Nanophase cobalt, nickel and zinc ferrites: synchrotron XAS study on the crystallite size dependence of metal distribution.

Nanophase cobalt, nickel and zinc ferrites, in which the crystallites are in the size range 4-25 nm, were synthesised by coprecipitation and subsequent annealing. X-Ray absorption spectroscopy using synchrotron radiation (supported by X-ray powder diffraction) was used to study the effects of particle size on the distributions of the metal atoms over the tetrahedral and octahedral sites of the spinel structure. Deviations from the bulk structure were found which are attributed to the significant influence of the surface on very small particles. Like the bulk material, nickel ferrite is an inverse spinel in the nanoregime, although the population of metals on the octahedral sites increases with decreasing particle size. Cobalt ferrite and zinc ferrite take the inverse and normal forms of the spinel structure respectively, but within the nanoregime both systems show similar trends in being partially inverted. Further, in zinc ferrite, unlike the normal bulk structure, the nanophase system involves mixed coordinations of zinc(ii) and iron(iii) consistent with increasing partial inversion with size.