Confinement effects in the hydrogen adsorption on paddle wheel containing metal–organic frameworks

Abstract

The confinement effects upon hydrogen adsorption in Cu(II)-paddle wheel containing metal–organic frameworks (MOFs) were evaluated and rationalized in terms of the structural properties (cavity types and pore diameters) of PCN-12, HKUST-1, MOF-505, NOTT-103 and NOTT-112. First-principles calculations were employed to identify the strongest adsorption positions at the paddle wheel inorganic building unit (IBU). The adsorption centres due to confinement were located through analysis of 3D occupancy maps obtained from the hydrogen trajectories computed via molecular dynamics simulations. It was found that the confinement enhances the adsorption on the weakest adsorption centres around the IBU in regions close to the narrowest windows and promotes the formation of new adsorption regions into the small cavities. Our results indicate that at low pressure, the high H₂ uptake in these materials is partly due to the presence of small cavities (5.3–8.5 Å) or narrow windows where the long-range contribution to the adsorption becomes important. Conversely, confinement effects in cavities with diameters >12 Å were not observed.