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

Pierre Letellier (1) , Mireille Turmine (1)

1 LISE - Laboratoire Interfaces et Systèmes Electrochimiques

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 nanopar-ticles and in particular to voltammetry. We proposed here a generalization of Plieth’s relationship fornon-spherical aggregates by assuming that the interface between the particle and its environment isfuzzy. Thus, the relations of non-extensive thermodynamics can quantitatively account for the displace-ments of electro-oxidation potentials of metal nanoparticles deposited on electrodes, according to theirmeasured size. Our approach also permits to formally justify the stability of the particles may increase astheir size decreases, ( < 0). This is usually found when the aggregates are in close contact with a matrix(in the case, for example, of embedded particles).

Mots clés: Nonextensive thermodynamicsSize effectElectro-oxidationNanoparticles

Domaines: Chimie; Autre

Pierre Letellier, Mireille Turmine. Displacement of voltammetric peaks with nanoparticles size: a nonextensive thermodynamic approach. Electrochimica Acta, 2014, 127, pp.384-389. ⟨10.1016/j.electacta.2014.02.041⟩. ⟨hal-01079086⟩