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Titolo:
Influence of spatial redox distribution on the electrochemical behavior ofelectroactive self-assembled monolayers
Autore:
Calvente, JJ; Andreu, R; Molero, M; Lopez-Perez, G; Dominguez, M;
Indirizzi:
Univ Sevilla, Fac Quim, Dept Quim Fis, Seville 41012, Spain Univ Sevilla Seville Spain 41012 im, Dept Quim Fis, Seville 41012, Spain
Titolo Testata:
JOURNAL OF PHYSICAL CHEMISTRY B
fascicolo: 39, volume: 105, anno: 2001,
pagine: 9557 - 9568
SICI:
1520-6106(20011004)105:39<9557:IOSRDO>2.0.ZU;2-0
Fonte:
ISI
Lingua:
ENG
Soggetto:
INTERFACIAL POTENTIAL DISTRIBUTION; ADSORBED MOLECULES; DOUBLE-LAYER; ALKANETHIOL MONOLAYERS; VOLTAMMETRIC RESPONSE; MODIFIED ELECTRODES; CYCLIC VOLTAMMETRY; SWEEP VOLTAMMETRY; ION ASSOCIATION; GOLD ELECTRODES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
48
Recensione:
Indirizzi per estratti:
Indirizzo: Calvente, JJ Univ Sevilla, Fac Quim, Dept Quim Fis, Seville 41012, Spain Univ Sevilla Seville Spain 41012 Fis, Seville 41012, Spain
Citazione:
J.J. Calvente et al., "Influence of spatial redox distribution on the electrochemical behavior ofelectroactive self-assembled monolayers", J PHYS CH B, 105(39), 2001, pp. 9557-9568

Abstract

Packing restrictions and hydrophobic interactions are likely to lead to a spatial distribution of redox centers in electroactive monolayers. A mean field analysis of the electrochemical implications of spatial redox dispersion in SAMs, including the possibility of surface ion pair formation, has been carried out. The boundary value problem associated with a layered distribution of potential-induced charges has been solved by using the orthogonalcollocation technique under equilibrium conditions. Spreading of the redoxcenters into a 3D dielectric slab results in broader and asymmetric Voltammograms, reflecting a layer-by-layer redox conversion. It is also shown that the voltammetric shape is sensitive to the specific features of the spatial redox distribution, and theoretical requirements for the appearance of asymmetric broadening are examined in terms of the electrostatic properties of the monolayer. It is suggested that this type pf spatial inhomogeneity may cause some of the broad and asymmetric voltammetric shapes that often characterize the electrochemical behavior of electroactive SAMs, and that some structural information can be gained from the analysis of these voltammograms, as long as electrolyte ions do not permeate the organic monolayer. The effect of surface ion association on the voltammetric features is also examined, and it is interpreted in terms of the distinct sensitivity of the potential at each redox plane with respect to the local counterion concentration. Comparison is made with the experimental results of Chidsey et al. (J. Am. Chem. Soc. 1990, 112, 4301) for the oxidation of FcCO(2)(CH2)(11)SH/CH3(CH2)(9)SH and Fc(CH2)(16)SH/CH3(CH2)(15)SH mixed monolayers.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 09/12/19 alle ore 14:39:08