Zn-Site Determination in Protein Encapsulated ZnxFe3-xO4 Nanoparticles

The X-ray absorption spectra of the Fe and Zn L-edges for 6.7 nm Fe{sub 3}O{sub 4} nanoparticles grown inside 12 nm ferritin protein cages with 10%, 15%, 20% and 33% zinc doping, shows that the Zn is substitutional as Zn{sup 2+} within the iron oxide host structure. A Neel-Arrhenius plot of the blocking temperature in the frequency dependent ac-susceptibility measurements show that the particles are non-interacting and that the anisotropy energy barrier is reduced with Zn loading. X-ray magnetic circular dichroism (XMCD) of the Fe displays a linear decrease with Zn-doping in sharp contrast to the initial increase present in the bulk system. The most plausible explanation for the moment decrease is that Zn substitutes preferentially into the tetrahedral A-site as a Zn{sup 2+} cation, generating a mixed spinel.