Crystal/magnetic structure and cation inversion in hydrothermally synthesized MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanoparticles: a neutron powder diffraction study

The crystal and magnetic structures of MnFe2O4, CoFe2O4, NiFe2O4 and ZnFe2O4 nanocrystallites are reported based on joint structural modelling of powder X-ray diffraction and neutron powder diffraction data. The nanoparticle samples were prepared using equivalent precursor preparation routes (co-pre...

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Autores: Andersen, Henrik L., Saura-Múzquiz, M., Granados-Miralles, Cecilia, Klemmt, R., Bøjesen, E.D., Christensen, M.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/422487
Acceso en línea:http://hdl.handle.net/10261/422487
https://www.scopus.com/inward/record.uri?eid=2-s2.0-85218306811&doi=10.1039%2Fd4ce01001a&partnerID=40&md5=a3cb5646da9c437b77e9c3140d345e33
Access Level:acceso abierto
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dc.title.none.fl_str_mv Crystal/magnetic structure and cation inversion in hydrothermally synthesized MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanoparticles: a neutron powder diffraction study
title Crystal/magnetic structure and cation inversion in hydrothermally synthesized MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanoparticles: a neutron powder diffraction study
spellingShingle Crystal/magnetic structure and cation inversion in hydrothermally synthesized MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanoparticles: a neutron powder diffraction study
Andersen, Henrik L.
title_short Crystal/magnetic structure and cation inversion in hydrothermally synthesized MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanoparticles: a neutron powder diffraction study
title_full Crystal/magnetic structure and cation inversion in hydrothermally synthesized MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanoparticles: a neutron powder diffraction study
title_fullStr Crystal/magnetic structure and cation inversion in hydrothermally synthesized MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanoparticles: a neutron powder diffraction study
title_full_unstemmed Crystal/magnetic structure and cation inversion in hydrothermally synthesized MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanoparticles: a neutron powder diffraction study
title_sort Crystal/magnetic structure and cation inversion in hydrothermally synthesized MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanoparticles: a neutron powder diffraction study
dc.creator.none.fl_str_mv Andersen, Henrik L.
Saura-Múzquiz, M.
Granados-Miralles, Cecilia
Klemmt, R.
Bøjesen, E.D.
Christensen, M.
author Andersen, Henrik L.
author_facet Andersen, Henrik L.
Saura-Múzquiz, M.
Granados-Miralles, Cecilia
Klemmt, R.
Bøjesen, E.D.
Christensen, M.
author_role author
author2 Saura-Múzquiz, M.
Granados-Miralles, Cecilia
Klemmt, R.
Bøjesen, E.D.
Christensen, M.
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Danish National Research Foundation
Innovation Fund Denmark
Danish Center for Synchrotron and Neutron Science
Comunidad de Madrid
Agencia Estatal de Investigación (España)
European Commission
Carlsberg Foundation
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The crystal and magnetic structures of MnFe2O4, CoFe2O4, NiFe2O4 and ZnFe2O4 nanocrystallites are reported based on joint structural modelling of powder X-ray diffraction and neutron powder diffraction data. The nanoparticle samples were prepared using equivalent precursor preparation routes (co-precipitation of transition metal hydroxides using NH4OH) and identical hydrothermal synthesis conditions (steel autoclave, 200 °C, 1 hour), allowing the isolated effect of the divalent cation to be evaluated. The study uncovers how variations in cation site preferences, spinel inversion degree, and crystallite size, which are challenging to discern using conventional characterization techniques, distinctly influence the magnetic structures. Diffraction peak profile analysis and scanning transmission electron microscopy images show how MnFe2O4 forms the largest crystallites (17.13(2) nm), followed by NiFe2O4 (10.31(1) nm) and CoFe2O4 (7.92(1) nm), while ZnFe2O4 forms ultrafine nanoparticles of only 3.70(1) nm. The transition metal ions have different affinities for the tetrahedral and octahedral crystallographic sites as evident from the obtained spinel inversion degrees, x, [M2+1−xFe3+x]tet[M2+xFe3+2−x]octO4. The MnFe2O4 and CoFe2O4 nanocrystallites exhibit mixed/semi-inverse spinel structures with x = 0.87(3) and 0.954(6), respectively, while NiFe2O4 is fully inverse (x = 1.00) and ZnFe2O4 is closer to a normal spinel (x = 0.138(4)). The combination of neutron diffraction and magnetic measurements illustrates how cation identity impacts site occupancy, crystallite size, and magnetization, providing new insights into the design of ferrite-based nanomaterials for magnetic applications.
publishDate 2025
dc.date.none.fl_str_mv 2025
2026
2026
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url http://hdl.handle.net/10261/422487
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dc.publisher.none.fl_str_mv Royal Society of Chemistry (UK)
publisher.none.fl_str_mv Royal Society of Chemistry (UK)
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spelling Crystal/magnetic structure and cation inversion in hydrothermally synthesized MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanoparticles: a neutron powder diffraction studyAndersen, Henrik L.Saura-Múzquiz, M.Granados-Miralles, CeciliaKlemmt, R.Bøjesen, E.D.Christensen, M.The crystal and magnetic structures of MnFe2O4, CoFe2O4, NiFe2O4 and ZnFe2O4 nanocrystallites are reported based on joint structural modelling of powder X-ray diffraction and neutron powder diffraction data. The nanoparticle samples were prepared using equivalent precursor preparation routes (co-precipitation of transition metal hydroxides using NH4OH) and identical hydrothermal synthesis conditions (steel autoclave, 200 °C, 1 hour), allowing the isolated effect of the divalent cation to be evaluated. The study uncovers how variations in cation site preferences, spinel inversion degree, and crystallite size, which are challenging to discern using conventional characterization techniques, distinctly influence the magnetic structures. Diffraction peak profile analysis and scanning transmission electron microscopy images show how MnFe2O4 forms the largest crystallites (17.13(2) nm), followed by NiFe2O4 (10.31(1) nm) and CoFe2O4 (7.92(1) nm), while ZnFe2O4 forms ultrafine nanoparticles of only 3.70(1) nm. The transition metal ions have different affinities for the tetrahedral and octahedral crystallographic sites as evident from the obtained spinel inversion degrees, x, [M2+1−xFe3+x]tet[M2+xFe3+2−x]octO4. The MnFe2O4 and CoFe2O4 nanocrystallites exhibit mixed/semi-inverse spinel structures with x = 0.87(3) and 0.954(6), respectively, while NiFe2O4 is fully inverse (x = 1.00) and ZnFe2O4 is closer to a normal spinel (x = 0.138(4)). The combination of neutron diffraction and magnetic measurements illustrates how cation identity impacts site occupancy, crystallite size, and magnetization, providing new insights into the design of ferrite-based nanomaterials for magnetic applications.The authors are grateful for the obtained beamtime at the Cold Neutron Powder Diffractometer (DMC) instrument at the Swiss Spallation Neutron Source (SINQ), Paul Scherrer Institute (PSI), Villigen, Switzerland. Lukas Keller and Emmanuel Canévet are thanked for their support during the beamtime. This work was financially supported by the Danish National Research Foundation (Center for Materials Crystallography, DNRF93), Innovation Fund Denmark (Green Chemistry for Advanced Materials, GCAM-4107-00008B), Independent Research Fund Denmark (Small and Smart Magnet Design), Danish Center for Synchrotron and Neutron Science (DanScatt), and Comunidad de Madrid, Spain, through an “Atracción de Talento Investigador” fellowship (2020-T2/IND-20581). C. G.-M. acknowledges financial support from grant RYC2021–031181-I funded by MCIN/AEI/10.13039/501100011033 and by the “European Union NextGenerationEU/PRTR”. This project has received funding from the European Union's Horizon Europe research and innovation programme under grant agreement No 101063369 (OXYPOW) and No 101109595 (MAGWIRE). Affiliation with the Center for Integrated Materials Research (iMAT) at Aarhus University is gratefully acknowledged. EDB and RK acknowledge funding from the Carlsberg Foundation (CF18-0705), Aarhus University Centre for Integrated Materials Research and the Interdisciplinary Nanoscience Center.Peer reviewedRoyal Society of Chemistry (UK)Danish National Research FoundationInnovation Fund DenmarkDanish Center for Synchrotron and Neutron ScienceComunidad de MadridAgencia Estatal de Investigación (España)European CommissionCarlsberg FoundationConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202620262025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/422487https://www.scopus.com/inward/record.uri?eid=2-s2.0-85218306811&doi=10.1039%2Fd4ce01001a&partnerID=40&md5=a3cb5646da9c437b77e9c3140d345e33reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement///info:eu-repo/grantAgreement/AEI//info:eu-repo/grantAgreement/EC/HE/101063369info:eu-repo/grantAgreement/EC/HE/101109595CrystEngCommhttps://doi.org/10.1039/d4ce01001aSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/4224872026-05-22T06:33:51Z
score 15,811543

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