Molecular simulations of very high pressure hydrogen storage using metal–organic frameworks

Abstract

Hydrogen adsorption isotherms in 20 metal–organic frameworks (MOFs) were obtained from grand canonical Monte Carlo simulations and used to develop quantitative correlations to quickly estimate the H 2 uptake of MOFs at 120 bar from the free volume of the adsorbent. These correlations were then verified with a diverse set of 22 MOFs that were not used in developing the correlations. The simulated high-pressure H 2 isotherms in five representative MOFs show that extremely high pressures (∼80,000 bar) are required to completely fill the MOF pores with H 2 at 298 K. Nevertheless, much lower pressures (several 100 bar) are sufficient to attain the H 2 storage targets for MOFs with large free volumes. For IRMOF-16 with a large free volume (4.322 cm 3/g), only modest pressures (170 and 280 bar) are required to achieve the 2010 and 2015 gravimetric targets. However, considerably higher pressures are required for attaining the volumetric targets. In addition, three interesting pressure regions, which are observed in the H 2 densities within the MOFs ( ρ ad ) up to very high pressures, are analyzed by radial distribution functions between the adsorbed H 2 molecules as well as those between H 2 molecules and metal corners.