Nitrogen Bubbles at Pt Nanoelectrodes in a Nonaqueous Medium: Oscillating Behavior and Geometry of Critical Nuclei.

Gas bubble evolution is present in many electrochemical and photoelectrochemical processes. We previously reported the formation of individual H2, N2, and O2 nanobubbles generated from electrocatalytic reduction of H+ and oxidation of N2H4 and H2O2, respectively, at Pt nanodisk electrodes in an aqueous solution. All the nanobubbles formed display a dynamic stationary state of a three-phase boundary with an invariant residual current. Here, we test the hypothesis that gas nanobubbles can also be electrogenerated in a nonaqueous medium. Interestingly, we found oscillating bubble behavior corresponding to nucleation, growth, and dissolution in dimethyl sulfoxide and methanol. One possible explanation of the oscillation mechanism is provided by the instable dynamic equilibrium between the gas influx due to supersaturation and outflux due to Laplace pressure. Furthermore, the critical gas concentrations for N2 nanobubble nucleation are estimated to be 148, 386, 200, and 16 times supersaturation and the contact angles of the critical nuclei to be 164°, 151°, 160°, and 174° in water, dimethyl sulfoxide, ethylene glycol, and methanol, respectively. This is the first report on electrochemical nucleation of gas bubbles in nonaqueous solvents. Our electrochemical gas bubble study based on a nanoelectrode platform has proven to be a prototypical example of single-entity electrochemistry.