Abstract:

Mn−Co−O nanocrystals, with a defective rock salt-type structure, were prepared by anodic electrodeposition. The structural and chemical stability of the as-deposited oxide nanocrystals were investigated using wavelength dispersive spectroscopy (WDS), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The rock salt−spinel structural transformation occurred in the oxide nanocrystals annealed at a temperature of 500 °C. A cubic Fd3̅m spinel-type structure was obtained in the Co-rich, Mn−Co−O oxide nanocrystals, while a distorted tetragonal-type spinel phase with a space group of I4₁/amd, induced by the Jahn–Teller effect, formed in their Mn-rich counterparts. It is noted that the structural transformation involves the migration of Mn/Co cations from the octahedral interstices to the tetrahedral interstices, which is accompanied by the reduction of Mn/Co cations and oxygen evolution. A novel mechanism for the structural transformation and reaction scheme is proposed in this work.