Thermocapillary convection during hydrogen evolution at microelectrodes

Abstract The origin of strong electrolyte flow during water electrolysis is investigated, that arises at the interface between electrolyte and hydrogen bubbles evolving at microelectrodes. This Marangoni convection was unveiled only recently (Yang et al., PCCP, 2018, [1]) and is supposed to be driven by shear stress at the gas-liquid interface caused by thermal and concentration gradients. The present work firstly allows a quantification of the thermocapillary effect and discusses further contributions to the Marangoni convection which may arise also from the electrocapillary effect. Hydrogen gas bubbles were electrolytically generated at a horizontal Pt microelectrode in a 1 M H2SO4 solution. Simultaneous measurements of the velocity and the temperature field of the electrolyte close to the bubble interface were performed by means of particle tracking velocimetry and luminescent lifetime imaging. Additionally, corresponding numerical simulations of the temperature distribution in the cell and the electrolyte flow resulting from thermocapillary stress only were performed. The results confirm significant Ohmic heating near the micro-electrode and a strong flow driven along the interface away from the microelectrode. The results further show an excellent match between simulation and experiment for both the velocity and the temperature field within the wedge-like electrolyte volume at the bubble foot close to the electrode, thus indicating the thermocapillary effect as the major driving mechanism of the convection. Further away from the microelectrode, but still below the bubble equator, however, quantitative differences between experiment and simulation appear in the velocity field, whereas the temperature gradient still matches well. Thus, additional effects must act on the interface, which are not yet included in the present simulation. The detailed discussion tends to rule out solution-based effects, generally referred to as solutal effects, whereas electrocapillary effects are likely to play a role. Finally, the thermocapillary effect is found to exert a force on the bubble which is retarding its departure from the electrode.