Electrochemically Active Polyelectrolyte‐Modified Electrodes

Tagliazucchi, Mario; Calvo, Ernesto J.

doi:10.1002/9783527627059.ch2

Cited by 8 publications

(8 citation statements)

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“…Following the first examples of LbL-modified electrodes in 1997, the toolbox of redox-active building blocks has grown to include redox proteins, [2][3][4][5] inorganic complexes, [6,7] nanocrystals, [8] and several types of redox polyelectrolytes. [2,[9][10][11][12][13][14] Electrochemically active polyelectrolyte multilayers [15] have received widespread interest due to their potential applications in sensing, [2,4,9,10] electrochromic devices, [7][8][9]11] and as platforms for fundamental studies of redox proteins. [5] The timescale required to electrochemically switch the oxidation state of surface-confined redox species is a parameter that directly impacts on device performance.…”

Section: Introductionmentioning

confidence: 99%

Charge Transport in Redox Polyelectrolyte Multilayer Films: The Dramatic Effects of Outmost Layer and Solution Ionic Strength

Tagliazucchi

Calvo

2010

ChemPhysChem

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The redox switching kinetics, that is, charge transfer and transport in layer-by-layer-deposited electroactive polyelectrolyte multilayers is systematically studied with variable-scan-rate cyclic voltammetry. The experiments are performed with films finished in the redox polycation (an osmium pyridine-bipyridine derivatized polyallylamine, PAH-Os) and the polyanion (polyvinyl sulfonate, PVS), in solutions of different electrolyte concentrations. A modified diffusion model is developed to account for the experimentally observed dependence of the average peak potential with the scan rate. This model is able to describe both the redox peak potential and the current, providing information on the electron-transfer rate constants and the diffusion coefficient for the electron-hopping mechanism. While the former does not vary with the ionic strength or the nature of the outmost layer, polyanion-capped films present an electron-hopping diffusion coefficient at low ionic strength that is three orders of magnitude smaller than that for PAH-Os-capped films. The effect is offset at high ionic strength. We discuss the possible causes of the effect and the important consequences for electrochemical devices built by layer-by-layer self-assembly, such as amperometric biosensors or electrochromic devices.

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Section: Introductionmentioning

confidence: 99%

Charge Transport in Redox Polyelectrolyte Multilayer Films: The Dramatic Effects of Outmost Layer and Solution Ionic Strength

Tagliazucchi

Calvo

2010

ChemPhysChem

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“…Electrochemical charging/discharging of Fc groups in the Pt T film may be exploited to obtain quantitative information about the overall electrochemical activity and to study the coupled transport of counterions and solvent in and out of the films. 12,41 Moreover, analyses of the current−voltage shapes may reveal details regarding interactions between Fc and generated Fc + functionalities. 16 Figure 2A shows the response in Δf during the recording of three consecutive cyclic voltammetric cycles at a Pt T electrode in a blank electrolyte solution consisting of 0.1 M Bu 4 NBF 4 / MeCN.…”

Section: ■ Resultsmentioning

confidence: 99%

On Electrogenerated Acid-Facilitated Electrografting of Aryltriazenes to Create Well-Defined Aryl-Tethered Films

et al. 2013

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The mechanism of electrogenerated acid-facilitated electrografting (EGAFE) of the aryltriazene, 4-(3,3-dimethyltriaz-1-enyl)benzyl-1-ferrocene carboxylate, was studied in detail using electrochemical quartz crystal microbalance (EQCM) and cyclic voltammetry. The measurements support the previously suggested mechanism that electrochemical oxidation of the EGA agent (i.e., N,N'-diphenylhydrazine) occurs on the forward oxidative sweep to generate protons, which in turn protonate the aryltriazene to form the corresponding aryldiazonium salt close to the electrode surface. On the reverse sweep, the electrochemical reduction of the aryldiazonium salt takes place, resulting in the electrografting of aryl groups. The EGAFE-generated film consists of a densely packed layer of ferrocenyl groups with nearly ideal electrochemical properties. The uncharged grafted film contains no solvent and electrolyte, but counterions and solvent can easily enter and be accommodated in the film upon charging. It is shown that all ferrocene moieties present in the multilayered film are electrochemically active, suggesting that the carbon skeleton possesses a sufficiently high flexibility to allow the occurrence of fast electron transfers between the randomly located redox stations. In comparison, EQCM measurements on aryldiazonium-grafted films reveal that they have a substantially smaller electrolyte uptake during charging and that they contain only 50% electroactive ferrocenyl groups relative to weight. Hence, half of these films consist of entrapped supporting electrolyte/solvent and/or simply electrochemically inactive material due to solvent inaccessibility.

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“…Polymer-and polyelectrolyte-modified electrodes and supramolecular polymers on top of electrodes have been reviewed recently [423,424].…”

Section: Electrochemically Induced Complexationmentioning

confidence: 99%

Porous Carbons – Hyperbranched Polymers – Polymer Solvation

Long

Voit

Okay

2015

Advances in Polymer Science

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Electrochemically Active Polyelectrolyte‐Modified Electrodes

Cited by 8 publications

References 209 publications

Charge Transport in Redox Polyelectrolyte Multilayer Films: The Dramatic Effects of Outmost Layer and Solution Ionic Strength

Charge Transport in Redox Polyelectrolyte Multilayer Films: The Dramatic Effects of Outmost Layer and Solution Ionic Strength

On Electrogenerated Acid-Facilitated Electrografting of Aryltriazenes to Create Well-Defined Aryl-Tethered Films

Porous Carbons – Hyperbranched Polymers – Polymer Solvation

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