Free-Energy-Averaged Potentials for Adsorption in Heterogeneous Slit Pores Using PC-SAFT Classical Density Functional Theory

This study analyzes the adsorption behavior in two-dimensional heterogeneous slit pores using nonlocal density functional theory based on the perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state. Both chemical heterogeneity and surface roughness on small atomistic scales are investigated. The solid structure is considered as individual solid interaction sites whereby chemical heterogeneity is introduced through the presence of different solid-fluid sites and molecular roughness by varying the position of the interaction sites in the first solid layers. The effect of both forms of heterogeneity on the adsorption behavior is assessed individually. Effective one-dimensional solid-fluid potentials provide a way to reduce the dimensionality and computational demand of the density functional theory (DFT) calculations. We determine one-dimensional free-energy-averaged (FEA) solid-fluid potentials of methane and n-butane in the low-density limit for solid systems with molecular roughness and chemical heterogeneity. Using this effective one-dimensional solid-fluid potential at any density, we find excellent agreement of adsorption isotherms for both solid descriptions in systems with homogeneous slit pores. Subcritical adsorption isotherms of n-butane in slit pores with surface roughness show deviations at higher pressures due to the formation of fluid layers in the one-dimensional FEA potential. Chemical heterogeneity introduces a shift of the capillary condensation pressure below the saturation pressure of the bulk liquid, which is well described by the free-energy-averaged system.

Automated summary

This study investigates the adsorption behavior in two-dimensional heterogeneous slit pores using nonlocal density functional theory, taking into account chemical heterogeneity and molecular roughness. By determining one-dimensional solid-fluid potentials, the computational demand of the density functional theory calculations is reduced. The research shows that adsorption isotherms in systems with homogeneous slit pores exhibit excellent agreement, but deviations occur in systems with surface roughness.