The dynamical behavior of an array of microelectrodes is investigated under controlled current conditions during CO electrooxidation, a bistable electrochemical reaction with an S-shaped negative differential resistance (S-NDR) current-potential curve. Under these conditions, the total current constitutes a globally conserved quantity, thus coupling all microelectrodes globally. Upon increasing the total current, the microelectrodes activate one by one, with a single microelectrode being on its intermediate S-NDR current branch and the other ones being either on their passive or their active branches. When a few coupled microelectrodes are activated, the electrochemical system exhibits spontaneous potential oscillations. Mathematical analysis shows that oscillations arise already in a two group approximation of the dynamics, the two groups consisting of 1 electrode and n – 1 electrodes with n ≥ 3, respectively, with each group being described by a single evolution equation. In this minimal representation, oscillations occur when the single electrode is on the intermediate branch and the larger group is on the active branch.
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