Bimetallic Nanoparticle Oxidation in Three Dimensions by Chemically Sensitive Electron Tomography and in Situ Transmission Electron Microscopy.

The formation of hollow-structured oxide nanoparticles is primarily governed by the Kirkendall effect. However, the degree of complexity of the oxidation process multiplies in the bimetallic system because of the incorporation of more than one element. Spatially dependent oxidation kinetics controls the final morphology of the hollow nanoparticles, and the process is highly dependent on the elemental composition. Currently, a theoretical framework that can predict how different metal elements result in different oxide morphologies remains elusive. In this work, utilizing a combination of state-of-the-art in situ environmental transmission electron microscopy and three-dimensional (3D) chemically sensitive electron tomography, we provide an in situ and 3D investigation of the oxidation mechanism of the Ni-Fe nanoparticles. The direct measurements allow us to correlate the 3D elemental segregation in the particles with the oxidation morphologies, that is, single-cavity or dual-cavity hollow structure, and multicavity porous structures. Our findings in conjunction with theoretical calculations show that metal concentration, diffusivity, and particle size are important parameters that dictate the mechanical and phase stabilities of the hollow oxide shell, which in turn determine its barrier properties and the final hollow oxide morphology. It sheds light on how to use multielemental oxidation to control morphology in nanomaterials and demonstrates the power of 3D chemical imaging.