The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth

The nucleation, crystallization, and growth mechanisms of MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanocrystallites prepared from coprecipitated transition metal (TM) hydroxide precursors treated at sub-, near-, and supercritical hydrothermal conditions have been studied by in situ X-ray total scatter...

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Autores: Andersen, Henrik L., Granados-Miralles, Cecilia, Jensen, K.M.I., Saura-Múzquiz, M., Christensen, M.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/380768
Acceso en línea:http://hdl.handle.net/10261/380768
https://www.scopus.com/inward/record.uri?eid=2-s2.0-85188660354&doi=10.1021%2facsnano.3c08772&partnerID=40&md5=c1ac6236b76a36828778ecabedacc07b
Access Level:acceso abierto
Palabra clave:hydrothermal synthesis
in situ total scattering
nucleation mechanism
pair distribution function (PDF)
size control
spinel ferrite nanoparticles
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dc.title.none.fl_str_mv The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth
title The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth
spellingShingle The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth
Andersen, Henrik L.
hydrothermal synthesis
in situ total scattering
nucleation mechanism
pair distribution function (PDF)
size control
spinel ferrite nanoparticles
title_short The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth
title_full The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth
title_fullStr The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth
title_full_unstemmed The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth
title_sort The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth
dc.creator.none.fl_str_mv Andersen, Henrik L.
Granados-Miralles, Cecilia
Jensen, K.M.I.
Saura-Múzquiz, M.
Christensen, M.
author Andersen, Henrik L.
author_facet Andersen, Henrik L.
Granados-Miralles, Cecilia
Jensen, K.M.I.
Saura-Múzquiz, M.
Christensen, M.
author_role author
author2 Granados-Miralles, Cecilia
Jensen, K.M.I.
Saura-Múzquiz, M.
Christensen, M.
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Lund University
Danish National Research Foundation
Innovation Fund Denmark
Danish Center for Synchrotron and Neutron Science
Ministerio de Ciencia, Innovación y Universidades (España)
Comunidad de Madrid
Agencia Estatal de Investigación (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv hydrothermal synthesis
in situ total scattering
nucleation mechanism
pair distribution function (PDF)
size control
spinel ferrite nanoparticles
topic hydrothermal synthesis
in situ total scattering
nucleation mechanism
pair distribution function (PDF)
size control
spinel ferrite nanoparticles
description The nucleation, crystallization, and growth mechanisms of MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanocrystallites prepared from coprecipitated transition metal (TM) hydroxide precursors treated at sub-, near-, and supercritical hydrothermal conditions have been studied by in situ X-ray total scattering (TS) with pair distribution function (PDF) analysis, and in situ synchrotron powder X-ray diffraction (PXRD) with Rietveld analysis. The in situ TS experiments were carried out on 0.6 M TM hydroxide precursors prepared from aqueous metal chloride solutions using 24.5% NH4OH as the precipitating base. The PDF analysis reveals equivalent nucleation processes for the four spinel ferrite compounds under the studied hydrothermal conditions, where the TMs form edge-sharing octahedrally coordinated hydroxide units (monomers/dimers and in some cases trimers) in the aqueous precursor, which upon hydrothermal treatment nucleate through linking by tetrahedrally coordinated TMs. The in situ PXRD experiments were carried out on 1.2 M TM hydroxide precursors prepared from aqueous metal nitrate solutions using 16 M NaOH as the precipitating base. The crystallization and growth of the nanocrystallites were found to progress via different processes depending on the specific TMs and synthesis temperatures. The PXRD data show that MnFe2O4 and CoFe2O4 nanocrystallites rapidly grow (typically <1 min) to equilibrium sizes of 20-25 nm and 10-12 nm, respectively, regardless of applied temperature in the 170-420 °C range, indicating limited possibility of targeted size control. However, varying the reaction time (0-30 min) and temperature (150-400 °C) allows different sizes to be obtained for NiFe2O4 (3-30 nm) and ZnFe2O4 (3-12 nm) nanocrystallites. The mechanisms controlling the crystallization and growth (nucleation, growth by diffusion, Ostwald ripening, etc.) were examined by qualitative analysis of the evolution in refined scale factor (proportional to extent of crystallization) and mean crystallite volume (proportional to extent of growth). Interestingly, lower kinetic barriers are observed for the formation of the mixed spinels (MnFe2O4 and CoFe2O4) compared to the inverse (NiFe2O4) and normal (ZnFe2O4) spinel structured compounds, suggesting that the energy barrier for formation may be lowered when the TMs have no site preference. © 2024 The Authors. Published by American Chemical Society.
publishDate 2024
dc.date.none.fl_str_mv 2024
2025
2025
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url http://hdl.handle.net/10261/380768
https://www.scopus.com/inward/record.uri?eid=2-s2.0-85188660354&doi=10.1021%2facsnano.3c08772&partnerID=40&md5=c1ac6236b76a36828778ecabedacc07b
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dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
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spelling The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and GrowthAndersen, Henrik L.Granados-Miralles, CeciliaJensen, K.M.I.Saura-Múzquiz, M.Christensen, M.hydrothermal synthesisin situ total scatteringnucleation mechanismpair distribution function (PDF)size controlspinel ferrite nanoparticlesThe nucleation, crystallization, and growth mechanisms of MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanocrystallites prepared from coprecipitated transition metal (TM) hydroxide precursors treated at sub-, near-, and supercritical hydrothermal conditions have been studied by in situ X-ray total scattering (TS) with pair distribution function (PDF) analysis, and in situ synchrotron powder X-ray diffraction (PXRD) with Rietveld analysis. The in situ TS experiments were carried out on 0.6 M TM hydroxide precursors prepared from aqueous metal chloride solutions using 24.5% NH4OH as the precipitating base. The PDF analysis reveals equivalent nucleation processes for the four spinel ferrite compounds under the studied hydrothermal conditions, where the TMs form edge-sharing octahedrally coordinated hydroxide units (monomers/dimers and in some cases trimers) in the aqueous precursor, which upon hydrothermal treatment nucleate through linking by tetrahedrally coordinated TMs. The in situ PXRD experiments were carried out on 1.2 M TM hydroxide precursors prepared from aqueous metal nitrate solutions using 16 M NaOH as the precipitating base. The crystallization and growth of the nanocrystallites were found to progress via different processes depending on the specific TMs and synthesis temperatures. The PXRD data show that MnFe2O4 and CoFe2O4 nanocrystallites rapidly grow (typically <1 min) to equilibrium sizes of 20-25 nm and 10-12 nm, respectively, regardless of applied temperature in the 170-420 °C range, indicating limited possibility of targeted size control. However, varying the reaction time (0-30 min) and temperature (150-400 °C) allows different sizes to be obtained for NiFe2O4 (3-30 nm) and ZnFe2O4 (3-12 nm) nanocrystallites. The mechanisms controlling the crystallization and growth (nucleation, growth by diffusion, Ostwald ripening, etc.) were examined by qualitative analysis of the evolution in refined scale factor (proportional to extent of crystallization) and mean crystallite volume (proportional to extent of growth). Interestingly, lower kinetic barriers are observed for the formation of the mixed spinels (MnFe2O4 and CoFe2O4) compared to the inverse (NiFe2O4) and normal (ZnFe2O4) spinel structured compounds, suggesting that the energy barrier for formation may be lowered when the TMs have no site preference. © 2024 The Authors. Published by American Chemical Society.The authors are grateful for the obtained beamtimes at beamline I711, MAXlab synchrotron radiation source, Lund University, Sweden; and beamline P02.1, PETRA III, DESY, Hamburg, Germany (ref. I-20150335 EC). Hanns-Peter Liermann, Jozef Bednarcik, Ann-Christin Dippel, Carsten Gundlach, Dorthe Haase, Diana Thomas, and Francisco Martinez are thanked for their support during the respective beamtimes. 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) and the Danish Center for Synchrotron and Neutron Science (DanScatt), The Spanish Ministry of Universities (Ministerio de Universidades) and the European UnionyNextGenerationEU through a Maria Zambrano attraction of international talent fellowship grant, and Comunidad de Madrid, Spain, through an "Atraccion de Talento Investigador" fellowship (2020-T2/IND-20581). This project has received funding from the European Union's Horizon Europe research and innovation programme under project No. 101063369 (OXYPOW). 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". C.G.-M. and M.S.-M. also acknowledge support from the Spanish Ministry of Science and Innovation through Grant TED2021-130957B-C51 and TED2021-130957B-C52 (NANOBOND) funded by MCIN/AEI/10.13039/501100011033 and by the "European Union NextGenerationEU/PRTR". Affiliation with the Center for Integrated Materials Research (iMAT) at Aarhus University is gratefully acknowledged.Supporting InformationPeer reviewedAmerican Chemical SocietyLund UniversityDanish National Research FoundationInnovation Fund DenmarkDanish Center for Synchrotron and Neutron ScienceMinisterio de Ciencia, Innovación y Universidades (España)Comunidad de MadridAgencia Estatal de Investigación (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/380768https://www.scopus.com/inward/record.uri?eid=2-s2.0-85188660354&doi=10.1021%2facsnano.3c08772&partnerID=40&md5=c1ac6236b76a36828778ecabedacc07breponame:DIGITAL.CSIC. 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