General Way To Construct Micro- and Mesoporous Metal-Organic Framework-Based Porous Liquids

We report a new class of porous liquids (PLs) using internally functionalized metal-organic framework (MOF) particles as pore carriers and poly(dimethylsiloxane) as bulky solvents. Using a generalizable noncovalent surface-initiated controlled radical polymerization technique, a series of isoreticular UiO-66 particles were dispersed in a liquid PDMS matrix with excellent homogeneity and colloidal stability. Benefiting from the inherent properties of PDMS, the PLs exhibit low vapor pressure, high thermal stability, and fluidity down to -35 °C. Attributed to the bulkiness of PDMS and its inherent high permeability, the sorption properties of the MOF fillers can be largely retained in their respective PLs as confirmed by low-pressure CO₂, N₂, Xe, and H₂O sorption isotherms. The permanent porosity of the PLs can also be largely preserved even after 15 months of storage. Finally, we demonstrate that by tuning the molecular weight and polymer chain architecture of PDMS, it is possible to preserve the permanent porosity of a mesoporous MOF, MIL-101(Cr), within a PL.