Core@shell nanocomposites Fe7C3 / FexOy /C obtained by high pressure-high temperature treatment of ferrocene Fe(C5H5)2

Abstract

The core@shell nanostructures were obtained in the process of transformation of ferrocene Fe(C5H5)2 at high pressure (HP) of 8 GPa and high temperature (HT) of 900 °C with an isothermal exposure time t varying from 10 to 10000 s. At t > 300 s, the iron carbide o-Fe7C3 nanoparticles with an orthorhombic crystal structure (sp.gr. Pnma) can be created, which are dispersed in highly defective carbon matrix. After opening the high-pressure cell, a series of redox reactions occurs, leading to a formation of iron oxides on the surface of the iron carbide core. When the size of Fe7C3 nanoparticle is less than critical one the nanoparticle is fully oxidized, while in the larger particle an amorphous iron oxide shell is formed. A sequential increase in t initiates crystallization processes both in the iron carbide subsystem and in the carbon subsystem, resulting in the formation of core@shell Fe7C3/FexOy/C structures. Iron oxides with a cubic spinel-type structure (Fe3O4/γ-Fe2O3) appear in the shell. However, under oxygen reduction, part of magnetite can be transformed into wüstite FeO. The magnetic properties of magnetite and wüstite are radically different, and by varying the thickness of these layers, structures with the desired functional properties can be obtained.