Synthesis and Characterization of Co₃O₄-Mn_xCo_3-xO₄ Core-Shell Nanoparticles

Abstract

The mixed-valence oxide Co₃O₄ nanoparticles, having the normal spinel structure, possess large surface area, active-site surface adsorption properties, and fast ion diffusivities. Consequently, they are widely used in lithium-ion batteries, as well as for gas sensing and heterogeneous catalysis applications. In our research, we use a two-step method to synthesize Co₃O₄–based core-shell nanoparticles (CSNs). Cobalt oxide (Co₃O₄) nanoparticles were successfully synthesized using a wet synthesis method employing KOH and cobalt acetate. Manganese was incorporated into the Co₃O₄ structure to synthesize inverted Co₃O₄@Mn_xCo_3-xO₄ CSNs using a hydrothermal method. By adjustment of pH value, we obtained two different morphologies of CSNs, one resulting in pseudo-spherical and octahedron-shaped nanoparticles (PS type) whereas the second type predominantly have a nanoplate (NP type) morphology. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and x-ray photoelectron spectroscopy (XPS) have been performed in order to determine the morphological and structural properties of our CSNs, whereas the magnetic properties have been characterized using a superconducting quantum interference device (SQUID) magnetometer. XRD and TEM results show that the CSNs have the same spinel crystal structure throughout the core and shell with an average particle size of ∼19.8 nm. Our Co₃O₄ nanoparticles, as measured prior to CSN formation, are shown to be antiferromagnetic (AFM) in nature as shown by the magnetization data. Our SQUID data indicate that the core-shell nanoparticles have both AFM (due to the Co₃O₄ core) and ferrimagnetic properties (of the shell) with a coercivity field of 300 Oe and 150 Oe at 5 K for the PS and NP samples, respectively. The magnetization vs temperature data show a spin order-disorder transition at ∼33 K and a superparamagnetic blocking temperature of ∼90 K for both batches.