In electrochemical systems, an understanding of the underlying transport processes is required to aid in their better design. This includes knowledge of possible near-electrode convective mixing that can enhance measured currents. Here, for a binary acidic electrolyte in contact with a platinum electrode, we provide evidence of electroconvective instability during electrocatalytic proton reduction. The current-voltage characteristics indicate that electroconvection, visualized with a fluorescent dye, drives current densities larger than the diffusion transport limit. The onset and transition times of the instability do not follow the expected inverse-square dependence on the current density, but, above a bulk-reaction-limited current density, are delayed by the water dissociation reaction, that is, the formation of H+ and OH- ions. The dominant size of the electroconvective patterns is also measured and found to vary with the diffusion length scale, confirming previous predictions on the size of electroconvective vortices.