Nanoscale Dynamics versus Surface Interactions: What Dictates Osmotic Transport?

The classical paradigm for osmotic transport has long related the induced-flow direction to the solute membrane interactions, with the low-to-high concentration flow a direct consequence of the solute rejection from the semipermeable membrane. In principle, the same was thought to occur for the newly demonstrated membrane-free osmotic transport named diffusio-osmosis. Using a recently proposed nanofluidic setup, we revisit this cornerstone of osmotic transport by studying the diffusio-osmotic flows generated at silica surfaces by either poly(ethylene)glycol polymers or ethanol molecules in aqueous solutions. Strikingly, both neutral solutes yield osmotic flows in the usual low to high concentration direction, in contradiction with their propensity to adsorb on silica. Considering theoretically and numerically the intricate nature of the osmotic response that combines molecular-scale surface interaction and near-wall dynamics, these findings are rationalized within a generalized framework. These elements constitute a step forward toward a finer understanding of osmotically driven flows, at the core of rapidly growing fields ranging from energy harvesting to active matter.