In situ static and dynamic light scattering and scanning electron microscopy study on the crystallization of the dense zinc imidazolate framework ZIF-zni

Abstract

The kinetics and mechanism of crystallization of the dense zinc imidazolate framework with zni topology, from comparatively dilute methanol solutions containing Zn(NO₃)·6H₂O and imidazole with variation of the zinc-to-imidazole ratio, were followed in situ by time-resolved static and dynamic light scattering. The light scattering data revealed that metastable primary particles of about 100 nm in diameter form rapidly upon mixing the component solutions. After a lag time that is dependent on the imidazole concentration, the primary particles aggregate into secondary particles by a monomer addition mechanism with the primary particles as the monomers. Complementary scanning electron microscopy revealed that further evolution of the secondary particles is a complex process involving polycrystalline intermediates, the non-spherical morphologies of which depend on the initial zinc-to-imidazole ratio. Time and location of the first appearance of crystalline order could so far not be established. The pure-phase ZIF-zni crystals obtained after 240 min are twins. The aspect ratio of the tetragonal crystals can be controlled via the zinc-to-imidazole ratio.