Molecular Surgery at Microporous MOF for Mesopore Generation and Renovation

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.