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Abstract:

A probe beam deflection (PBD) study of ion exchange between an electroactive polymer poly(allylamine)bipyridyl-pyridine osmium complex film and liquid electrolyte is reported. The PBD measurements were made simultaneously to chronoamperometric oxidation-reduction cycles, to be able to detect kinetic effects in the ion exchange. Layer-by-layer (LbL) self-assembled redox polyelectrolyte films with osmium bipyridyl complex covalently attached to poly(allylamine) (PAH-Os) and poly(styrene sulfonate) (PSS) have been built by alternate electrostatic adsorption from soluble polyelectrolytes. The ionic exchange during initial conditioning of the film ("break-in") undergoing oxidation-reduction cycles and recovery after equilibration in the reduced state have shown an exchange of anions and cations with time lag between them. The effect of the nature of cation on the ionic exchange has been investigated with dilute HCl, LiCl, NaCl, and CsCl electrolytes. The ratio of anion to cation exchanged at the film-electrolyte interface has a strong dependence on the nature of charge in the topmost layer, that is, when negatively charged PSS is the capping layer, a larger proportion of cation exchange is observed. This demonstrates that the electrical potential distribution at the redox polyelectrolyte multilayer (PEM)/electrolyte interface determines the ionic flux in response to charge injection in the film. © 2006 American Chemical Society.

Registro:

Documento: Artículo
Título:Dynamics of ion exchange between self-assembled redox polyelectrolyte multilayer modified electrode and liquid electrolyte
Autor:Grumelli, D.E.; Garay, F.; Barbero, C.A.; Calvo, E.J.
Filiación:INQUIMAE, Departamento de Química Inorgánica, Analítica y Química Física, Ciudad Universitaria, AR-1428 Buenos Aires, Argentina
INFIQC, Departamento de Fisicoquimica, Ciudad Universitaria, 5000-Cordoba, Argentina
Departamento de Química, Universidad Nacional de Río Cuarto (UNRC), Agencia Postal No. 3, AR-5800 Río Cuarto, Argentina
Palabras clave:Adsorption; Chemical bonds; Electric potential; Ion exchange; Multilayers; Polystyrenes; Self assembly; Electrostatic adsorption; Liquid electrolyte; Poly(styrene sulfonate) (PSS); Probe beam deflection (PBD); Polyelectrolytes
Año:2006
Volumen:110
Número:31
Página de inicio:15345
Página de fin:15352
DOI: http://dx.doi.org/10.1021/jp062282g
Título revista:Journal of Physical Chemistry B
Título revista abreviado:J Phys Chem B
ISSN:15206106
CODEN:JPCBF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15206106_v110_n31_p15345_Grumelli

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Citas:

---------- APA ----------
Grumelli, D.E., Garay, F., Barbero, C.A. & Calvo, E.J. (2006) . Dynamics of ion exchange between self-assembled redox polyelectrolyte multilayer modified electrode and liquid electrolyte. Journal of Physical Chemistry B, 110(31), 15345-15352.
http://dx.doi.org/10.1021/jp062282g
---------- CHICAGO ----------
Grumelli, D.E., Garay, F., Barbero, C.A., Calvo, E.J. "Dynamics of ion exchange between self-assembled redox polyelectrolyte multilayer modified electrode and liquid electrolyte" . Journal of Physical Chemistry B 110, no. 31 (2006) : 15345-15352.
http://dx.doi.org/10.1021/jp062282g
---------- MLA ----------
Grumelli, D.E., Garay, F., Barbero, C.A., Calvo, E.J. "Dynamics of ion exchange between self-assembled redox polyelectrolyte multilayer modified electrode and liquid electrolyte" . Journal of Physical Chemistry B, vol. 110, no. 31, 2006, pp. 15345-15352.
http://dx.doi.org/10.1021/jp062282g
---------- VANCOUVER ----------
Grumelli, D.E., Garay, F., Barbero, C.A., Calvo, E.J. Dynamics of ion exchange between self-assembled redox polyelectrolyte multilayer modified electrode and liquid electrolyte. J Phys Chem B. 2006;110(31):15345-15352.
http://dx.doi.org/10.1021/jp062282g