Adsorption and Solvation Modulate Rhodamine B Diffusion in Ethanol/Water-Filled Anodic Alumina Nanopores

Rashidi, Hamid; Nathani, Akash; Wang, Xiaoyu; Servis, Michael J.; Ito, Takashi; Higgins, Daniel A.

doi:10.1021/acs.jpcc.4c03189

Adsorption and Solvation Modulate Rhodamine B Diffusion in Ethanol/Water-Filled Anodic Alumina Nanopores

Journal Article · Wed Aug 14 00:00:00 EDT 2024 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.4c03189· OSTI ID:2467341

Rashidi, Hamid ^[1]; Nathani, Akash ^[2]; ^[3]; ^[3]; ^[2]; ^[2]

Kansas State University, Manhattan, KS (United States); Kansas State University; Kansas State University
Kansas State University, Manhattan, KS (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Confinement of solvents and solutes within nanoporous materials frequently leads to the emergence of unique mass transport behaviors that, once fully understood, may lead to improved chemical separations. Here, the diffusion of Rhodamine B (RhB) dye within 10 and 20 nm diameter anodic aluminum oxide (AAO) nanopores filled with binary ethanol/water mixtures is investigated. Mixture compositions spanning from pure ethanol to pure water are employed. The results of confocal fluorescence correlation spectroscopy studies reveal that RhB diffusion occurs by a two-component mechanism comprising composition-dependent fast and slow motions, characterized by diffusion coefficients D_f and D_s. The results are consistent with those of previous studies performed under more limited conditions [J. Phys. Chem. C, 2023, 127, 411-420]. The fast component scales with mixture viscosity and is assigned to hindered bulk-like diffusion in central pore regions. Slow diffusion likely involves adsorption of RhB to the pore surface and may be described by a desorption mediated mechanism. The occurrence of RhB adsorption to the AAO surface is verified at the single-molecule level by wide-field fluorescence imaging of membrane cross-sectional surfaces. Unique composition dependent trends in the autocorrelation amplitude and in D_s that mimic bulk RhB solubility are revealed. D_s is found to be smallest in pure ethanol and pure water and largest in intermediate mixtures. These results suggest that RhB surface adsorption is strongest in the pure liquids and weakest in mixtures of intermediate composition, where the dye is least soluble, and most soluble, respectively. As a result, molecular dynamics simulations reveal that a water layer appears on the pore surface under most conditions, while RhB is solvated primarily by ethanol. The composition dependence of RhB diffusion is concluded to reflect its solvation dependent interactions with the pore walls.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Kansas State University, Manhattan, KS (United States)

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

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

OSTI ID:: 2467341

Alternate ID(s):: OSTI ID: 2475562

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 34 Vol. 128; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Adsorption and Solvation Modulate Rhodamine B Diffusion in Ethanol/Water-Filled Anodic Alumina Nanopores

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