Unraveling the Mn2+ substitution effect on the anisotropy control and magnetic hyperthermia of MnxFe3−xO4 nanoparticles

Composition is a key parameter to effectively tune the magnetic anisotropy of magnetic nanoparticles, which in turn can modulate their structural–magnetic properties and final applications. The Mn2+ content of manganese ferrite nanoparticles (MnxFe3−xO4) deeply impacts their structure, anisotropy, m...

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Autores: Odio, Oscar F., Tommasini, Giuseppina, Teran, Francisco J., Ovejero, Jesús G., Rubín, Javier, Moros, María, Del Sol-Fernández, Susel
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/404543
Acesso em linha:http://hdl.handle.net/10261/404543
Access Level:acceso abierto
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dc.title.none.fl_str_mv Unraveling the Mn2+ substitution effect on the anisotropy control and magnetic hyperthermia of MnxFe3−xO4 nanoparticles
title Unraveling the Mn2+ substitution effect on the anisotropy control and magnetic hyperthermia of MnxFe3−xO4 nanoparticles
spellingShingle Unraveling the Mn2+ substitution effect on the anisotropy control and magnetic hyperthermia of MnxFe3−xO4 nanoparticles
Odio, Oscar F.
title_short Unraveling the Mn2+ substitution effect on the anisotropy control and magnetic hyperthermia of MnxFe3−xO4 nanoparticles
title_full Unraveling the Mn2+ substitution effect on the anisotropy control and magnetic hyperthermia of MnxFe3−xO4 nanoparticles
title_fullStr Unraveling the Mn2+ substitution effect on the anisotropy control and magnetic hyperthermia of MnxFe3−xO4 nanoparticles
title_full_unstemmed Unraveling the Mn2+ substitution effect on the anisotropy control and magnetic hyperthermia of MnxFe3−xO4 nanoparticles
title_sort Unraveling the Mn2+ substitution effect on the anisotropy control and magnetic hyperthermia of MnxFe3−xO4 nanoparticles
dc.creator.none.fl_str_mv Odio, Oscar F.
Tommasini, Giuseppina
Teran, Francisco J.
Ovejero, Jesús G.
Rubín, Javier
Moros, María
Del Sol-Fernández, Susel
author Odio, Oscar F.
author_facet Odio, Oscar F.
Tommasini, Giuseppina
Teran, Francisco J.
Ovejero, Jesús G.
Rubín, Javier
Moros, María
Del Sol-Fernández, Susel
author_role author
author2 Tommasini, Giuseppina
Teran, Francisco J.
Ovejero, Jesús G.
Rubín, Javier
Moros, María
Del Sol-Fernández, Susel
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv European Commission
European Research Council
Agencia Estatal de Investigación (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Universidad de Zaragoza
Gobierno de Aragón
Consejo Nacional de Humanidades, Ciencias y Tecnologías (México)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Composition is a key parameter to effectively tune the magnetic anisotropy of magnetic nanoparticles, which in turn can modulate their structural–magnetic properties and final applications. The Mn2+ content of manganese ferrite nanoparticles (MnxFe3−xO4) deeply impacts their structure, anisotropy, magnetism, and their heating capacity. However, a direct correlation between Mn2+ content, magnetic properties and heating efficiency is not yet clear. Herein, we report the synthesis of a wide range of MnxFe3−xO4 with x = 0.14 to 1.40, with similar polyhedral morphologies and sizes (13 to 15 nm). By varying the Mn2+ content (in the range of x = 0.0 up to 0.70), we successfully tuned the effective anisotropy while maintaining saturation magnetization nearly constant. Highest Mn2+ levels (x = 1.40) lead to structural changes and strain defects reflected in their poor saturation magnetization. Mn2+ substitution is not uniform, instead promotes a compositional gradient across the MNPs, with the surface layers having a higher concentration of Mn2+ than the core. The Mn2+-rich surface likely exhibits superparamagnetic (SPM) relaxation, while the core remains predominantly ferrimagnetic (FiM). Water transference results in cation leaching, promoting vacancies and changes in the local ferrite structure but with a minor impact on the magnetic properties compared with initial MNPs. We obtained the optimal Mn2+ content that maximizes anisotropy toward improved specific loss power (SLP) values. The Néel relaxation mechanism is warranted regarding variable composition when sizes and shapes are maintained. Our detailed analysis provides a better understanding of the effect of Mn2+ substitution on the heating efficiency through anisotropy modulation and straightforward guidance on optimizing MNP design for magnetic hyperthermia.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025
2025
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dc.language.none.fl_str_mv Inglés
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info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-122508NB-I00
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The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1039/D5NH00254K
https://doi.org/10.1039/D5NH00254K
Sí
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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 Unraveling the Mn2+ substitution effect on the anisotropy control and magnetic hyperthermia of MnxFe3−xO4 nanoparticlesOdio, Oscar F.Tommasini, GiuseppinaTeran, Francisco J.Ovejero, Jesús G.Rubín, JavierMoros, MaríaDel Sol-Fernández, SuselComposition is a key parameter to effectively tune the magnetic anisotropy of magnetic nanoparticles, which in turn can modulate their structural–magnetic properties and final applications. The Mn2+ content of manganese ferrite nanoparticles (MnxFe3−xO4) deeply impacts their structure, anisotropy, magnetism, and their heating capacity. However, a direct correlation between Mn2+ content, magnetic properties and heating efficiency is not yet clear. Herein, we report the synthesis of a wide range of MnxFe3−xO4 with x = 0.14 to 1.40, with similar polyhedral morphologies and sizes (13 to 15 nm). By varying the Mn2+ content (in the range of x = 0.0 up to 0.70), we successfully tuned the effective anisotropy while maintaining saturation magnetization nearly constant. Highest Mn2+ levels (x = 1.40) lead to structural changes and strain defects reflected in their poor saturation magnetization. Mn2+ substitution is not uniform, instead promotes a compositional gradient across the MNPs, with the surface layers having a higher concentration of Mn2+ than the core. The Mn2+-rich surface likely exhibits superparamagnetic (SPM) relaxation, while the core remains predominantly ferrimagnetic (FiM). Water transference results in cation leaching, promoting vacancies and changes in the local ferrite structure but with a minor impact on the magnetic properties compared with initial MNPs. We obtained the optimal Mn2+ content that maximizes anisotropy toward improved specific loss power (SLP) values. The Néel relaxation mechanism is warranted regarding variable composition when sizes and shapes are maintained. Our detailed analysis provides a better understanding of the effect of Mn2+ substitution on the heating efficiency through anisotropy modulation and straightforward guidance on optimizing MNP design for magnetic hyperthermia.S. D.S.-F. acknowledges Marie Skłodowska-Curie Postdoctoral Fellowships (HORIZON-MSCA-2021-PF-01-01, Grant agreement No. 101064735) funded by the European Union. This work has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (Grant agreement No. 853468), MCIN/AEI/10.13039/501100011033 and FSE+ (PID2021-122508NB-I00) and project CNS2022-135700 funded by MICIU/AEI /10.13039/501100011033 and the European Union NextGenerationEU/PRTR. The authors would like to acknowledge Fondo Social del Gobierno de Aragón (grupo DGA E15_23R) and MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) promoted by the Government of Aragon and CEX2023-001286-S funding from MICIU/AEI/10.13039/501100011033. The project CONAHCyT LNC-2023-95 partially supported this study. The authors would like to acknowledge the use of Advanced Microscopy Laboratory (Universidad de Zaragoza), for access to their instrumentation and expertise and the use of Servicio General de Apoyo a la Investigacion-SAI, Universidad de Zaragoza. Likewise, the authors thank LNCAE (Laboratorio Nacional de Conversión y Almacenamiento de Energía) of the IPN (Instituto Politécnico Nacional) for access to its XPS experimental facility.With funding from the Spanish government through the "Severo Ochoa Centre of Excellence" accreditation (CEX2023-001286-S).Peer reviewedRoyal Society of Chemistry (UK)European CommissionEuropean Research CouncilAgencia Estatal de Investigación (España)Ministerio de Ciencia, Innovación y Universidades (España)Universidad de ZaragozaGobierno de AragónConsejo Nacional de Humanidades, Ciencias y Tecnologías (México)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/404543reponame: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##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/EC/HE/101064735info:eu-repo/grantAgreement/EC/H2020/853468info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-122508NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CNS2022-135700info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2023-001286-SThe underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1039/D5NH00254Khttps://doi.org/10.1039/D5NH00254KSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/4045432026-05-22T06:33:51Z
score 15.812455

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