Nanostructured spinel cobalt ferrite samples having crystallite size ranging between 5.6 and 14.1 nm were characterized by X-ray photoelectron spectroscopy and X-ray induced Auger electron spectroscopy in order to determine the chemical state of the elements, the iron/cobalt ratio and the cation distribution within tetrahedral and octahedral sites. The presence of size-dependent trends in the binding energy of the main photoelectron peaks and in the kinetic energy of the X-ray induced O KLL signal was also investigated. The results showed that iron is present as FeIII and cobalt is present as CoII. The iron/cobalt ratio determined by XPS ranges between 1.8 and 1.9 and it is in very good agreement, within experimental uncertainty, with the expected 2 : 1 ratio. The percentage of Fe in octahedral sites ranges between 62% and 64% for all samples. The kinetic energy of the O KLL signals increases with crystallite size. These results are explained in terms of changes in the ionicity of the metal–oxygen bonds. The results of this investigation highlight how the XPS technique represents a powerful tool to investigate the composition, the chemical state and inversion degree of cobalt spinel ferrites, contributing to the comprehension of their properties.

Nanostructured spinel cobalt ferrites: Fe and Co chemical state, cation distribution and size effects by X-ray photoelectron spectroscopy

Marzia Fantauzzi
Primo
;
Antonella Rossi
Ultimo
;
Carla Cannas
Penultimo
;
Marco Sanna Angotzi;Fausto Secci
Secondo
;
2019-01-01

Abstract

Nanostructured spinel cobalt ferrite samples having crystallite size ranging between 5.6 and 14.1 nm were characterized by X-ray photoelectron spectroscopy and X-ray induced Auger electron spectroscopy in order to determine the chemical state of the elements, the iron/cobalt ratio and the cation distribution within tetrahedral and octahedral sites. The presence of size-dependent trends in the binding energy of the main photoelectron peaks and in the kinetic energy of the X-ray induced O KLL signal was also investigated. The results showed that iron is present as FeIII and cobalt is present as CoII. The iron/cobalt ratio determined by XPS ranges between 1.8 and 1.9 and it is in very good agreement, within experimental uncertainty, with the expected 2 : 1 ratio. The percentage of Fe in octahedral sites ranges between 62% and 64% for all samples. The kinetic energy of the O KLL signals increases with crystallite size. These results are explained in terms of changes in the ionicity of the metal–oxygen bonds. The results of this investigation highlight how the XPS technique represents a powerful tool to investigate the composition, the chemical state and inversion degree of cobalt spinel ferrites, contributing to the comprehension of their properties.
2019
MAGNETIC-PROPERTIES; COFE2O4 NANOPARTICLES; INVERSION DEGREE; BINDING-ENERGY; PARTICLE-SIZE; AUGER LINES; XPS; SPECTROMETERS; CALIBRATION; DEPENDENCE
File in questo prodotto:
File Dimensione Formato  
RSC Adv_2019.pdf

accesso aperto

Descrizione: Articolo Principale
Tipologia: versione editoriale
Dimensione 904.94 kB
Formato Adobe PDF
904.94 kB Adobe PDF Visualizza/Apri
RSC Adv_2019_Supporting Info.pdf

accesso aperto

Descrizione: Supporting Information
Tipologia: versione editoriale
Dimensione 490.09 kB
Formato Adobe PDF
490.09 kB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11584/271118
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 95
  • ???jsp.display-item.citation.isi??? 92
social impact