A molecular theory of chemically modified electrodes with self-assembled redox polyelectrolye thin films: Reversible cyclic voltammetry

Mario Tagliazucchi, Ernesto J. Calvo*, Igal Szleifer

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

A molecular theory of chemically modified electrodes is applied to study redox polyelectroyte modified electrodes. The molecular approach explicitly includes the size, shape, charge distribution, and conformations of all of the molecular species in the system as well as the chemical equilibria (redox and acid-base) and intermolecular interactions. An osmium pyridine-bipyridine complex covalently bound to poly(allyl-amine) backbone (PAH-Os) adsorbed onto mercapto-propane sulfonate (MPS) thiolated gold electrode is described. The potential and electrolyte composition dependent redox and nonredox capacitance can be calculated with the molecular theory in very good agreement with voltammetric experiments under reversible conditions without the use of freely adjustable parameter. Unlike existing phenomenological models the theory links the electrochemical behavior with the structure of the polymer layer. The theory predicts a highly inhomogeneous distribution of acid-base and redox states that strongly couples with the spatial arrangement of the molecular species in the nanometric redox film.

Original languageEnglish (US)
Pages (from-to)6740-6752
Number of pages13
JournalElectrochimica Acta
Volume53
Issue number23
DOIs
StatePublished - Oct 1 2008

Keywords

  • Charge regulation
  • Modified electrode
  • Molecular theory
  • Polyelectrolyte
  • Redox

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Electrochemistry

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