Directional growth and reconstruction of ultrafine uranium oxide nanorods within single-walled carbon nanotubes.

Abstract

Understanding the atomic structures and dynamic evolution of uranium oxides is crucial for the reliable operation of fission reactors. Among them, U4O9-as an important intermediate in the oxidation of UO2 to UO2+x -plays an important role in the nucleation and conversion of uranium oxides. Herein, we realize the confined assembly of uranyl within SWCNTs in liquid phase and reveal the directional growth and reconstruction of U4O9 nanorods in nanochannels, enabled by in situ scanning transmission electron microscopy (STEM) e-beam stimulation. The nucleation and crystallization of U4O9 nanorods in nanochannels obey the "non-classical nucleation" mechanism and exhibit remarkably higher growth rate compared to those grown outside. The rapid growth process is found to be accompanied by the formation and elimination of U atom vacancies and strain, aiming to achieve the minimum interfacial energy. Eventually, the segments of U4O9 nanorods in SWCNTs merge into single-crystal U4O9 nanorods via structural reconstruction at the interfaces, and 79% of them exhibit anisotropic growth along the specific 〈11̄0〉 direction. These findings pave the way for tailoring the atomic structures and interfaces of uranium oxides during the synthesis process to help improve the mechanical properties and stability of fission reactors.