Abstract
A combination of manometry, X-ray powder diffraction (XRPD), and molecular modeling has been used to show that the functionalization of the flexible MIL-53(Fe)-X materials (MIL stands for Materials of the Lavoisier Institute; X = CH3, Cl, Br, NH2) modifies the adsorption process of normal alkanes, by facilitating pores filling as compared to that of the nonmodified MIL-53(Fe) analogue. The adsorption isotherms show that these materials undergo steps at pressures specific for each guest and functional group, associated with structural transitions as corroborated by the simulated isotherms and XRPD data. With the exception of methane, a transition from the closed pore form to the large pore form occurs through one intermediate pore form upon adsorption, thus differing from the case of the nonmodified MIL-53(Fe) where two intermediate pore forms are observed. The transitions are governed by a combination of factors, including energetic, kinetic, and steric aspects with, however, transition pressures becoming...
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