Non-Nernstian Two-Electron Transfer Reactions for Immobilized Molecules: A Theoretical Study in Cyclic Voltammetry

作者：Gonzalez Joaquin; Lopez Tenes Manuela; Molina Angela^*

来源：Journal of Physical Chemistry C, 2013, 117(10): 5208-5220.

DOI：10.1021/jp312621u

A very simple recurrent theoretical treatment for non-Nernstian two-electron transfer reactions for surface confined molecules is presented and applied to cyclic voltammetry (CV). A systematic kinetic study via the influence on the voltammograms of the variation of the heterogeneous rate constants of both electron transfers (ETs) and the scan rate has been made. The influence of the difference between the formal potentials (Delta E-0) and of the rate constants on the degree of cooperativity of the ETs is analyzed. An illustrative zone diagram that enables a direct view of the number of peaks in the voltammogram as a function of Delta E-0 and the heterogeneous rate constants as well as methods for determining thermodynamic and kinetic parameters are proposed. This treatment is very useful for any two redox center molecules and is hugely important for modeling noncatalytic voltammetry of redox enzymes attached to the electrode that represent a starting point for understanding more complex situations like coupled catalytic and intramolecular ETs processes.

• 出版日期2013-3-14