Random Walks and Sticky Surfaces: Single-Molecule Measurements of Solute Diffusion in Ethanol/Water-Filled Anodic Alumina Nanopores

Abstract

Nanoporous anodic aluminum oxide (AAO) membranes are now being explored for use in advanced chemical separations, including in the dehydration of biofuels such as ethanol. Optimization of membrane performance requires an in-depth understanding of how solvent mixtures and solutes behave under nanoconfinement. In this work, the diffusion of rhodamine B (RhB) dye through 10 and 20 nm AAO nanopores filled with a series of ethanol/water mixtures (0–33% water) is explored by fluorescence correlation spectroscopy (FCS). RhB was found to diffuse through the pores by two distinct mechanisms with mean diffusion coefficients, Df and Ds, reflecting fast and slow diffusive motions, respectively, with values that differ by nearly 2 orders of magnitude. Both Df and Ds increased with pore size and were significantly smaller than Db, the RhB diffusion coefficient in bulk liquid. Mean Df values follow a composition-dependent trend that closely mimics the viscosity dependence of Db. Additional slowing of fast RhB diffusion is attributed to both hydrodynamic drag and electrostatic interactions with the nanopore surface. The mean Ds values exhibit a different trend with increasing water content, revealing an increase in Ds and a decrease in the contributions of slow diffusion to the observed dynamics. The fluorescence time transient data used in the analysis show that the slow diffusion process is strongly hindered and likely involves frequent adsorption of RhB to the pore surfaces. These results provide new insights into the detailed molecular-level mechanisms of mass transport in nanoporous AAO membranes.