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Abstract:

A molecular theory of chemically modified electrodes is applied to study redox polyelectroyte modified electrodes. The molecular approach explicitly includes the size, shape, charge distribution, and conformations of all of the molecular species in the system as well as the chemical equilibria (redox and acid-base) and intermolecular interactions. An osmium pyridine-bipyridine complex covalently bound to poly(allyl-amine) backbone (PAH-Os) adsorbed onto mercapto-propane sulfonate (MPS) thiolated gold electrode is described. The potential and electrolyte composition dependent redox and nonredox capacitance can be calculated with the molecular theory in very good agreement with voltammetric experiments under reversible conditions without the use of freely adjustable parameter. Unlike existing phenomenological models the theory links the electrochemical behavior with the structure of the polymer layer. The theory predicts a highly inhomogeneous distribution of acid-base and redox states that strongly couples with the spatial arrangement of the molecular species in the nanometric redox film. © 2008 Elsevier Ltd. All rights reserved.

Registro:

Documento: Artículo
Título:A molecular theory of chemically modified electrodes with self-assembled redox polyelectrolye thin films: Reversible cyclic voltammetry
Autor:Tagliazucchi, M.; Calvo, E.J.; Szleifer, I.
Filiación:INQUIMAE, DQIAyQF Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires, Argentina
Department of Biomedical Engineering, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United States
Palabras clave:Charge regulation; Modified electrode; Molecular theory; Polyelectrolyte; Redox; Amines; Bioelectric phenomena; Charge distribution; Cyclic voltammetry; Electrodes; Electrolysis; Gold; Gold compounds; Metallizing; Molecular structure; Organic compounds; Osmium; Parameter estimation; Propane; Size distribution; Thick films; Voltammetry; (001) parameter; (e ,2e) theory; (I ,J) conditions; Acid base; Applied (CO); bipyridine; Chemical equilibriums; Chemically modified electrode (CME); Covalently bound; Electrochemical behaviors; Electrolyte compositions; Elsevier (CO); Gold electrodes; Inhomogeneous distribution; Intermolecular interactions (IMI); Modified electrodes; Molecular approach; Molecular species; Molecular theory; Nanometric; Phenomenological modeling; Polymer layers; Redox states; Self-assembled; Spatial arrangements; voltammetric experiments; Molecules
Año:2008
Volumen:53
Número:23
Página de inicio:6740
Página de fin:6752
DOI: http://dx.doi.org/10.1016/j.electacta.2008.01.041
Título revista:Electrochimica Acta
Título revista abreviado:Electrochim Acta
ISSN:00134686
CODEN:ELCAA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00134686_v53_n23_p6740_Tagliazucchi

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Citas:

---------- APA ----------
Tagliazucchi, M., Calvo, E.J. & Szleifer, I. (2008) . A molecular theory of chemically modified electrodes with self-assembled redox polyelectrolye thin films: Reversible cyclic voltammetry. Electrochimica Acta, 53(23), 6740-6752.
http://dx.doi.org/10.1016/j.electacta.2008.01.041
---------- CHICAGO ----------
Tagliazucchi, M., Calvo, E.J., Szleifer, I. "A molecular theory of chemically modified electrodes with self-assembled redox polyelectrolye thin films: Reversible cyclic voltammetry" . Electrochimica Acta 53, no. 23 (2008) : 6740-6752.
http://dx.doi.org/10.1016/j.electacta.2008.01.041
---------- MLA ----------
Tagliazucchi, M., Calvo, E.J., Szleifer, I. "A molecular theory of chemically modified electrodes with self-assembled redox polyelectrolye thin films: Reversible cyclic voltammetry" . Electrochimica Acta, vol. 53, no. 23, 2008, pp. 6740-6752.
http://dx.doi.org/10.1016/j.electacta.2008.01.041
---------- VANCOUVER ----------
Tagliazucchi, M., Calvo, E.J., Szleifer, I. A molecular theory of chemically modified electrodes with self-assembled redox polyelectrolye thin films: Reversible cyclic voltammetry. Electrochim Acta. 2008;53(23):6740-6752.
http://dx.doi.org/10.1016/j.electacta.2008.01.041