Abstract
Defects in the crystal structures of metal–organic frameworks (MOFs), whether present intrinsically or introduced via so-called defect engineering, can play strong roles in the properties of MOFs for various applications. Unfortunately, direct experimental detection and characterization of defects in MOFs are very challenging. We show that in many cases, the differences between experimentally observed and computationally predicted water stabilities of MOFs can be used to deduce information on the presence of point defects in real materials. Most computational studies of MOFs consider these materials to be defect-free, and in many cases, the resulting structures are predicted to be hydrophobic. Systematic experimental studies, however, have shown that many MOFs are hydrophilic. We show that the existence of chemically plausible point defects can often account for this discrepancy and use this observation in combination with detailed molecular simulations to assess the impact of local defects and flexibility in a variety of MOFs for which defects had not been considered previously.
