Nucleation of surface nanobubbles in electrochemistry: Analysis with nucleation theorem

The formation of single bubbles at nanoelectrodes during electrochemical reactions allows to accurately identify the critical nucleus for bubble formation. As demonstrated before, combining nanoelectrode experiments and an analysis approach based on classical nucleation theory (CNT) delivers useful insight into bubble nucleation. In this work we propose an alternative approach to analyze the critical nuclei by applying the nucleation theorem (NT), which is able to overcome the inherent shortcomings of CNT. The size of the critical nucleus can be calculated more accurately by fitting experimental data in a simple form of the NT. Simulating the local gas concentration using a finite element approach, and considering the effect of gas oversaturation on the interfacial tension and the real gas compressibility, we obtain a more realistic estimation of the critical nuclei morphology. With the NT-based analysis presented, we re-analyze the nucleation data reported before. The properties of the critical nuclei obtained here are roughly consistent with those obtained from the CNT-based approach. In addition, we confirm that the critical nucleus for bubble formation in high gas oversaturation is featured with a contact angle much larger than Young's contact angle.