Crystalline and magnetic structure-property relationship in spinel ferrite nanoparticles

Henrik Lyder Andersen, Matilde Saura-Múzquiz, Cecilia Granados, Emmanuel Canévet, Nina Lock, Mogens Christensen*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Magnetic spinel ferrite MFe2O4 (M = Mn, Co, Ni, Zn) nanoparticles have been prepared via simple, green and scalable hydrothermal synthesis pathways utilizing sub- and supercritical conditions to attain specific product characteristics. The crystal-, magnetic- and micro-structures of the prepared crystallites have been elucidated through meticulous characterization employing several complementary techniques. Analysis of energy dispersive X-ray spectroscopy (EDS) and X-ray absorption near edge structure (XANES) data verifies the desired stoichiometries with divalent M and trivalent Fe ions. Robust structural characterization is carried out by simultaneous Rietveld refinement of a constrained structural model to powder X-ray diffraction (PXRD) and high-resolution neutron powder diffraction (NPD) data. The structural modeling reveals different affinities of the 3d transition metal ions for the specific crystallographic sites in the nanocrystallites, characterized by the spinel inversion degree, x, [M2+ 1−xFe3+ x]tet[M2+ xFe3+ 2−x]octO4, compared to the well-established bulk structures. The MnFe2O4 and CoFe2O4 nanocrystallites exhibit random disordered spinel structures (x = 0.643(3) and 0.660(6)), while NiFe2O4 is a completely inverse spinel (x = 1.00) and ZnFe2O4 is close to a normal spinel (x = 0.166(10)). Furthermore, the size, size distribution and morphology of the nanoparticles have been assessed by peak profile analysis of the diffraction data, transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The differences in nanostructure, spinel inversion and distinct magnetic nature of the M2+ ions directly alter the magnetic structures of the crystallites at the atomic-scale and consequently the macroscopic magnetic properties of the materials. The present study serves as an important structural benchmark for the rapidly expanding field of spinel ferrite nanoparticle research.

Original languageEnglish
JournalNanoscale
Volume10
Issue number31
Pages (from-to)14902-14914
Number of pages13
ISSN2040-3364
DOIs
Publication statusPublished - 2018

Cite this

Andersen, H. L., Saura-Múzquiz, M., Granados, C., Canévet, E., Lock, N., & Christensen, M. (2018). Crystalline and magnetic structure-property relationship in spinel ferrite nanoparticles. Nanoscale, 10(31), 14902-14914. https://doi.org/10.1039/c8nr01534a
Andersen, Henrik Lyder ; Saura-Múzquiz, Matilde ; Granados, Cecilia ; Canévet, Emmanuel ; Lock, Nina ; Christensen, Mogens. / Crystalline and magnetic structure-property relationship in spinel ferrite nanoparticles. In: Nanoscale. 2018 ; Vol. 10, No. 31. pp. 14902-14914.
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title = "Crystalline and magnetic structure-property relationship in spinel ferrite nanoparticles",
abstract = "Magnetic spinel ferrite MFe2O4 (M = Mn, Co, Ni, Zn) nanoparticles have been prepared via simple, green and scalable hydrothermal synthesis pathways utilizing sub- and supercritical conditions to attain specific product characteristics. The crystal-, magnetic- and micro-structures of the prepared crystallites have been elucidated through meticulous characterization employing several complementary techniques. Analysis of energy dispersive X-ray spectroscopy (EDS) and X-ray absorption near edge structure (XANES) data verifies the desired stoichiometries with divalent M and trivalent Fe ions. Robust structural characterization is carried out by simultaneous Rietveld refinement of a constrained structural model to powder X-ray diffraction (PXRD) and high-resolution neutron powder diffraction (NPD) data. The structural modeling reveals different affinities of the 3d transition metal ions for the specific crystallographic sites in the nanocrystallites, characterized by the spinel inversion degree, x, [M2+ 1−xFe3+ x]tet[M2+ xFe3+ 2−x]octO4, compared to the well-established bulk structures. The MnFe2O4 and CoFe2O4 nanocrystallites exhibit random disordered spinel structures (x = 0.643(3) and 0.660(6)), while NiFe2O4 is a completely inverse spinel (x = 1.00) and ZnFe2O4 is close to a normal spinel (x = 0.166(10)). Furthermore, the size, size distribution and morphology of the nanoparticles have been assessed by peak profile analysis of the diffraction data, transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The differences in nanostructure, spinel inversion and distinct magnetic nature of the M2+ ions directly alter the magnetic structures of the crystallites at the atomic-scale and consequently the macroscopic magnetic properties of the materials. The present study serves as an important structural benchmark for the rapidly expanding field of spinel ferrite nanoparticle research.",
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Andersen, HL, Saura-Múzquiz, M, Granados, C, Canévet, E, Lock, N & Christensen, M 2018, 'Crystalline and magnetic structure-property relationship in spinel ferrite nanoparticles', Nanoscale, vol. 10, no. 31, pp. 14902-14914. https://doi.org/10.1039/c8nr01534a

Crystalline and magnetic structure-property relationship in spinel ferrite nanoparticles. / Andersen, Henrik Lyder; Saura-Múzquiz, Matilde; Granados, Cecilia; Canévet, Emmanuel; Lock, Nina; Christensen, Mogens.

In: Nanoscale, Vol. 10, No. 31, 2018, p. 14902-14914.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Crystalline and magnetic structure-property relationship in spinel ferrite nanoparticles

AU - Andersen, Henrik Lyder

AU - Saura-Múzquiz, Matilde

AU - Granados, Cecilia

AU - Canévet, Emmanuel

AU - Lock, Nina

AU - Christensen, Mogens

PY - 2018

Y1 - 2018

N2 - Magnetic spinel ferrite MFe2O4 (M = Mn, Co, Ni, Zn) nanoparticles have been prepared via simple, green and scalable hydrothermal synthesis pathways utilizing sub- and supercritical conditions to attain specific product characteristics. The crystal-, magnetic- and micro-structures of the prepared crystallites have been elucidated through meticulous characterization employing several complementary techniques. Analysis of energy dispersive X-ray spectroscopy (EDS) and X-ray absorption near edge structure (XANES) data verifies the desired stoichiometries with divalent M and trivalent Fe ions. Robust structural characterization is carried out by simultaneous Rietveld refinement of a constrained structural model to powder X-ray diffraction (PXRD) and high-resolution neutron powder diffraction (NPD) data. The structural modeling reveals different affinities of the 3d transition metal ions for the specific crystallographic sites in the nanocrystallites, characterized by the spinel inversion degree, x, [M2+ 1−xFe3+ x]tet[M2+ xFe3+ 2−x]octO4, compared to the well-established bulk structures. The MnFe2O4 and CoFe2O4 nanocrystallites exhibit random disordered spinel structures (x = 0.643(3) and 0.660(6)), while NiFe2O4 is a completely inverse spinel (x = 1.00) and ZnFe2O4 is close to a normal spinel (x = 0.166(10)). Furthermore, the size, size distribution and morphology of the nanoparticles have been assessed by peak profile analysis of the diffraction data, transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The differences in nanostructure, spinel inversion and distinct magnetic nature of the M2+ ions directly alter the magnetic structures of the crystallites at the atomic-scale and consequently the macroscopic magnetic properties of the materials. The present study serves as an important structural benchmark for the rapidly expanding field of spinel ferrite nanoparticle research.

AB - Magnetic spinel ferrite MFe2O4 (M = Mn, Co, Ni, Zn) nanoparticles have been prepared via simple, green and scalable hydrothermal synthesis pathways utilizing sub- and supercritical conditions to attain specific product characteristics. The crystal-, magnetic- and micro-structures of the prepared crystallites have been elucidated through meticulous characterization employing several complementary techniques. Analysis of energy dispersive X-ray spectroscopy (EDS) and X-ray absorption near edge structure (XANES) data verifies the desired stoichiometries with divalent M and trivalent Fe ions. Robust structural characterization is carried out by simultaneous Rietveld refinement of a constrained structural model to powder X-ray diffraction (PXRD) and high-resolution neutron powder diffraction (NPD) data. The structural modeling reveals different affinities of the 3d transition metal ions for the specific crystallographic sites in the nanocrystallites, characterized by the spinel inversion degree, x, [M2+ 1−xFe3+ x]tet[M2+ xFe3+ 2−x]octO4, compared to the well-established bulk structures. The MnFe2O4 and CoFe2O4 nanocrystallites exhibit random disordered spinel structures (x = 0.643(3) and 0.660(6)), while NiFe2O4 is a completely inverse spinel (x = 1.00) and ZnFe2O4 is close to a normal spinel (x = 0.166(10)). Furthermore, the size, size distribution and morphology of the nanoparticles have been assessed by peak profile analysis of the diffraction data, transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The differences in nanostructure, spinel inversion and distinct magnetic nature of the M2+ ions directly alter the magnetic structures of the crystallites at the atomic-scale and consequently the macroscopic magnetic properties of the materials. The present study serves as an important structural benchmark for the rapidly expanding field of spinel ferrite nanoparticle research.

U2 - 10.1039/c8nr01534a

DO - 10.1039/c8nr01534a

M3 - Journal article

VL - 10

SP - 14902

EP - 14914

JO - Nanoscale

JF - Nanoscale

SN - 2040-3364

IS - 31

ER -

Andersen HL, Saura-Múzquiz M, Granados C, Canévet E, Lock N, Christensen M. Crystalline and magnetic structure-property relationship in spinel ferrite nanoparticles. Nanoscale. 2018;10(31):14902-14914. https://doi.org/10.1039/c8nr01534a