Impact of Tannic Acid on Iron Oxide Nanoclusters Synthesized by a Polyol Solvothermal Method

Raspberry-shaped iron oxide nanostructures (RSNs) correspond to oriented aggregated and hollow clusters of nanograins exhibiting a high saturation magnetization and a superparamagnetic behaviour. These nanostructures are promising for a wide range of applications, such as magnetic separation, catalysis, pollution control, and nanomedicine. However, for most applications, particularly nanomedecine and depollution, high colloidal stability is required, and the isoelectric point of iron oxide is around 6–7. Therefore, these nanoclusters need to be coated with a surfactant to obtain colloidal suspensions in water. Here, we have developed a one-pot polyol solvothermal synthesis process to coat these promising nanoclusters with tannic acid (TA), a natural compound with antimicrobial properties, which has been little studied with these nanoclusters. Different parameters of the synthesis were adjusted, such as the molar ratio TA:Fe, the synthesis temperature and duration. We showed that TA interferes deeply in the RSNs synthesis mechanism with the observed reduction of iron(III) to iron(II), the complexation of TA with iron, the formation of intermediate phases, as well as the growth of a parasitic iron carbonate phase and the loss of the oriented aggregation and hollowness of the iron oxide RSNs. Considering all these parameters, the optimal synthesis conditions were thus established (TA:Fe ratio = 0.010, temperature of 200°C and duration of 10.5h), leading to RSNs with small nanograins, a rather high surface area (82 m2/g), high saturation magnetization (74emu/g) and good colloidal stability. By combining different characterization techniques, a new synthesis mechanism was proposed different from previously established for RSNs without TA, based on strong TA-iron oxide interfaces.