Proving and interpreting the spontaneous formation of bulk nanobubbles in aqueous organic solvent solutions: effects of solvent type and content.

We show that the mixing of organic solvents with pure water leads to the spontaneous formation of suspended nano-entities which exhibit long-term stability on the scale of months. A wide range of solvents representing different functional groups are studied: methanol, ethanol, propanol, acetone, DMSO and formamide. We use various physical and chemical analytical techniques to provide compounded evidence that the nano-entities observed in all these aqueous solvent solutions must be gas-filled nanobubbles as they cannot be attributed to solvent nanodroplets, impurities or contamination. The nanobubble suspensions are characterized in terms of their bubble size distribution, bubble number density and zeta potential. The bubble number density achieved is a function of the type of solvent. It increases sharply with solvent content, reaching a maximum at an intermediate solvent concentration, before falling off to zero. We show that, whilst bulk nanobubbles can exist in pure water, they cannot exist in pure organic solvents and they disappear at some organic solvent-water ratio depending on the type of solvent. The gas solubility of the solvent relative to water as well as the molecular structure of the solvent are determining factors in the formation and stability of bulk nanobubbles. These phenomena are discussed and interpreted in the light of the experimental results obtained.