Electrolyte design for the manipulation of gas bubble detachment during hydrogen evolution reaction

During electrochemical gas evolution reactions, the continuous and vigorous formation of gas bubbles hugely impacts the efficiency of the underlying electrochemical processes. In particular, enhancing the detachment of gas bubbles from the electrode surface has emerged as an effective strategy to improve reaction efficiency. In this study, we demonstrate that the detachment of H₂ gas bubbles can be controlled by the electrolyte composition, which can be optimized. We employ a well-defined Pt microelectrode and utilize electrochemical oscillation analysis to elucidate the features of H₂ gas bubble detachment. Our investigation explores how the behaviour of H₂ gas bubbles responds to variations in electrolyte composition and concentration. The coalescence efficiency of electrochemically generated microbubbles, a critical factor determining the mode of H₂ gas bubble detachment (random detachment vs. single H₂ gas bubble detachment), is profoundly influenced by the electrolyte composition. Specifically, coalescence efficiency follows the Hofmeister series concerning anions and coalescence is consistently inhibited in the presence of alkali metal cations. Furthermore, we establish a comprehensive model that accounts for both thermal and solutal Marangoni effects, allowing us to rationalize the trend of detachment size and period of single H₂ gas bubbles under various conditions.