Molecular Simulation of Sorption-Induced Deformation in Atomistic Nanoporous Materials.

Abstract

An atomistic slit pore model is built to study the sorption-induced deformation of nanoporous materials with the help of molecular simulation. Both sorption and strain isotherms are determined to probe the anisotropic deformation behavior induced upon molecular adsorption. A detailed analysis shows that the driving microscopic mechanisms at different sorption stages are different. At high relative pressure, as expected from the classical macroscopic picture, the pore deformation is governed by the Laplace pressure as the pore gets filled with liquid because of capillary condensation. In such situation, the strain in normal and longitudinal directions can be predicted from the stiffness modulus in the corresponding direction. At low pressure, when liquid films are adsorbed at the pore surfaces and separated by the vapor phase, the strain is driven by the attractive solid-fluid forces and in-plane pressure within the film, and the deformation is confined in the direction parallel to the film-solid interface. Because of the interplay of the two factors, the strain changes from shrinkage to expansion upon increase of pressure. Analysis of isosteric heat of adsorption shows that the contribution arising from the deformation is small compared to the sorption contribution, which indicates that the influence of deformation on the sorption process is limited.