Joo, Jaeyong Kim, Hyungjun Han, Sang Soo 2024-01-20T11:04:17Z 2024-01-20T11:04:17Z 2021-09-05 2013-11 1463-9076 https://pubs.kist.re.kr/handle/201004/127495 Using a density functional theory calculation including van der Waals (vdW) corrections, we report that H-2 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 H-2 along with the H-2-H-2 interaction, rather than the Madelung-type electrostatic interaction. At low temperatures, H-2 molecules adsorbed in the MOF-5 form highly symmetrical interlinked nanocages that change from a cube-like shape to a sphere-like shape with H-2 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). English ROYAL SOC CHEMISTRY NEGATIVE THERMAL-EXPANSION DENSITY-FUNCTIONAL THEORY HYDROGEN STORAGE ADSORPTION SEPARATION PRESSURE METHANE CO2 Volume shrinkage of a metal-organic framework host induced by the dispersive attraction of guest gas molecules Article 10.1039/c3cp53256a 1 PHYSICAL CHEMISTRY CHEMICAL PHYSICS, v.15, no.43, pp.18822 - 18826 PHYSICAL CHEMISTRY CHEMICAL PHYSICS 15 43 18822 18826 scie scopus 000325943200008 2-s2.0-84886897359 Chemistry, Physical Physics, Atomic, Molecular & Chemical Chemistry Physics Article NEGATIVE THERMAL-EXPANSION DENSITY-FUNCTIONAL THEORY HYDROGEN STORAGE ADSORPTION SEPARATION PRESSURE METHANE CO2 Metal-organic framework Volume shrinkage Host Guest Dispersive attraction Density functional theory