Synthesis of Cu ₃ N and Cu ₃ N–Cu ₂ O multicomponent mesocrystals: non-classical crystallization and nanoscale Kirkendall effect

Mesocrystals are superstructures of crystallographically aligned nanoparticles and are a rapidly emerging class of crystalline materials displaying sophisticated morphologies and properties, beyond those originating from size and shape of nanoparticles alone. This study reports the first synthesis of Cu₃N mesocrystals employing structure-directing agents with a subtle tuning of the reaction parameters. Detailed structural characterizations carried out with a combination of transmission electron microscopy techniques (HRTEM, HAADF-STEM-EXDS) reveal that Cu₃N mesocrystals form by non-classical crystallization, and variations in their sizes and morphologies are traced back to distinct attachment scenarios of corresponding mesocrystal subunits. In the presence of oleylamine, the mesocrystal subunits in the early reaction stages prealign in a crystallographic fashion and afterwards grow into the final mesocrystals, while in the presence of hexadecylamine the subunits come into contact through misaligned attachment, and subsequently, to some degree, realign in crystallographic register. Upon prolonged heating both types of mesocrystals undergo chemical conversion processes resulting in structural and morphological changes. A two-step mechanism of chemical conversion is proposed, involving Cu₃N decomposition and anion exchange driven by the nanoscale Kirkendall effect, resulting first in multicomponent/heterostructured Cu₃N-Cu₂O mesocrystals, which subsequently convert into Cu₂O nanocages. It is anticipated that combining nanostructured Cu₃N and Cu₂O in a mesocrystalline and hollow morphology will provide a platform to expand their application potential.