Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes
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 infra...
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2006
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15334880_v6_n6_p1731_Tagliazucchi http://hdl.handle.net/20.500.12110/paper_15334880_v6_n6_p1731_Tagliazucchi |
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paper:paper_15334880_v6_n6_p1731_Tagliazucchi2023-06-08T16:19:57Z Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes 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 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. 2006 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15334880_v6_n6_p1731_Tagliazucchi http://hdl.handle.net/20.500.12110/paper_15334880_v6_n6_p1731_Tagliazucchi |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
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 |
| spellingShingle |
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 Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes |
| topic_facet |
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 |
| description |
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. |
| title |
Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes |
| title_short |
Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes |
| title_full |
Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes |
| title_fullStr |
Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes |
| title_full_unstemmed |
Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes |
| title_sort |
oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes |
| publishDate |
2006 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15334880_v6_n6_p1731_Tagliazucchi http://hdl.handle.net/20.500.12110/paper_15334880_v6_n6_p1731_Tagliazucchi |
| _version_ |
1768543865210404864 |