Validating the Mechanism Underlying the Slacking of the Gate-Opening Behavior in Flexible Metal–Organic Frameworks Arising from the Application of External Force

Flexible metal–organic frameworks (MOFs) are innovative adsorbents expected to revolutionize conventional separation systems as they exhibit stepwise adsorption arising from structural transitions, commonly known as “gate opening.” However, because MOFs are typically obtained in powder form, they require shaping for industrial applications. In our previous study, we reported that the stepwise uptake observed in the CO2 gate opening of ELM-11 ([Cu(BF4)2(4,4′-bipyridine)2]) became less distinct when molded with polymer binders and found that this slacking phenomenon could be caused by the polymer binder inhibiting the structural change of the ELM-11 particles. In this study, we aimed to fully validate and generalize the mechanism behind the slacking of gate adsorption from both theoretical and experimental perspectives. First, we conducted grand canonical molecular dynamics simulations for a simplified MOF model to directly calculate free energy profiles of the particle to validate the slacking theory without any assumptions. The results confirmed the fundamental assumption made in our previous study that the deformation of the flexible motifs within the MOF particles occurs sequentially, which is a key factor contributing to the slacking phenomenon. The second part of the study focused on the relationship between the volume expansion ratio of MOFs and the degree of slacking. The relationship predicted by the theory was experimentally validated by comparing ELM-11, which exhibits 30% volume expansion, to another MOF with a mutually interpenetrating jungle-gym structure, which exhibits 10% volume expansion. These findings strengthened and generalized the understanding of the mechanism underlying the slacking of gate adsorption induced upon the application of external force, which could guide the fabrication of molded MOFs while maintaining a high adsorption efficiency for various industrial applications.