Combined effects of electrode morphology and electrolyte composition on single H₂ gas bubble detachment during hydrogen evolution reaction

During the hydrogen evolution reaction, H₂ gas bubbles form on the electrode surface, significantly affecting electrochemical processes, particularly at high current densities. While promoting bubble detachment has been shown to enhance the current density, the mechanisms governing gas bubble detachment at the electrochemical interface remain poorly understood. In this study, we investigated the interplay between electrode surface morphology and electrolyte composition on single H₂ gas bubble detachment during hydrogen evolution reaction (HER). Using well-defined Pt microelectrodes as model systems, we systematically modify and enhance their surface roughness through mechanical polishing to investigate these effects in detail. By modulating the Marangoni effect through variations in electrolyte composition and applied potential, we identified two distinct detachment behaviours. When the Marangoni force acts towards the electrodes, H₂ gas bubbles are positioned closer to the electrode surface and exhibit roughness-dependent detachment, with smaller bubbles detaching earlier on rougher surfaces. Conversely, when the Marangoni force is directed away from the electrode, H₂ gas bubbles are located farther from the electrode surface and show roughness-independent detachment sizes. These findings highlight the importance of considering both electrode and electrolyte effects to optimize gas bubble detachment during electrochemical reactions.