Flow Microreactor Synthesis of Zeolitic Imidazolate Framework (ZIF)@ZIF Core–Shell Metal–Organic Framework Particles and Their Adsorption Properties

Metal–organic frameworks (MOFs) with core–shell structures enable to enhance intrinsic properties of constituent MOFs and impart additional functional activities. Although shell thickness is a key factor for regulating the properties of core–shell MOF particles, controlling it has been challenging. The widely used batch reactor synthesis cannot produce core–shell particles with uniform shell thickness because of poor reactant mixing. A microreactor could ensure excellent mixing, and that would allow to control shell thickness. In this study, we synthesized zeolitic imidazolate framework-8 (ZIF-8)@ZIF-67 and ZIF-67@ZIF-8 core–shell particles using a microreactor and investigated the effects of the mixing performance on the shell thickness of the obtained particles. Our results demonstrated that rapid mixing was critical for the uniformity of the synthesized particles. The concentration of core particles is another key factor that can preferentially induce heterogeneous nucleation on the surface of the core particles without inducing self-nucleation in the bulk solution, particularly when the self-nucleation rate of the shell MOF is high. The N2 adsorption isotherms of the synthesized particles revealed their unique adsorption properties, which were ascribed to the core–shell structures obtained at low shell formation rates. Our simple and versatile synthesis technique not only allowed the preparation of ZIF@ZIF particles with novel functionalities but also can be extended to synthesize core–shell MOF particles with different combinations of core particles and shells.