Flexibility of a Metal–Organic Framework Enhances Gas Separation and Enables Quantum SievingClick to copy article linkArticle link copied!
- Omid T. QazviniOmid T. QazviniMacDiarmid Institute for Advanced Materials and Nanotechnology, School of Fundamental Sciences, Massey University, Palmerston North 4410, New ZealandDepartment of Chemical Engineering and Analytical Science, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.More by Omid T. Qazvini
- Victoria-Jayne ScottVictoria-Jayne ScottMacDiarmid Institute for Advanced Materials and Nanotechnology, School of Fundamental Sciences, Massey University, Palmerston North 4410, New ZealandMore by Victoria-Jayne Scott
- Linda BondorfLinda BondorfMax Planck Institute for Intelligent Systems, Heisenbergstraße 3, 70569 Stuttgart, GermanyMore by Linda Bondorf
- Maxime DucampMaxime DucampChimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, FranceMore by Maxime Ducamp
- Michael HirscherMichael HirscherMax Planck Institute for Intelligent Systems, Heisenbergstraße 3, 70569 Stuttgart, GermanyMore by Michael Hirscher
- François-Xavier CoudertFrançois-Xavier CoudertChimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, FranceMore by François-Xavier Coudert
- Shane G. Telfer*Shane G. Telfer*Email: [email protected]MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Fundamental Sciences, Massey University, Palmerston North 4410, New ZealandMore by Shane G. Telfer
Abstract
Flexible metal–organic frameworks (MOFs) undergo reversible structural transformations triggered by external stimuli. An interesting feature of some MOFs is their ability to flex in response to specific guests, which can enable selective separation. Here, we introduce MUF-15-OMe ([Co6(μ3-OH)2(ipa-OMe)5(H2O)4]), a variant of MUF-15 that comprises hexanuclear cobalt(II) clusters connected by 5-methoxyisophthalate (ipa-OMe) ligands. MUF-15 itself has isophthalate linkers and is inflexible upon uptake of common gases. On the other hand, MUF-15-OMe flexes upon the uptake of gases such as CO2 and C2 hydrocarbons at pressures less than 1 bar, as revealed by distinct steps in its gas adsorption isotherms. Computational analysis showed that the underlying mechanism involves partial detachment of one of the carboxyl groups of the framework linkers. The gas pressure required to induce framework dynamics can be tuned by replacing some of the ipa-OMe by isophthalate ligands in multivariate frameworks. The flexing of MUF-15-OMe opens up space for the adsorption of specific additional gas molecules. This enhances the separation of CO2 and N2 and enables the differentiation of H2 and D2 by quantum sieving. By providing a clear illustration of how flexibility allows the discrimination of gas mixtures, this study underpins the use of dynamic MOFs for challenging separations.
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