Pressure-Induced Amorphization of MOF-5: A First Principles Study

İngilizce (OpenAlex)

Abstract Amorphous metal‐organic frameworks (MOFs) and the amorphization of crystalline MOFs under mechanical stimuli are attracting considerable interest in last few years. However, we still have limited knowledge on their atomic arrangement and the physical origin of crystalline‐to‐amorphous phase transitions under mechanical stimuli. In this study, ab initio simulations within a generalized gradient approximation are carried out to investigate the high‐pressure behavior of MOF‐5. Similar to the previous experimental findings, a pressure‐induced amorphization is observed at 2 GPa through the simulations. The phase transformation is an irreversible first order transition and accompanied by around 68% volume collapse. Remarkably, the transition arises from local distortions and, contrary to previous suggestions, does not involve any bond breaking and formation. Additionally, a drastic band gap closure is perceived for the amorphous state. This study has gone some way towards enhancing our understanding of pressure‐induced amorphization in MOFs.