Unravelling the Thermal Decomposition Parameters for The Synthesis of Anisotropic Iron Oxide Nanoparticles

Iron oxide nanoparticles are widely used as a contrast agent in magnetic resonance imaging (MRI), and may be used as therapeutic agent for magnetic hyperthermia if they display in particular high magnetic anisotropy. Considering the effect of nanoparticles shape on anisotropy, a reproducible shape control of nanoparticles is a current synthesis challenge. By investigating reaction parameters, such as the iron precursor structure, its water content, but also the amount of the surfactant (sodium oleate) reported to control the shape, iron oxide nanoparticles with different shape and composition were obtained, in particular, iron oxide nanoplates. The effect of the surfactant coming from precursor was taking into account by using in house iron stearates bearing either two or three stearate chains and the negative effect of water on shape was confirmed by considering these precursors after their dehydration. Iron stearates with three chains in presence of a ratio sodium oleate/oleic acid 1:1 led mainly to nanocubes presenting a core-shell Fe(1−x)O@Fe(3−x)O(4) composition. Nanocubes with straight faces were only obtained with dehydrated precursors. Meanwhile, iron stearates with two chains led preferentially to the formation of nanoplates with a ratio sodium oleate/oleic acid 4:1. The rarely reported flat shape of the plates was confirmed with 3D transmission electronic microscopy (TEM) tomography. The investigation of the synthesis mechanisms confirmed the major role of chelating ligand and of the heating rate to drive the cubic shape of nanoparticles and showed that the nanoplate formation would depend mainly on the nucleation step and possibly on the presence of a given ratio of oleic acid and chelating ligand (oleate and/or stearate).