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Displacement of voltammetric peaks with nanoparticles size: a nonextensive thermodynamic approach

Authors
  • Letellier, Pierre
  • Turmine, Mireille1, 2, 3, 4
  • 1 Sorbonne Universités
  • 2 UPMC Univ Paris 06, UMR 8235
  • 3 Laboratoire Interfaces et Systèmes Electrochimiques, F-75005
  • 4 CNRS, UMR 8235, LISE, F-75005
Type
Published Article
Journal
Electrochimica Acta
Publisher
Elsevier
Publication Date
Jan 01, 2014
Accepted Date
Feb 08, 2014
Volume
127
Pages
384–389
Identifiers
DOI: 10.1016/j.electacta.2014.02.041
Source
Elsevier
Keywords
License
Unknown

Abstract

We show here that the concepts of nonextensive thermodynamics (NET), described previously (J. Phys. Chem. B, 2004, 108, 18980) and applied to redox behavior of nanoparticles (J. Phys. Chem. C, 2008, 112, 12116) can be used to express by a power law the variations to the electrochemical kinetics of nanoparticles and in particular to voltammetry. We proposed here a generalization of Plieth's relationship for non-spherical aggregates by assuming that the interface between the particle and its environment is fuzzy. Thus, the relations of non-extensive thermodynamics can quantitatively account for the displacements of electro-oxidation potentials of metal nanoparticles deposited on electrodes, according to their measured size. Our approach also permits to formally justify the stability of the particles may increase as their size decreases, (τ<0). This is usually found when the aggregates are in close contact with a matrix (in the case, for example, of embedded particles).

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