Sol-gel synthesis control of iron-cobalt alloy/ferrite core/shell nanoparticles supported by a carbon medium with semi-hard magnetic features

We explore a simple and optimized approach for obtaining magnetic nanoparticle-carbon composites by a novel one-pot sol-gel method. In them, various metal cations ratios of Fe3+ and Co2+ are evaluated. The ratio of Fe:Co is a critical parameter that governs the presence of different crystalline phases with tailored magnetic properties. Interestingly, the smallest introduction of Co into the synthesis (19Fe:1Co) provides an abrupt emergence of the body-centered cubic (bcc) Fe-Co alloy, instead of the orthorhombic Pnma structure characteristic of the Fe3C intermetallic compound (1Fe:0Co). Advanced structural and electronic characterizations reveal the formation of Fe-Co/Co-ferrite core/shell nanoparticle structures embedded in a carbon matrix. The sphere-like nanoparticles range from 10 to 45 nm and the shells show a spinel structure with a thickness of 2–3 nm. In addition, X-ray absorption spectroscopy unveils that the oxidation state of Fe and Co cations is close to zero, demonstrating their predominant metallic character. The magnetic properties can be modulated by a precise control of the alloy composition varying the Co content, displaying saturation magnetization values close to ∼137 emu/g. The nanoparticles are mainly single magnetic domain with a considerable coercive field (∼450 Oe), higher than those reported in the literature for Fe-Co nanoparticles. This semi-hard character is due to a notable spring exchange effect emerged by passivating the surface of Fe-Co-bcc cores with a thin Co-ferrite-like shell.