Nanoscopic Insights into the Collapse of Metal–Organic Frameworks during Solvent Evacuation: Molecular Simulation Investigation

Many metal-organic frameworks (MOFs) undergo structural collapse upon solvent evacuation during activation, which is attributed to the capillary force generated by the solvent. However, little effort has been devoted to unveiling the nature of such a force. Herein, we employ molecular dynamics (MD) simulations to investigate the evacuation of different solvents in two MOFs (MOF-5 and UMCM-9). The contractive stress induced by solvent evacuation is quantified and unraveled to positively correlate with the surface tension of the solvent. Moreover, the mechanical strength (or amorphization) of the MOF is calculated using reactive MD simulations. By comparing the contractive stress with the amorphization stress, for the first time, we predict the likelihood of collapse of MOFs during activation by different solvents, which agrees well with the experiments. The methodology developed provides nanoscopic insights into the activation process; it can assist in avoiding structural collapse by judiciously selecting a proper solvent for activation or by modifying a framework.