INVESTIGADORES
CALVO Ernesto Julio
artículos
Título:
Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayeer modified electrodes
Autor/es:
ERNESTO J. CALVO; MARIO TAGLIAZUCCHI; DORIS GRUMELLI; CECILIA BONAZZOLA
Revista:
Journal of Nanoscience and Nanotechnology
Editorial:
American Scientific Publishers
Referencias:
Año: 2006 vol. 6 p. 1731 - 1740
ISSN:
1533-4880
Resumen:
The oxidation¨Creduction dynamics of layer-by-layer (LbL) self-assembled redox polyelectrolyte
multilayer films on electrodes has been studied by cyclic voltammetry, chrono-amperometry, electrochemical
quartz crystal microbalance (EQCM), ellipsometry, and Fourier transform reflectionabsorption
infrared spectroscopy (FT-IRRAS). Thin layer electrochemistry with fast electron transfer
at the underlying metal-film interface and charge propagation by electron hopping between adjacent
redox sites in the finite thin film has been observed. An almost ideal cyclic voltammetry for a fixed
number of redox sites in the thin surface film suggests that the multilayer can be fully oxidized and
reduced in the time scale of the experiment (RT /vF ¡Ý 005 sec). The electron hopping diffusion
coefficient 3¡Á10−10 cm2 s−1 was obtained from the chronoamperometric current transient and the
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
coefficient 3¡Á10−10 cm2 s−1 was obtained from the chronoamperometric current transient and the
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
coefficient 3¡Á10−10 cm2 s−1 was obtained from the chronoamperometric current transient and the
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
RT /vF ¡Ý 005 sec). The electron hopping diffusion
coefficient 3¡Á10−10 cm2 s−1 was obtained from the chronoamperometric current transient and the
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
¡Á10−10 cm2 s−1 was obtained from the chronoamperometric current transient and the
ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl
redox concentration of Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.
Os = 4¡Á10−10 mol ¡¤cm−2 for (PAH-Os)5(PVS)4 film. Exchange of ions and
solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the
ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar
mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or
solvent which suggests an important flux of solvent during redox switching. An initial ¡°break in¡± effect
is observed for the first oxidation¨Creduction cycles when a newly self-assembled film equilibrates
with the electrolyte as charge is injected during the electrochemical perturbation.