%

New Insights into Evaluation of Kinetic Parameters for Potentiostatic Metal Deposition with Underpotential and Overpotential Deposition Processes

2000

View full text Add to dashboard Cite

Kinetics of copper deposition onto an Au(111) surface from sulfuric acid electrolyte, was evaluated using potentiostatic current transients. Measurements were conducted employing a new and nontraditional method, with gold electrode completely free from copper deposit at the beginning of the potential step (i.e., deposition process). The current transients obtained clearly show partial contribution from copper underpotential deposition (UPD) and copper overpotential deposition (OPD) processes. Quantitative evaluation of experimental transients was performed with the recently developed method for theoretical transient computer simulation. Detailed analysis of the kinetic parameters shows that copper UPD could be characterized as a two-dimensional nucleation and growth limited by the lattice incorporation (2D-LI) process and copper OPD as a three-dimensional nucleation process limited by diffusion-controlled growth (3D-DC). The UPD seems to be an inevitable part of the deposition process and takes place prior to OPD, regardless of the potential applied. Therefore, UPD should be treated as an early stage of the deposition process. Furthermore, our results show that the kinetics differs depending on whether deposition is initiated from a clean, bare Au(111) surface or from a gold surface already coated with a copper UPD adlayer. This indicates the role of the UPD process and the UPD adlayer on the course of OPD. Differences observed in deposition kinetics between electrolytic baths at pH 2 and 4 were likely due to adsorption of different sulfate species (sulfate or bisulfate anions) on the copper-deposit-modified Au(111) substrate (UPD, epitaxial monolayer) or bulk deposit adlayer (OPD).

show abstract

“…Also it has been argued that sites will become inactive if the concentration of the electroactive species in their vicinity has become low because of the consumption of the species by neighbouring growing sites (ingestion effect [3,5,8,11,15,18,[20][21][22][23].…”

mentioning

confidence: 99%

On the rate equation of nucleation and the concept of active sites in electrodeposition

Wijenberg

Mulder

Sluyters‐Rehbach

et al. 1988

Journal of Electroanalytical Chemistry and Interfacial Electroc

View full text Add to dashboard Cite

On the basis of the assumption that on a homogeneous surface area a probability 0 < P( E, c) <: 1 for nucleation can be defined which increases with the monomer concentration c and is also dependent on the potential E, it is shown both by a schematrc computer simulation and by an approximate analytical derivation that necessarily the number of nuclei has to attain a limiting value for long times. without having to resort to the existence of active sites. It follows that this limiting number arises from a concurrence between the probability of nucleation and the processes that accompany the growth of a nucleus and that decrease supersaturation. LIST OF SYMBOLSR(L u> nucleation rate per active site, s-' monomer concentration at a radial distance r from the centre of a lone nucleus at time t, mol cmm3 monomer bulk concentration, mol cmP3 diffusion coefficient, cm2 s-l growth constant of exclusion zone, cm s-' number density of nuclei at time t, cm-2 number density of active sites, cmP2 nucleation rate probability as a function of potential E and concentration c, cme2 s-' radius of a nucleus at time t, cm radius of exclusion zone at time t belonging to a lone nucleus, which is born at time u, cm l To whom correspondence should be addressed 0022-0728/88/$03.50 0 1988 Elsevier Sequoia S.A.

show abstract

Electrolytic nucleation of silver on a glassy carbon electrode

Cited by 110 publications

References 19 publications

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

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

New Insights into Evaluation of Kinetic Parameters for Potentiostatic Metal Deposition with Underpotential and Overpotential Deposition Processes

On the rate equation of nucleation and the concept of active sites in electrodeposition

Contact Info

Product

Resources

About