Changes in the Long-Range Order and Local Atomic Structure of Zeolitic Imidazolate Frameworks under Extreme Conditions

Zeolitic imidazolate frameworks (ZIFs), a subclass of metal–organic frameworks (MOFs), combine high porosity and chemical tunability with a resistance to harsh conditions. Understanding their response to extreme pressure and heat is critical for application development due to the conditions under which they may be required to work or for predicting their response to any processing before use. In this study, we characterize long- and short-range order in ZIF-8 and ZIF-62 under compression using Bragg X-ray diffraction and pair distribution function (PDF) analysis for a large pressure range (up to ∼5 GPa) previously attempted in very few works. X-ray absorption fine structure analysis was carried out under high-pressure-temperature conditions to probe the medium-range order, a novelty in MOFs. ZIF-8 demonstrated a crystalline–crystalline phase transition above 0.36 GPa but no full amorphization. In ZIF-62, pore intrusion of the silicone oil pressure-transmitting medium (PTM) was observed through negative compressibility and by retention of its open-pore configuration. Full amorphization was achieved, with heating lowering the amorphization threshold. Finally, a unique distortion in both MOFs was suggested by the spectroscopic data. These results provide insight into the thermomechanical stability of crystalline ZIFs and the mechanism underlying their amorphization.