Probing the meta-stability of oxide core/shell nanoparticle systems at atomic resolution

Abstract

Hybrid nanoparticles allow exploiting the interplay of confinement, proximity between different materials and interfacial effects. However, to harness their properties an in-depth understanding of their (meta)stability and interfacial characteristics is crucial. This is especially the case of nanosystems based on functional oxides working under reducing conditions, which may severely impact their properties. In this work, the in-situ electron-induced selective reduction of Mn_3O_4 to MnO is studied in magnetic Fe_3O_4/Mn_3O_4 and Mn_3O_4/Fe_3O_4 core/ shell nanoparticles by means of high-resolution scanning transmission electron microscopy combined with electron energy-loss spectroscopy. Such in-situ transformation allows mimicking the actual processes in operando environments. A multi-stage image analysis using geometric phase analysis combined with particle image velocity enables direct monitoring of the relationship between structure, chemical composition and strain relaxation during the Mn_3O_4 reduction. In the case of Fe3O4/Mn_3O_4 core/shell the transformation occurs smoothly without the formation of defects. However, for the inverse Mn_3O_4/Fe_3O_4 core/shell configuration the electron beam-induced transformation occurs in different stages that include redox reactions and void formation followed by strain field relaxation via formation of defects. This study highlights the relevance of understanding the local dynamics responsible for changes in the particle composition in order to control stability and, ultimately, macroscopic functionality.