Water adsorption fingerprinting of structural defects/capping functions in Zr-fumarate MOFs: a hybrid computational-experimental approach.

Engineering structural defects in MOFs has been intensively applied to modulate their adsorption-related properties. Zr-fumarate MOF (also known as MOF-801) is a prototypical defective MOF with proven versatile adsorption/separation performances depending on the synthetic conditions, however the relationship between the nature/concentration of both structure defects/capping functions and its adsorption features is still far from being fully understood. In this work, we first present a systematic theoretical exploration of the individual contributions of linker and cluster defects as well as of the capping functions to the overall water adsorption profile of the MOF-801 framework. This computational effort based on the construction of defective structure models and the use of Grand Canonical Monte Carlo simulations further enabled the identification of the overarching defective structure for two MOF-801 samples based on their experimental adsorption isotherms reported previously. An experimental effort was then deployed to synthesize two Zr-fumarate MOF samples with controlled nature and concentration of structural defects as well as capping functions. This computational-experimental hybrid strategy revealed the water adsorption isotherm as a fingerprint of the nature and concentration of structural defect/capping groups exhibited by the MOF adsorbent. We expect this study to deliver meaningful insights to further design MOFs with target adsorption features through a rational engineering of structural defects.