Abstract:
The oxidation-reduction 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 reflection-absorption 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 ≥ 0.05 sec The electron hopping diffusion coefficient 3 × 10 -10 cm 2 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 Γ Os = 4 × 10 -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-reduction cycles when a newly self-assembled film equilibrates with the electrolyte as charge is injected during the electrochemical perturbation. Copyright © 2006 American Scientific Publishers All rights reserved.
Registro:
Documento: |
Artículo
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Título: | Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes |
Autor: | Tagliazucchi, M.; Grumelli, D.; Bonazzola, C.; Calvo, E.J. |
Filiación: | INQUIMAE, Departamento de Química Inorgánica, Analítica y Química Física, Universidad de Buenos Aires, Argentina
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Palabras clave: | Ellipsometry; EQCM; Layer by Layer; Osmium Bipyridyl; Redox Polyelectrolyte; Self-Assembled; Electrochemical quartz crystal microbalance (EQCM); Electron hopping; Osmium Bipyridyl; Redox polyelectrolytes; Cyclic voltammetry; Ellipsometry; Fourier transform infrared spectroscopy; Multilayers; Oxidation; Polyelectrolytes; Redox reactions; Reduction; Self assembly; Electrochemical electrodes; electrolyte; organometallic compound; Os(Bpy)2CIPyCH2NH poly(allylamine); Os(Bpy)2CIPyCH2NH-poly(allylamine); osmium derivative; polymer; article; chemistry; electrochemistry; electrode; infrared spectrophotometry; infrared spectroscopy; methodology; nanotechnology; oxidation reduction reaction; Electrochemistry; Electrodes; Electrolytes; Nanotechnology; Organometallic Compounds; Osmium Compounds; Oxidation-Reduction; Polymers; Spectrophotometry, Infrared; Spectroscopy, Fourier Transform Infrared |
Año: | 2006
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Volumen: | 6
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Número: | 6
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Página de inicio: | 1731
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Página de fin: | 1740
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DOI: |
http://dx.doi.org/10.1166/jnn.2006.237 |
Título revista: | Journal of Nanoscience and Nanotechnology
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Título revista abreviado: | J. Nanosci. Nanotechnol.
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ISSN: | 15334880
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CAS: | Electrolytes; Organometallic Compounds; Os(Bpy)2CIPyCH2NH-poly(allylamine); Osmium Compounds; Polymers
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15334880_v6_n6_p1731_Tagliazucchi |
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Citas:
---------- APA ----------
Tagliazucchi, M., Grumelli, D., Bonazzola, C. & Calvo, E.J.
(2006)
. Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes. Journal of Nanoscience and Nanotechnology, 6(6), 1731-1740.
http://dx.doi.org/10.1166/jnn.2006.237---------- CHICAGO ----------
Tagliazucchi, M., Grumelli, D., Bonazzola, C., Calvo, E.J.
"Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes"
. Journal of Nanoscience and Nanotechnology 6, no. 6
(2006) : 1731-1740.
http://dx.doi.org/10.1166/jnn.2006.237---------- MLA ----------
Tagliazucchi, M., Grumelli, D., Bonazzola, C., Calvo, E.J.
"Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes"
. Journal of Nanoscience and Nanotechnology, vol. 6, no. 6, 2006, pp. 1731-1740.
http://dx.doi.org/10.1166/jnn.2006.237---------- VANCOUVER ----------
Tagliazucchi, M., Grumelli, D., Bonazzola, C., Calvo, E.J. Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes. J. Nanosci. Nanotechnol. 2006;6(6):1731-1740.
http://dx.doi.org/10.1166/jnn.2006.237