Iron Oxide Superparticles with Enhanced MRI Performance by Solution Phase Epitaxial Growth

Organized three-dimensional (3D) nanomaterial architectures are promising candidates for applications in optoelectronics, catalysis, or theranostics owing to their anisotropy and advanced structural features that allow tailoring their physical and chemical properties. The synthesis of such complex but well-organized nanomaterials is difficult because the interplay of interfacial strain and facet-specific reactivity must be considered. Especially the magnetic anisotropy with controlled size and morphology plays a decisive role for applications like magnetic resonance imaging (MRI) and advanced data storage. We present a solution phase seed mediated synthesis of colloidal, well dispersible iron oxide superparticles with flower- and hedgehog-like morphology starting from dispersible spherical maghemite (SPH) and nanoplate hematite (HEX) templates. In the superparticles the templates are epitaxially decorated with nanodomains and nanorods as shown by (high-resolution) transmission electron microscopy (TEM), orientation mapping, and electron diffraction (ED). While the templates determine the morphology of the superparticles, the solution chemistry determines the phase identity. Oxidation of Fe(CO)₅ during superparticle formation reaction leads to maghemite nanodomains and nanorods decorating the templates, unveiled by a combination of X-ray diffraction (XRD) and Mössbauer spectroscopy (MS). After hydrophilic surface functionalization the superparticles are well dispersible. The cytotoxicity of templates and superparticles is low. The magnetic resonance imaging R₂-relaxivity of the flower-like superparticles could be increased by a factor 2.5 compared to its spherical nanoparticle template due to direct interfacial connection resulting from the unique nanoarchitecture.