Local Structure of Core–Shell MnFe 2 O 4+δ -Based Nanocrystals: Cation Distribution and Valence States of Manganese Ions

Fernando H. Martins (1, 2) , Franciscarlos G. Silva (1) , Fábio L. O. Paula (1) , Juliano de A. Gomes (3) , Renata Aquino (1) , José Mestnik-Filho (4) , Pierre Bonville (5) , Florence Porcher (6) , Régine Perzynski (2) , Jérôme Depeyrot (1)

1 Instituto de Física [Brasilia]
2 PHENIX - PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX
3 Polıcia Civil do Distrito Federal
4 IPEN/CNEN-SP - Instituto de Pesquisas Energéticas e Nucleares [São Paulo]
5 LNO - Laboratoire Nano-Magnétisme et Oxydes
6 LLB - UMR 12 - Laboratoire Léon Brillouin

We investigate the local structure of nanoparticles based on a manganese ferrite core surrounded or not by a maghemite layer obtained after hydrothermal surface treatment. Results of X-ray powder diffraction (XRD) and neutron powder diffraction (NPD) measurements are crossed with those of in-field Mö ssbauer spectroscopy and X-ray absorption spectroscopy (XANES/EXAFS) to study the valence state of Mn ions and the cation distribution at interstitial sites of the core−shell nano-particle structure. Linear combination fitting of XANES data clearly indicates the existence of mixed valence states of Mn cations in the Mn ferrite phase. As a direct consequence, it induces nonequilibrium cation distributions in the nanoparticle core with the presence of a large amount of Mn cations at octahedral sites. The quantitative results of the inversion degree given by NPD, Mö ssbauer spectroscopy measurements, and EXAFS are in good accordance. It is also shown that both the proportions of each oxidation degree of Mn ions and their location at tetrahedral or octahedral sites of the spinel nanocrystal core can be modified by increasing the duration of the surface treatment.

Domaines: Physique [physics]

Fernando H. Martins, Franciscarlos G. Silva, Fábio L. O. Paula, Juliano de A. Gomes, Renata Aquino, et al.. Local Structure of Core–Shell MnFe 2 O 4+δ -Based Nanocrystals: Cation Distribution and Valence States of Manganese Ions. Journal of Physical Chemistry C, 2017, 121 (16), pp.8982 - 8991. ⟨10.1021/acs.jpcc.6b09274⟩. ⟨cea-01567847⟩