Details

Autor(en) / Beteiligte

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

Titel

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

Ist Teil von

• Advanced materials (Weinheim), 2022-03, Vol.34 (9), p.e2107878-n/a

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2022

Quelle

Wiley Online Library

Beschreibungen/Notizen

• 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. A new class of ion‐selective membrane that possesses an asymmetrical bi‐layer of functionalized metal‐organic frameworks (MOF‐on‐MOF) with heterostructured connections between the two MOFs is introduced. The membrane consists of natural asymmetrical nanochannels that exhibit both extraordinary high ionic current rectification and high monovalent ion selectivity.