Fabrication of Oriented Polycrystalline MOF Superstructures

Abstract The field of metal‐organic frameworks (MOFs) has progressed beyond the design and exploration of powdery and single‐crystalline materials. A current challenge is the fabrication of organized superstructures that can harness the directional properties of the individual constituent MOF crystals. To date, the progress in the fabrication methods of polycrystalline MOF superstructures has led to close‐packed structures with defined crystalline orientation. By controlling the crystalline orientation, the MOF pore channels of the constituent crystals can be aligned along specific directions: these systems possess anisotropic properties including enhanced diffusion along specific directions, preferential orientation of guest species, and protection of functional guests. In this perspective, we discuss the current status of MOF research in the fabrication of oriented polycrystalline superstructures focusing on the specific crystalline directions of orientation. Three methods are examined in detail: the assembly from colloidal MOF solutions, the use of external fields for the alignment of MOF particles, and the heteroepitaxial ceramic‐to‐MOF growth. This perspective aims at promoting the progress of this field of research and inspiring the development of new protocols for the preparation of MOF systems with oriented pore channels, to enable advanced MOF‐based devices with anisotropic properties.