Volume shrinkage of a metal–organic framework host induced by the dispersive attraction of guest gas molecules

Abstract

Using a density functional theory calculation including van der Waals (vdW) corrections, we report that H₂ adsorption in a cubic-crystalline microporous metal–organic framework (MOF-5) leads to volume shrinkage, which is in contrast to the intuition that gas adsorption in a confined system (e.g., pores in a material) increases the internal pressure and then leads to volumetric expansion. This extraordinary phenomenon is closely related to the vdW interactions between MOF and H₂ along with the H₂–H₂ interaction, rather than the Madelung-type electrostatic interaction. At low temperatures, H₂ molecules adsorbed in the MOF-5 form highly symmetrical interlinked nanocages that change from a cube-like shape to a sphere-like shape with H₂ loading, helping to exert centrosymmetric forces and hydrostatic (volumetric) stresses from the collection of dispersive interactions. The generated internal negative stress is sufficient to overcome the stiffness of the MOF-5 which is a soft material with a low bulk modulus (15.54 GPa).