Dynamic Equilibrium Model for Surface Nanobubbles in Electrochemistry

YQ Ma and ZJ Guo and QJ Chen and XR Zhang, LANGMUIR, 37, 2771-2779 (2021).

DOI: 10.1021/acs.langmuir.0c03537

Gas bubbles are ubiquitous in electrochemical processes, particularly in water electrolysis. Due to the development of gas-evolving electrocatalysis and energy conversion technology, a deep understanding of gas bubble behaviors at the electrode surface is highly desirable. In this work, by combining theoretical analysis and molecular simulations, we study the behaviors of a single nanobubble electrogenerated at a nanoelectrode. With the dynamic equilibrium model, the stability criteria for stationary surface nanobubbles are established. We show theoretically that a slight change in either the gas solubility or solute concentration results in various nanobubble dynamic states at a nanoelectrode: contact line pinning in aqueous and ethylene glycol solutions, oscillation of pinning states in dimethyl sulfoxide, and mobile nanobubbles in methanol. The above complex nanobubble behavior at the electrode/electrolyte interface is explained by the competition between gas influx into the nanobubble and outflux from the nanobubble.

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