Designing Angstrom-Scale Asymmetric MOF-on-MOF Cavities for High Monovalent Ion Selectivity

Mojtaba Abdollahzadeh; Milton Chai; Ehsan Hosseini; Mohammad Zakertabrizi; Munirah Mohammad; Hadi Ahmadi; Jingwei Hou; Sean Lim; Asghar Habibnejad Korayem; Vicki Chen; Mohsen Asadnia; Amir Razmjou

doi:10.1002/adma.202107878

Designing Angstrom-Scale Asymmetric MOF-on-MOF Cavities for High Monovalent Ion Selectivity

Adv Mater. 2022 Mar;34(9):e2107878. doi: 10.1002/adma.202107878. Epub 2022 Jan 20.

Authors

Affiliations

¹ School of Engineering, Macquarie University, Sydney, NSW, 2109, Australia.
² School of Chemical Engineering, University of Queensland, Brisbane, QLD, 4072, Australia.
³ UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering, University of New South Wales, Sydney, NSW, 2052, Australia.
⁴ Nanomaterials Research Centre, School of Civil Engineering, Iran University of Science and Technology, Tehran, 1684613114, Iran.
⁵ Electron Microscope Unit, Mark Wainright Analytical Centre, The University of New South Wales, Sydney, NSW, 2052, Australia.
⁶ Centre for Technology in Water and Wastewater, University of Technology Sydney, Sydney, NSW, 2007, Australia.

PMID: 34921462
DOI: 10.1002/adma.202107878

Abstract

Biological ion channels feature angstrom-scale asymmetrical cavity structures, which are the key to achieving highly efficient separation and sensing of alkali metal ions from aqueous resources. The clean energy future and lithium-based energy storage systems heavily rely on highly efficient ionic separations. However, artificial recreation of such a sophisticated biostructure has been technically challenging. Here, a highly tunable design concept is introduced to fabricate monovalent ion-selective membranes with asymmetric sub-nanometer pores in which energy barriers are implanted. The energy barriers act against ionic movements, which hold the target ion while facilitating the transport of competing ions. The membrane consists of bilayer metal-organic frameworks (MOF-on-MOF), possessing a 6 to 3.4-angstrom passable cavity structure. The ionic current measurements exhibit an unprecedented ionic current rectification ratio of above 100 with exceptionally high selectivity ratios of 84 and 80 for K⁺ /Li⁺ and Na⁺ / Li⁺ , respectively (1.14 Li⁺ mol m^-2 h^-1 ). Furthermore, using quantum mechanics/molecular mechanics, it is shown that the combined effect of spatial hindrance and nucleophilic entrapment to induce energy surge baffles is responsible for the membrane's ultrahigh selectivity and ion rectification. This work demonstrates a striking advance in developing monovalent ion-selective channels and has implications in sensing, energy storage, and separation technologies.

Keywords: asymmetric nanochannel; ion rectification; ion-selective membrane; lithium recovery; metal-organic frameworks.

Abstract

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