Metal−Organic Framework MIL-101 for Adsorption and Effect of Terminal Water Molecules: From Quantum Mechanics to Molecular Simulation

MIL-101 is a chromium terephthalate-based mesoscopic metal−organic framework and one of the most porous materials reported to date. In this study, we investigate the adsorption of CO2 and CH4 in dehydrated and hydrated MIL-101 and the effect of terminal water molecules on adsorption. The atomistic structures of MIL-101 are constructed from experimental crystallographic data, energy minimization, and quantum mechanical optimization. The adsorption isotherm of CO2 predicted from molecular simulation agrees well with experiment and is relatively insensitive to the method (Merz−Kollman or Mulliken) used to estimate the framework charges. Both the united-atom and five-site models of CH4 predict the isotherm fairly well, though the former overestimates and the latter underestimates. Adsorption first occurs in the microporous supertetrahedra at low pressures and then in the mesoscopic cages with increasing pressure. In the dehydrated MIL-101, more adsorbate molecules are located near the exposed Cr2 sites than the fluorine saturated Cr1 sites. The terminal water molecules in the hydrated MIL-101 act as additional interaction sites and enhance adsorption at low pressures. This enhancement is more pronounced for CO2 than for CH4, because CO2 is quadrapolar and interacts more strongly with the terminal water molecules. At high pressures, however, the reverse is observed, as the presence of terminal water molecules reduces free volume and adsorption. For the adsorption of CO2/CH4 mixture, a higher selectivity is found in the hydrated MIL-101.