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In electrochemical systems, an understanding of the underlying transportprocesses is required to aid in their better design. This includes knowledge ofpossible near-electrode convective mixing that can enhance measured currents.Here, for a binary acidic electrolyte in contact with a platinum electrode, weprovide evidence of electroconvective instability during electrocatalyticproton reduction. The current-voltage characteristics indicate thatelectroconvection, visualized with a fluorescent dye, drives current densitieslarger than the diffusion transport limit. The onset and transition times ofthe instability do not follow the expected inverse-square dependence on thecurrent density, but, above a bulk-reaction-limited current density are delayedby the water dissociation reaction. The dominant size of the electroconvectivepatterns is also measured and found to vary as the diffusion length scale,confirming previous predictions on the size of electroconvective vortices.

Electroconvective instability in water electrolysis: an evaluation of electroconvective patterns and their onset features