Metal–Organic Framework Materials with Ultrahigh Surface Areas: Is the Sky the Limit?

We have synthesized, characterized, and computationally simulated/validated the behavior of two new metal–organic framework (MOF) materials displaying the highest experimental Brunauer–Emmett–Teller (BET) surface areas of any porous materials reported to date (∼7000 m2/g). Key to evacuating the initially solvent-filled materials without pore collapse, and thereby accessing the ultrahigh areas, is the use of a supercritical CO2 activation technique. Additionally, we demonstrate computationally that by shifting from phenyl groups to “space efficient” acetylene moieties as linker expansion units, the hypothetical maximum surface area for a MOF material is substantially greater than previously envisioned (∼14600 m2/g (or greater) versus ∼10500 m2/g).