In Situ Monitoring of the Seeding and Growth of Silver Metal–Organic Nanotubes by Liquid-Cell Transmission Electron Microscopy

Metal–organic nanotubes (MONTs) are highly ordered one-dimensional crystalline porous frameworks. Despite being nanomaterials, virtually all studies of MONTs rely on characterization of the bulk crystalline material (micron-sized) by single-crystal X-ray diffraction. For MONTs to achieve their raison d’être as tunable one-dimensional nanomaterials, individual tubes or small finite bundles of tubes must be synthesized and characterized. Therefore, to directly observe their formation under a variety of reaction conditions in solution, we employ liquid-cell transmission electron microscopy (LCTEM), which allows the early stages of MONT assembly to be monitored in real time. Notably, changing the metal-to-ligand ratio alters the local concentrations of reactant monomers, resulting in multiple nucleation and growth pathways and diverse morphologies at the nanoscale. These various initial seeds grow to form the same nanocrystalline needle phase. This approach of employing LCTEM to study these nanomaterials is analogous to monitoring typical homogeneous solution phase reactions by NMR for controlled nanomaterial formation.