Prediction of Multiple Hydrogen Ligation at a Vanadium(II) Site in a Metal–Organic Framework

Densifying hydrogen in a metal–organic framework (MOF) at moderate pressures can circumvent challenges associated with high-pressure compression. The highly tunable structural and chemical composition in MOFs affords vast possibilities to optimize binding interactions. At the heart of this search are the nanoscale characteristics of molecular adsorption at the binding site(s). Using density functional theory (DFT) to model binding interactions of hydrogen to the exposed metal site of cation-exchanged MFU-4l, we predict multiple hydrogen ligation of H2 at the first coordination sphere of V(II) in V(II)-exchanged MFU-4l. We find that the strength of this binding between the metal site and H2 molecules can be tuned by altering the halide counterion adjacent to the metal site and that the fluoride containing node affords the most favorable interactions for high-density H2 storage. Using energy decomposition analysis, we delineate electronic contributions that enable multiple hydrogen ligation and demonstrate its benefits for hydrogen adsorption and release at modest pressures.