We report on a controlled synthesis of MAl2O4 (M = Mg, Co, Ni, Zn, Ba) nanopowders. The method includes
three
main steps: (i) growth of ultraporous nanofibrous Al2O3 (UPA) monoliths and their preliminary thermal treatment to
remove the adsorbed and structural water, (ii) liquid-phase M-nitrate
impregnation, and (iii) heat treatment allowing to form desirable
nanocrystallites. Small crystallites with a spinel structure and mean
size below 10 nm were obtained in Mg, Ni, and Zn aluminates after
heat treatment at 500 °C. The results suggest formation of fully
inverse MgAl2O4 spinels (inversion degree I ≈ 1) after the heat treatment at temperatures below
700 °C, followed by defect healing and formation of a normal
spinel (I ∼ 0.3) at higher temperatures above
the onset of the UPA bulk mass transport of ∼850 °C. This
behavior is due to the interplay between cation diffusion and phase
nucleation processes, in agreement with Ostwald’s rule. The
formation of metastable spinel phases in agreement with Ostwald’s
rule was confirmed after insertion of Co2+, Zn2+ (inverse spinel), and Ni2+ (normal spinel) cations. The
insertion of Ba2+ cations into the UPA precursor resulted
in the stuffed tridymite phase. The nanopowder synthesis route after
upgrading to a large scale can contribute to the fabrication of functional
materials for radiation-tolerant optics (M = Mg, Zn), catalysis (M
= Ni, Co), nanophosphors (M = Ba), etc.