Site determination and magnetism of Mn doping in protein encapsulated iron oxide nanoparticles

摘要

Soft x-ray absorption spectroscopy, soft x-ray magnetic circular dichroism, and alternating current magnetic susceptibility were performed on 6.7 nm iron oxide nanoparticles doped with (5%-33%) Mn grown inside the horse-spleen ferritin protein cages and compared to similarly protein encapsulated pure Fe-oxide and Mn-oxide nanoparticles to determine the site of the Mn dopant and to quantify the magnetic behavior with varying Mn concentration. The Mn dopant is shown to substitute preferentially as Mn~(+2) and prefers the octahedral site in the defected spinel structure. The Mn multiplet structure for the nanoparticles is simpler than for the bulk standards, suggesting that the nanoparticle lattices are relaxed from the distortions present in the bulk. Addition of Mn is found to alter the host Fe-oxide lattice from a defected ferrimagnetic spinel structure similar to γ-Fe_2O_3 to a nonferromagnetic spinel structure with a local Fe environment similar to Fe_3O_4.