Stabilization of nanobubbles under hydrophobic confinement

TL;DR

This study uses molecular simulations to understand how nanobubbles form and are stabilized within hydrophobic confinement, revealing critical volume thresholds and the roles of hydrophobicity and hydrogen bonding in their stability.

Contribution

It provides a molecular-level explanation for nanobubble stabilization under hydrophobic confinement, identifying critical volume and the effects of hydrophobic surfaces and hydrogen bonds.

Findings

Identification of a critical nanobubble volume where stability is thermodynamically favored.

Demonstration that hydrophobic surfaces and hydrogen bonds assist nanobubble stabilization.

Elucidation of the nucleation pathway and free energy profile of nanobubbles in confined water.

Abstract

It has been recently shown that nanobubbles exhibit a remarkable and unexpected stability. The lifetime of nanobubbles, formed either within liquids or on hydrophobic surfaces, can exceed by more than 10 orders of magnitude the theoretical expectation, which predicts an almost immediate dissolution due to the very high Laplace internal pressure in such small bubbles. This unexpected property of nanobubbles has made them leading candidates for energy applications, e.g. as high-pressure nanoreactors in fuel cells, and for biological systems, as transport systems for gas delivery to membranes and cells. Here we use molecular simulation to shed light on the molecular mechanisms accounting for the formation and stabilization of nanobubbles under an hydrophobic nanoconfinement. Using an entropic reaction coordinate, we elucidate the nucleation pathway and determine the formation free energy of nanobubbles in water confined in carbon nanotubes. We identify a critical volume for which the existence of nanobubbles is thermodynamically favored, as the free energy profile flattens around this critical volume, and mechanically favored, since the nanoconfined fluid pressure, along the nanotube axis, is positive at this juncture. We also show that the stabilization process is assisted by the hydrophobic nature of the carbon nanotube and by the formation of strong hydrogen bonds at the interface. Caroline Desgranges and Jerome Delhommelle