Encapsulation of Metal Nanoparticles by Metal–Organic Framework Imaged with In Situ Liquid Phase Transmission Electron Microscopy

Abstract Metal nanoparticle@metal−organic framework (NP@MOF) composites hold promise for potential applications in gas storage, catalysis, sensing, environmental monitoring, and biomedicine. Despite their importance, details of how MOFs encapsulate the NPs to form NP@MOF hybrid nanostructures are largely unexplored. Here, using ultra‐low electron‐flux in situ liquid phase transmission electron microscopy (LP‐TEM), the encapsulation of Au NPs with zeolitic imidazolate framework‐8 (ZIF‐8) is visualized. These observations reveal that the speeds at which MOFs nucleate on the NP's surface impact the shell's shape. At low concentrations of MOF precursor, NPs are encapsulated with well‐defined single‐crystalline MOF shells, while at high concentrations, MOFs tend to nucleate and grow from multiple sites on the NP surface, resulting in irregularly shaped polycrystalline MOF shells. This approach, which uses a very low electron flux to image the synthesis of Au@ZIF‐8 nanostructures, can be extended to imaging crucial processes in many other beam‐sensitive materials and help design hybrid systems for a broad range of applications.