Statistical Mechanics and Kinetic Modeling of Electrochemical Reactions on Single‐Crystal Electrodes Using the Lattice‐Gas Approximation

Koper, Marc T. M.

doi:10.1002/9783527680436.ch2

Cited by 5 publications

(5 citation statements)

References 62 publications

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“…Adsorbate−adsorbate interactions on electrode surfaces have been determined in the past by comparison of lattice gas models with experimental adsorption isotherms. 86 For example, this approach provided interaction parameters for Cl and Br on Ag(100), which were in agreement with the results of DFT calculations for various discrete coverages. 87,88 Here, the isotherms for Br could be fully explained by longrange electrostatic repulsion, whereas for Cl additional shortrange attractive interactions were necessary.…”

Section: Surfacesmentioning

confidence: 95%

Toward an Atomic-Scale Understanding of Electrochemical Interface Structure and Dynamics

2019

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For the knowledged-based development of electrochemical processes, a better fundamental understanding of the interfaces between electrodes and electrolytes is necessary. This requires insight into the interface structure and dynamics on the atomic-scale, including that of the liquid electrolyte in the near-surface region, i.e., in the inner and outer part of the electrochemical double layer. This perspective describes current studies of simple and well-defined electrochemical interfaces by first-principles electronic structure calculations and in situ structure-sensitive methods. It is shown that these experimental and theoretical studies are now approaching a level, where they can operate on the same footing, making direct comparison of the obtained results feasible. Using selected examples, progress in clarifying the structure and dynamics of the double layer, of adsorbed species on electrode surfaces, and of initial steps in electrochemical phase formation processes is discussed.

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Section: Surfacesmentioning

confidence: 95%

Toward an Atomic-Scale Understanding of Electrochemical Interface Structure and Dynamics

2019

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“…[17,23] In order to incorporate the influence of intermolecular interactions to the ideal situation (Eq. (6)), it is usually assumed that all adsorbates on the surface lattice are randomly mixed and uncorrelated and, under these conditions, the average interaction energy that an adsorbate feels from the others is proportional to the coverage f. [24,40,41] If we restrict to the nearest-neighbor interactions, an additional energy term should be added to the electrochemical potential thus giving rise to the Frumkin isotherm, which for a two adsorbates O and R and an electroinactive coadsorbate P takes the following expression: [40]…”

Section: Non-ideal Behaviormentioning

confidence: 99%

Square Wave Voltcoulommetry Analysis of the Influence of the Electrostatic Environment on the Electrochemical Functionality of Redox Monolayers

González

Sequí

2019

ChemElectroChem

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The analysis of effects of intermolecular interactions on square wave voltcoulommetric (SWVC) responses of electroactive monolayers under Nernstian conditions is presented. Theoretical expressions are given for the Faradaic and non‐Faradaic charge potential curves in terms of the potential perturbation variables and of the phenomenological interaction parameter G. Simple methods are proposed for determining the total excess of electroactive species, the apparent formal potential and the interaction parameter. The application of these methods to the analysis of the electrochemical behaviour of binary monolayers of ferrocenylundecanethiol/decanethiol at gold and platinum electrodes in two different non‐aqueous solvents allows us to obtain reliable values of the above parameters that clearly improve those determined by using Cyclic Voltammetry. Electrostatic insights into the interaction parameters is provided on the basis of a previously reported model. The importance of the presence of ion pairing processes in the value of the parameter G is discussed. The results obtained with SWVC technique point out the fact that intermolecular interactions are not avoided at low surface excesses of the redox probe, indicating that the impact of electrostatics in the appearance of non‐ideal electrochemical responses depends on the nature of the electrolytic media and on the structure of the monolayer in a complex way.

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“…To incorporate the influence of intermolecular interactions to the ideal situation (eqs 14 and 15), from a theoretical point of view, is usually assumed the so-called “mean-field approximation”, which considers that all adsorbates on the surface lattice are randomly mixed and uncorrelated. 50 As a result, the average interaction energy that an adsorbate feels from the others is proportional to the coverage f . If we restrict to the nearest-neighbor interactions, an additional energy term should be added to the electrochemical potential, thus giving rise to the Frumkin isotherm, which for two adsorbates O and R and an electroinactive coadsorbate P takes the following expression 51 with a OO , a RR , a OR , a OP , and a RP being the interaction coefficients for couples O–O, R–R, O–R/R–O, OP, and RP, respectively (with a ij being positive for attractions and negative for repulsions 30 ).…”

Section: Theorymentioning

confidence: 99%

“…To incorporate the influence of intermolecular interactions to the ideal situation (eqs and ), from a theoretical point of view, is usually assumed the so-called “mean-field approximation”, which considers that all adsorbates on the surface lattice are randomly mixed and uncorrelated . As a result, the average interaction energy that an adsorbate feels from the others is proportional to the coverage f .…”

Section: Theorymentioning

confidence: 99%

Kinetic Implications of the Presence of Intermolecular Interactions in the Response of Binary Self-Assembled Electroactive Monolayers

González

Sequí

2018

ACS Omega

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Quantitative analysis of the influence of intermolecular interactions on the response of electroactive binary monolayers, incorporating the presence of electroinactive coadsorbed species and Marcus–Hush kinetic formalism, has been deduced as an extension of previous models. An expression for the current–potential relationship in terms of two global phenomenological interaction parameters and the apparent charge-transfer rate constant and formal potential has been obtained and applied to multipotential chronoamperometry for the analysis of intermolecular interaction effects on the kinetics of the charge transfer. Experimental verification of the theoretical framework has been performed with binary ferrocenylundecanethiol/decanethiol monolayers on gold and platinum substrates for different coverage degrees of the redox probe. The increase of the ferrocene coverage gives rise to a slowing down of the charge-transfer process through a decrease of the apparent rate constant above a 90% for gold and platinum electrodes when the surface coverage increases from 1–2 to 15–30%. Significant differences in the magnitude of intermolecular interactions and the symmetry degree of the charge-transfer process are observed between gold and platinum electrodes. Moreover, for high surface coverages of ferrocene, two different domains appear, from which it is possible to carry out a kinetic discrimination of the two responses. Values of the interaction and kinetic parameters have been obtained for the different monolayers under study, and the limit of applicability of this treatment is discussed.

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Statistical Mechanics and Kinetic Modeling of Electrochemical Reactions on Single‐Crystal Electrodes Using the Lattice‐Gas Approximation

Cited by 5 publications

References 62 publications

Toward an Atomic-Scale Understanding of Electrochemical Interface Structure and Dynamics

Toward an Atomic-Scale Understanding of Electrochemical Interface Structure and Dynamics

Square Wave Voltcoulommetry Analysis of the Influence of the Electrostatic Environment on the Electrochemical Functionality of Redox Monolayers

Kinetic Implications of the Presence of Intermolecular Interactions in the Response of Binary Self-Assembled Electroactive Monolayers

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