Oxidation of magnetite nanoparticles: impact on surface and crystal properties

Iron oxide nanoparticles are of great scientific interest due to their huge versatility of applications. The oxidation process of magnetite to maghemite is difficult to monitor as both iron oxide polymorphs possess connatural chemical properties. Especially the surface composition and reactivity of these nanosystems, which are most relevant for interactions with their environment, are not completely understood. Here, the oxidation of magnetite is investigated under mild and harsh conditions in order to understand the oxidation behaviour and the chemical stability of transition forms. Therefore, the oxidation process, is investigated with Raman, Mossbauer and X-ray photoelectron spectroscopy as well as X-ray diffraction and magnetometry. The multi-analytical approach allows new insights into surface composition and rearrangement according to respective different depth profiles. For both conditions investigated, the ferrous iron components are oxidised prior to structural changes in the Fe-O vibrations and crystal structure. The process starts from the outer layers and is acid catalysed. Oxidation leads to a decrease of magnetisation which still remains higher than 54 emu g-1. The charge and surface reactivity can be affected by the different oxidation methods and the irreversible adsorption of acid molecules. Biocompatibility and catalytic properties of iron oxide nanoparticles open doors to future applications.