Oriented attachment interfaces of zeolitic imidazolate framework nanocrystals

Abstract

Understanding the growth and coarsening mechanisms of metal–organic framework (MOF) nanoparticles is crucially important for the design and fabrication of MOF materials with diverse functionalities and controllable stability. Oriented attachment (OA) growth is a common manner of MOF nanocrystal coarsening and agglomeration, but the underlying molecular mechanisms have not been well understood to date. Here we report the molecular-scale characterization of the OA interfaces of zeolitic imidazolate framework (ZIF) crystals by state-of-the-art low-dose aberration-corrected transmission electron microscopy. A series of OA interfaces with different molecular structures are captured, implying that multiple kinetic steps are involved in the OA growth of ZIF crystals from non-directional physical attractions between primary nanocrystals, lattice-aligned attachment of the ligand-capped nanocrystals, to coherent interfaces with perfect lattice alignment or stacking faults. It was found that the surface-capping organic ligands not only play an essential role in crystal lattice alignment by near-field directional interactions, but also dominate the interfacial reaction kinetics by interfacial diffusion-controlled elimination of excess surface-capping ligands. These observations provide molecular-scale insights into the OA growth mechanisms of ZIF crystals, which is important for engineering MOF crystal growth pathways by designing surface-capping ligands.