Confined Electrochemical Behaviors of Single Platinum Nanoparticles Revealing Ultrahigh Density of Gas Molecules inside a Nanobubble

Understanding the basic physicochemical properties of gas molecules confined within nanobubbles is of fundamental importance for chemical and biological processes. Here, we successfully monitored the nanobubble-confined electrochemical behaviors of single platinum nanoparticles (PtNPs) at a carbon fiber ultramicroelectrode in HClO4 and H2O2 solution. Due to the catalytic decomposition of H2O2, a single oxygen nanobubble was formed on individual PtNPs to block the active surface of particles for proton reduction and to suppress their stochastic motion, resulting in significantly distinguished current traces. Furthermore, the combination of theoretical calculations and high resolution electrochemical measurements allowed the nanobubble size and the oxygen gas density inside a single nanobubble to be quantified. Moreover, the ultrahigh oxygen density inside (1046 kg/m3) was revealed, indicating that gas molecules in a nanosized space existed with a high state of aggregation. Our approach sheds light on the gas aggregation behaviors of nanoscale bubbles using single-entity electrochemical measurements.