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The Dissociation Rate of Acetylacetonate Ligands Governs the Size of Ferrimagnetic Zinc Ferrite Nanocubes

submitted on 24.09.2019, 08:40 and posted on 27.09.2019, 17:13 by Aidin Lak, Tamara Kahmann, Simon Jakob Schaper, Jaroslava Obel, Frank Ludwig, Peter Müller-Buschbaum, Jan Lipfert
Magnetic nanoparticles are critical to a broad range of applications, from medical diagnostics and therapeutics to biotechnological processes and single molecule manipulation. To advance these applications, facile and robust routes to synthesize highly magnetic nanoparticles over a wide size range are needed. Here, we demonstrate that changing the degassing temperature of thermal decomposition of metal acetylacetonate precursors from 90 to 25°C tunes the size of ferrimagnetic ZnxFe3-xO4 nanocubes from 25 to 100 nm, respectively. We show that degassing at 90°C nearly entirely removes acetylacetone ligands from the reaction, which results in an early formation of monomers and a reaction-controlled growth following LaMer's model towards small nanocubes. In contrast, degassing at 25°C only partially dissociates acetylacetone ligands from the metal center and triggers a delayed formation of monomers, which leads to intermediate assembled structures made of tiny irregular crystallites and an eventual formation of large nanocubes via a diffusion-controlled growth mechanism. Using complementary techniques, we determine the substitution fraction x of Zn2+ to be in the range of 0.35-0.37. Our method reduces the complexity of the thermal decomposition method by narrowing the synthesis parameter space to a single physical parameter and enables fabrication of highly magnetic and uniform zinc ferrite nanocubes over a broad size range. The resulting particles are promising for a range of applications, from magnetic fluid hyperthermia to actuation of macromolecules.


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Department of Physics, LMU Munich



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Declaration of Conflict of Interest

No conflict of interest