Electrochemical Nucleation of Stable N2 Nanobubbles at Pt Nanoelectrodes.

Abstract

Exploring the nucleation of gas bubbles at interfaces is of fundamental interest. Herein, we report the nucleation of individual N2 nanobubbles at Pt nanodisk electrodes (6–90 nm) via the irreversible electrooxidation of hydrazine (N2H4 → N2 + 4H(+) + 4e(–)). The nucleation and growth of a stable N2 nanobubble at the Pt electrode is indicated by a sudden drop in voltammetric current, a consequence of restricted mass transport of N2H4 to the electrode surface following the liquid-to-gas phase transition. The critical surface concentration of dissolved N2 required for nanobubble nucleation, CN2,critical(s), obtained from the faradaic current at the moment just prior to bubble formation, is measured to be ∼0.11 M and is independent of the electrode radius and the bulk N2H4 concentration. Our results suggest that the size of stable gas bubble nuclei depends only on the local concentration of N2 near the electrode surface, consistent with previously reported studies of the electrogeneration of H2 nanobubbles. CN2,critical(s) is ∼160 times larger than the N2 saturation concentration at room temperature and atmospheric pressure. The residual current for N2H4 oxidation after formation of a stable N2 nanobubble at the electrode surface is proportional to the N2H4 concentration as well as the nanoelectrode radius, indicating that the dynamic equilibrium required for the existence of a stable N2 nanobubble is determined by N2H4 electrooxidation at the three phase contact line.