On the role of history-dependent adsorbate distribution and metastable states in switchable mesoporous metal-organic frameworks

F Walenszus and V Bon and JD Evans and S Krause and J Getzschmann and S Kaskel and M Dvoyashkin, NATURE COMMUNICATIONS, 14, 3223 (2023).

DOI: 10.1038/s41467-023-38737-6

A unique feature of metal-organic frameworks (MOFs) in contrast to rigid nanoporous materials is their structural switchabilty offering a wide range of functionality for sustainable energy storage, separation and sensing applications. This has initiated a series of experimental and theoretical studies predominantly aiming at understanding the thermodynamic conditions to transform and release gas, but the nature of sorption-induced switching transitions remains poorly understood. Here we report experimental evidence for fluid metastability and history- dependent states during sorption triggering the structural change of the framework and leading to the counterintuitive phenomenon of negative gas adsorption (NGA) in flexible MOFs. Preparation of two isoreticular MOFs differing by structural flexibility and performing direct in situ diffusion studies aided by in situ X-ray diffraction, scanning electron microscopy and computational modelling, allowed assessment of n-butane molecular dynamics, phase state, and the framework response to obtain a microscopic picture for each step of the sorption process. Switchable porous materials offer adaptive voids mutating in size and shape in response to molecular stimuli. Here authors use PFG NMR to reveal the decisive role of metastable states leading to counterintuitive negative gas adsorption transitions in responsive MOFs.

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