Investigating H₂ Sorption in a Fluorinated Metal–Organic Framework with Small Pores Through Molecular Simulation and Inelastic Neutron Scattering

Simulations of H₂ sorption were performed in a metal–organic framework (MOF) consisting of Zn²⁺ ions coordinated to 1,2,4-triazole and tetrafluoroterephthalate ligands (denoted [Zn­(trz)­(tftph)] in this work). The simulated H₂ sorption isotherms reported in this work are consistent with the experimental data for the state points considered. The experimental H₂ isosteric heat of adsorption (<i>Q</i>_st) values for this MOF are approximately 8.0 kJ mol^–1 for the considered loading range, which is in the proximity of those determined from simulation. The experimental inelastic neutron scattering (INS) spectra for H₂ in [Zn­(trz)­(tftph)] reveal at least two peaks that occur at low energies, which corresponds to high barriers to rotation for the respective sites. The most favorable sorption site in the MOF was identified from the simulations as sorption in the vicinity of a metal–coordinated H₂O molecule, an exposed fluorine atom, and a carboxylate oxygen atom in a confined region in the framework. Secondary sorption was observed between the fluorine atoms of adjacent tetrafluoroterephthalate ligands. The H₂ molecule at the primary sorption site in [Zn­(trz)­(tftph)] exhibits a rotational barrier that exceeds that for most neutral MOFs with open-metal sites according to an empirical phenomenological model, and this was further validated by calculating the rotational potential energy surface for H₂ at this site