Opening the Gate: Framework Flexibility in ZIF-8 Explored by Experiments and Simulations

ZIF-8 is a zeolitic imidazole-based metal–organic framework with large cavities interconnected by narrow windows. Because the small size of the windows, it allows in principle for molecular sieving of gases such as H₂ and CH₄. However, the unexpected adsorption of large molecules on ZIF-8 suggests the existence of structural flexibility. ZIF-8 flexibility is explored in this work combining different experimental techniques with molecular simulation. We show that the ZIF-8 structure is modified by gas adsorption uptake in the same way as it is at a very high pressure (i.e., 14 700 bar) due to a swing effect in the imidazolate linkers, giving access to the porosity. Tuning the flexibility, and so the opening of the small windows, has a further impact on the design of advanced molecular sieving membrane materials for gas separation, adjusting the access of fluids to the porous network.