Molecular Surgery at Microporous MOF for Mesopore Generation and Renovation. Issue 26 (17th May 2021)

• Record Type: Journal Article
• Authors: Albolkany, Mohamed K.; Liu, Congyan; Wang, Yang; Chen, Chun‐Hui; Zhu, Chaofeng; Chen, Xihai; Liu, Bo
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 26(2021)
• Page Start: 14601
• Page End: 14608
• Publication Date: 2021-05-17
• Subjects: hierarchically porous MOFs -- mesopore engineering -- molecular surgery -- molecules encapsulation -- plane-oriented etching; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202103104
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Hierarchically porous MOFs (HP‐MOFs) present advantageous synergism of micro‐ and mesopore but challenging in synthetic control at molecular scale. Herein, we present the first example of reversible and controllable mesopore generation and renovation in a microporous MOF of HKUST‐1 via synthetic manipulation at molecular scale. An ammonia‐gas etching strategy is proposed to create mesopores in carboxylate‐based microporous MOFs and thus produce HP‐MOFs. Gas‐phase etching ensures uniform mesopore formation inside the MOF crystals via plane‐oriented cutting the carboxylate‐metal bonds off without affecting the crystal size and morphology. The mesopore size is controlled by the etching temperature, while the mesopore volume could be tuned by adjusting etchant pressure. The generated mesopores could be renovated using MOF precursors solutions so that to achieve controllable mesopore generation/closure, and encapsulation of the adsorbed molecules. This work demonstrates a powerful protocol for precisely tailoring and tuning the properties of MOF materials at molecular scale. Abstract : Plane‐oriented mesopore formation and closure in microporous MOFs were demonstrated mimicking the surgical operation but at molecular level. The established strategy enables formation of hierarchical MOF with tunable porosity. The anisotropic nature of the MOF lattice planes enabled not only engineering the mesopore size and volume, but also controlling the pore shape that could be beneficial for certain kind of new applications in the MOF field.