Abstract

Mass transport at infinite regular arrays of microband electrodes was investigated theoretically and experimentally in unstirred solutions. Even in the absence of forced hydrodynamics, natural convection limits the convection-free domain up to which diffusion layers may expand. Hence, several regimes of mass transport may take place according to the electrode size, gap between electrodes, time scale of the experiment, and amplitude of natural convection. They were identified through simulation by establishing zone diagrams that allowed all relative contributions to mass transport to be delineated. Dynamic and steady-state regimes were compared to those achieved at single microband electrodes. These results were validated experimentally by monitoring the chronoamperometric responses of arrays with different ratios of electrode width to gap distance and by mapping steady-state concentration profiles above their surface through scanning electrochemical microscopy.

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