Enhancing Selective Hydrofluorocarbon Greenhouse Gas Capture via Halogenation of Metal-Organic Frameworks

Hydrofluorocarbons (HFCs) are anthropogenically produced greenhouse gases with longer atmospheric lifetimes and higher global warming potentials than carbon dioxide. General strategies to abate their emissions from industrial point sources, such as via adsorptive capture, remain scarce. Herein, we uncover the key structure-property relationships that lead to strong binding of HFCs such as fluoroform (CHF3) and difluoromethane (CH2F2) in metal-organic frameworks (MOFs) under the low pressures relevant to flue gas scrubbing. Extensive gas sorption and computational studies support that the Zr-based microporous framework MOF-801-Br or HHU-2-Br (HHU = Heinrich-Heine-University Düsseldorf) strongly binds HFCs due to its synergistic combination of Zr–OH sites on the nodes and bromine sites on the linkers. As such, MOF-801-Br demon-strates record-setting performance for separating CHF3 from N2 under dilute conditions. Our work highlights that the combi-nation of multiple hydrogen-bonding sites in microporous MOFs represents a generalizable strategy for HFC capture, ena-bling their selective removal from industrial waste streams