Molecular simulation of capillary phase transitions in flexible porous materials.

ABSTRACT

We used flat-histogram sampling Monte Carlo to study capillary phase transitions in deformable adsorbent materials. Specifically, we considered a pure adsorbate fluid below its bulk critical temperature within a slit pore of variable pore width. The instantaneous pore width is dictated by a number of factors, such as adsorbate loading, reservoir pressure, fluid-wall interaction, and bare adsorbent properties. In the slit pores studied here, the bare adsorbent free energy was assumed to be biparabolic, consisting of two preferential pore configurations, namely, the narrow pore and the large pore configurations. Four distinct phases could be found in the adsorption isotherms. We found a low-pressure phase transition, driven primarily by capillary condensation/evaporation and accompanied by adsorbent deformation in response. The deformation can be a relatively small contraction/expansion as seen in elastic materials, or a large-scale structural transformation of the adsorbent. We also found a high-pressure transition driven by excluded volume effects, which tends to expand the material and thus results in a large-scale structural transformation of the adsorbent. The adsorption isotherms and osmotic free energies can be rationalized by considering the relative free energy differences between the basins of the bare adsorbent free energy.