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

Rashidi, Hamid; Howard, Kampbell J.; Ito, Takashi; Higgins, Daniel A.

doi:10.1021/acs.jpcc.2c07083

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

Journal Article · Tue Dec 27 00:00:00 EST 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c07083· OSTI ID:1907562

Rashidi, Hamid ^[1]; Howard, Kampbell J. ^[1];

^[1];

^[1]

Kansas State Univ., Manhattan, KS (United States)

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 nm 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, $$D_f$$ and $$D_s$$, reflecting fast and slow diffusive motions, respectively, with values that differ by nearly two orders of magnitude. Further, both $$D_f$$ and $$D_s$$ increased with pore size and were significantly smaller than $$D_b$$, the RhB diffusion coefficient in bulk liquid. Mean $$D_f$$ values follow a composition-dependent trend that closely mimics the viscosity dependence of $$D_b$$. Additional slowing of fast RhB diffusion is attributed to both hydrodynamic drag and electrostatic interactions with the nanopore surface. The mean $$D_s$$ values exhibit a different trend with increasing water content, revealing an increase in $$D_s$$ 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.

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Research Organization:: Kansas State Univ., Manhattan, KS (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: SC0002362; AC02-06CH11357; CHE-1852182

OSTI ID:: 1907562

Journal Information:: Journal of Physical Chemistry. C, Vol. 127, Issue 1; Related Information: https://pubs.acs.org/doi/10.1021/acs.jpcc.2c07083; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
fluorescence correlation spectroscopy
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Title: Random Walks and Sticky Surfaces: Single-Molecule Measurements of Solute Diffusion in Ethanol/Water-Filled Anodic Alumina Nanopores

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