Molecular simulation of the adsorption and diffusion in cylindrical nanopores – effect of shape and fluid-solid interactions
File(s)molecules-24-00608-v3.pdf (2.7 MB)
Published version
Author(s)
Cardenas, Harry
Muller, Erich
Type
Journal Article
Abstract
We report on molecular simulations of model fluids composed of three tangentially bonded Lennard-Jones interaction sites with three distinct morphologies: a flexible “pearl-necklace” chain, a rigid “stiff” linear configuration, and an equilateral rigid triangular ring. The adsorption of these three models in cylindrical pores of diameters 1, 2, and 3 nm and with varying solid–fluid strength was determined by direct molecular dynamics simulations, where a sample pore was placed in contact with a bulk fluid. Adsorption isotherms of Type I, V, and H1 were obtained depending on the choice of pore size and solid–fluid strength. Additionally, the bulk-phase equilibria, the nematic order parameter of the adsorbed phase, and the self-diffusion coefficient in the direction of the pore axis were examined. It was found that both the molecular shape and the surface attractions play a decisive role in the shape of the adsorption isotherm. In general, the ring molecules showed a larger adsorption, while the fully flexible model showed the smallest adsorption. Morphology and surface strength were found to have a lesser effect on the diffusion of the molecules. An exceptional high adsorption and diffusion, suggesting an enhanced permeability, was observed for the linear stiff molecules in ultraconfinement, which was ascribed to a phase transition of the adsorbed fluid into a nematic liquid crystal.
Date Issued
2019-02-09
Date Acceptance
2019-02-07
Citation
Molecules, 2019, 24 (3)
ISSN
1420-3049
Publisher
MDPI AG
Journal / Book Title
Molecules
Volume
24
Issue
3
Copyright Statement
© 2019by the authors. Submitted for possible open access publication under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/E016340/1
EP/J014958/1
Subjects
adsorption
diffusion
molecular dynamics
nanopores
0305 Organic Chemistry
Organic Chemistry
Publication Status
Published
Article Number
ARTN 608
Date Publish Online
2019-02-09