The coupling behavior of multiple working electrodes with a reference and counter electrode has been explored in several different electrochemical systems (Cruz, Rivera, & Parmananda, 2007; I. Z. Kiss & Hudson, 2002). Many phenomena are known to exist at far-from-equilibrium conditions such as in-phase(István Z Kiss & Hudson, 2001; I.Z. Kiss, Zhai, & Hudson, 2005), anti-phase(I.Z. Kiss et al., 2005), and out-of-phase(István Z Kiss, Lv, & Hudson, 2005) synchronization, clustering(Wang, Kiss, & Hudson, 2000), and chimera states (Wickramasinghe & Kiss, 2013, 2014). Large majority of these studies was performed in the traditional ‘three-electrode’ configuration with reference, counter, and a multi-electrode array as a working electrode. The coupling among the working electrodes typically occurs through an external resistance interface (I. Z. Kiss, Wang, & Hudson, 1999) or through potential drops in the electrolyte (Jain, Kiss, Breidenich, & Hudson, 2009). In this contribution, we explore the nonlinear dynamics of oscillatory Ni dissolution in a multi-electrode array anode system; instead of the traditional reference/counter electrodes, we apply a single nickel cathode. Kinetic models for the multi-anode single cathode reaction system reveal that the cathode reaction acts as coupling element through dynamical quorum sensing (Tinsley, Taylor, Huang, Wang, & Showalter, 2010) mechanism. We explore the nonlinear dynamics of the coupled system with oscillatory anodic Ni dissolution on the anodes and hydrogen reduction reaction on the cathode. In experiments with two anodes we observe phase drifting (desynchronized), phase slipping (weak coupling), and phase locking (both in-phase and anti-phase) between the two anodes depending on the individual resistance in the system. In a system with 40 electrodes we have seen desynchronized and synchronized one-cluster and two-cluster patterns. With increasing the number of anodes we see a transition from a stationary state to desynchronized or synchronized oscillations depending on the individual resistance of the anodes. The experiments thus show that changing the number of anodes can induce a quorum-type (population dependent) transition into synchrony. The results also imply that description of nontrivial cathode-anode interactions in the form of dynamical quorum sensing provides an efficient way of predicting the dynamical response of complex, interacting electrochemical reactions.<br/>

Synchrony transitions due to dynamical quorum sensing in single-cathode multi-anode nickel dissolution system

251st National Meeting (2016)

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