Liquid-Phase Adsorption and Separation of Xylene Isomers by the Flexible Porous Metal–Organic Framework MIL-53(Fe)

We report a study of the use of the porous metal–organic framework material MIL-53(Fe), Fe III (OH) 0.8 F 0.2 [O 2 C–C 6 H 4 –CO 2 ], for the separation of BTEX mixtures (benzene, toluene, ethylbenzene, and the three xylene isomers). Crystal structures of the three host:guest materials MIL-53(Fe)[xylene], where xylene = the ortho, meta, or para isomer of dimethylbenzene, have been solved and refined from powder X-ray diffraction. Each exhibits a fully expanded form with a variety of host:guest and guest:guest interactions responsible for stabilizing the structure. While the ortho - and meta - isomers present a similar arrangement when occluded in the MIL-53 host, the para -xylene shows a distinctly different set of interactions with the host. Upon thermal treatment, xylenes are partially lost to give crystalline phases MIL-53(Fe)[xylene] 0.5, the structures of which have also been solved. The kinetics of uptake of each xylene by MIL-53(Fe)[H 2 O], in which the water is replaced by the organic guest, have been studied using time-resolved energy-dispersive X-ray diffraction: this shows differences in kinetics of the adsorption of the three isomers. Under chromatographic conditions in heptane at 293 K, anhydrous MIL-53(Fe) is able to separate the three xylene isomers with elution of the para -xylene before the other two isomers, and at 323 K the host is able to resolve all components of the BTEX mixture.