title: Modeling the concentration dependence of the methanol self-diffusivity in faujasite systems: comparison with the liquid phase.
abstract: Molecular dynamics simulations were performed to understand further the concentration dependence of the self-diffusion of methanol in the faujasite zeolite systems. The evolution of the self-diffusivity was investigated as a function of coverage for DAY and NaY systems to study the effect of both the pore confinement and the presence of the extraframework cations within the supercage. It was found that the self-diffusivity decreases with loading for DAY, whereas for NaY it passes through a maximum at intermediate coverage, in agreement with pulse-field gradient NMR and quasi elastic neutron scattering data reported in similar systems. The activation energies of the methanol diffusion corresponding to a combination of both intra- and intercage motions were evaluated as a function of the coverage. The simulated trends are interpreted on the basis of the predominant interactions which take place in both systems. Finally, the preferential arrangement of the adsorbate molecules are provided and compared with those simulated in the liquid phase. For the fully loaded materials, it was seen that the methanol molecules form a one-dimensional hydrogen-bonded chain along the channels in DAY whereas only dimers are present in NaY.
authors.affiliation: The Davy Faraday Research Laboratory, Royal Institution of Great Britain, 21 Albemarle Street, London W1S 4BS, United Kingdom.
authors.forename: D F
authors.initials: DF
authors.lastname: Plant
authors.forename: G
authors.initials: G
authors.lastname: Maurin
authors.forename: R G
authors.initials: RG
authors.lastname: Bell