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Updated: Mar 28, 2026

Author Spotlight: Characterizing Porous Materials for Aiding the Development of Robust Metal-Organic Frameworks with Adsorption Behavior
Published on: March 8, 2024
Stress-Based Model for the Breathing of Metal-Organic Frameworks
Alexander V Neimark1,2, François-Xavier Coudert1, Anne Boutin3
1Chimie ParisTech (École nationale supérieure de chimie de Paris), CNRS and Université Pierre et Marie Curie, 11 rue Pierre et Marie Curie, 75005 Paris, France.
Abstract:
Gas adsorption in pores of flexible metal-organic frameworks (MOF) induces elastic deformation and structural transitions associated with stepwise expansion and contraction of the material, known as breathing transitions between large pore (lp) and narrow pore (np) phases. We present here a simple yet instructive model for the physical mechanism of this enigmatic phenomenon considering the adsorption-induced stress exerted on the material as a stimulus that triggers breathing transitions. The proposed model implies that the structural transitions in MOFs occur when the stress reaches a certain critical threshold. We showcase this model by drawing on the example of Xe adsorption in MIL-53 (Al) at 220 K, which exhibits two consecutive hysteretic breathing transitions between lp and np phases. We also propose an explanation for the experimentally observed coexistence of np and lp phases in MIL-53 materials.
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