Fluctuation enhanced electrochemical reaction rates at the nanoscale.
The electrode potential constitutes a dynamical variable whenever an electrode is resistively coupled to the electric circuit. We show that at the nanoscale, the discreteness and stochasticity of an electron transfer event causes fluctuations of the electrode potential that render all elementary electrochemical reactions to be faster on a nanoelectrode than predicted by the macroscopic (Butler-Volmer) electrochemical kinetics. This phenomenon is substantiated by means of a generalized (electro)chemical master equation.
García-Morales
Vladimir
V
Physik-Department E19a, Technische Universität München, James-Franck-Strasse 1, D-85748 Garching, Germany. vmorales@ph.tum.de
Krischer
Katharina
K
D000465:Algorithms; D004553:Electric Conductivity; D055664:Electrochemical Techniques / Q000295:instrumentation / Q000379:methods*; D004566:Electrodes; D006861:Hydrogen Peroxide / Q000737:chemistry; D007700:Kinetics; D008956:Models, Chemical; D036103:Nanotechnology / Q000379:methods*; D010084:Oxidation-Reduction
D006861:Hydrogen Peroxide