We demonstrate that fluorous metal-organic frameworks (FMOFs) are highly hydrophobic porous materials with a high capacity and affinity to C(6)-C(8) hydrocarbons of oil components. FMOF-1 exhibits reversible adsorption with a high capacity for n-hexane, cyclohexane, benzene, toluene, and p-xylene, with no detectable water adsorption even at near 100% relative humidity, drastically outperforming activated carbon and zeolite porous materials. FMOF-2, obtained from annealing FMOF-1, shows enlarged cages and channels with double toluene adsorption vs FMOF-1 based on crystal structures. The results suggest great promise for FMOFs in applications such as removal of organic pollutants from oil spills or ambient humid air, hydrocarbon storage and transportation, water purification, etc. under practical working conditions.

A fluorous metal−organic framework, FMOF-1, is obtained by reaction of Ag(I) with 3,5-bis(trifluoromethyl)-1,2,4-triazolate, giving rise to a neutral, hydrogen-free, extended 3D nanotubular porous framework consisting of tetranuclear clusters [Ag4Tz6] connected by three-coordinate Ag(I) centers. The fluoro-lined channels and cavities of the framework show hysteretic adsorption of H2 with a volumetric capacity of 41 kg/m3 at 77 K and 64 bar. The framework also exhibits very high adsorptions for O2 and N2 with volumetric uptake of ∼550 and 400 kg/m3 at 77 K even at very low pressures (<10-2 bar).

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