New approach towards the polyol route to fabricate MFe₂O₄ magnetic nanoparticles: The use of MCl₂ and Fe(acac)₃ as chemical precursors

A new more efficient approach of the polyol route to generate MFe₂O₄ (M=Mn, Fe, Co, Ni, Cu, Zn) nanoparticles in triethylene glycol (TREG) is presented. The selected thermal procedure is based on the Fe metalorganic precursor (iron(III) acetylacetonate) decomposition in presence of an inorganic transition metal chloride salt (MCl₂, M=Mn, Fe, Co, Ni, Cu, Zn) to produce high quality polar dispersible nanoparticles with lower production cost. In addition, the nanoparticles are stabilized by ionic (from the Cl⁻) and steric (TREG as capping ligand) effects inducing into the nanoparticles an extraordinary stability in different polar solvents. As result of this optimized methodology, the colloidal polar dispersible nanoparticles present a size around 10 nm with an adequate size dispersion demonstrated by analyzing transmission electron microscopy (TEM) images. X-ray powder diffraction (XRPD) results corroborate the absence of secondary phases and the high crystalline degree obtained for the spinel structure, fact proved by using synchrotron X-ray diffraction. The high magnetic performance at low and room temperature of the nanoparticles studied by magnetometry proves the high internal crystal order of the spinel. Parallel to this, the influence of the heating ramp and annealing time in the thermal procedure were also investigated for the CuFe₂O₄ case, where a relationship between these two parameters and the final size and their associated diameter distribution was found, allowing a possible size control of the final ferrite magnetic nanoparticles synthesized. - Highlights: • An optimized one-pot methodology is presented to produce pure MFe₂O₄ nanoparticles. • MCl₂ and Fe(acac)₃ precursors in TREG are used for a more efficient process. • Polar dispersible nanoparticles are obtained with high physicochemical properties. • The influence of the temperature ramp and rate on the final size is studied