Spatiotemporal self-organization in the oscillatory HCOOH oxidation on a Pt ribbon electrode - Theory and experiments

Abstract

Since the current density near the edges of ribbon and disk electrodes is enhanced, the resulting stationary and non-stationary double layer potential is generally inhomogeneous in all electrochemical reactions. We investigate the impact of this edge effect induced spatial inhomogeneity on the pattern formation of the oscillatory formic acid oxidation on thin Pt ribbon electrodes. In order to be able to theoretically describe the spatiotemporal behavior of the double layer potential distribution, we derive and discuss the properties of the electrochemical ribbon coupling function for various distances of the reference electrode. The resulting reaction-migration equation is analyzed in connection with a chemical model accounting for the specific reaction mechanism of the formic acid oxidation. The interaction of structural inhomogeneity, chemically induced temporal instability and nonlocal spatial coupling due to ion migration gives rise to novel types of spatiotemporal behavior. The results compare favorably with experiments conducted so far, which are presented as well and can be explained within the framework of reaction-migration equations. © 2009 Elsevier B.V. All rights reserved.