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Controlling Cation Distribution and Morphology in Colloidal Zinc Ferrite Nanocrystals

[Image: see text] This paper describes the first synthetic method to achieve independent control over both the cation distribution (quantified by the inversion parameter x) and size of colloidal ZnFe(2)O(4) nanocrystals. Use of a heterobimetallic triangular complex of formula ZnFe(2)(μ(3)-O)(μ(2)-O(...

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Autores principales: Sanchez-Lievanos, Karla R., Knowles, Kathryn E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9417087/
https://www.ncbi.nlm.nih.gov/pubmed/36039100
http://dx.doi.org/10.1021/acs.chemmater.2c01568
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author Sanchez-Lievanos, Karla R.
Knowles, Kathryn E.
author_facet Sanchez-Lievanos, Karla R.
Knowles, Kathryn E.
author_sort Sanchez-Lievanos, Karla R.
collection PubMed
description [Image: see text] This paper describes the first synthetic method to achieve independent control over both the cation distribution (quantified by the inversion parameter x) and size of colloidal ZnFe(2)O(4) nanocrystals. Use of a heterobimetallic triangular complex of formula ZnFe(2)(μ(3)-O)(μ(2)-O(2)CCF(3))(6)(H(2)O)(3) as a single-source precursor, solvothermal reaction conditions, absence of hydroxyl groups from the reaction solvent, and the presence of oleylamine are required to achieve well-defined, crystalline, and monodisperse ZnFe(2)O(4) nanoparticles. The size of the ZnFe(2)O(4) nanocrystals increases as the ratio of oleic acid and oleylamine ligands to precursor increases. The inversion parameter increases with increasing solubility of the precursor in the reaction solvent, with the presence of oleic acid in the reaction mixture, and with decreasing reaction temperature. These results are consistent with a mechanism in which ligand exchange between oleic acid and carboxylate ligands bound to the precursor complex influences the degree to which the reaction produces a kinetically trapped or thermodynamically stable cation distribution. Importantly, these results indicate that preservation of the triangular Zn–O–Fe(2) core structure of the precursor in the reactive monomer species is crucial to the production of a phase-pure ZnFe(2)O(4) product and to the ability to tune the cation distribution. Overall, these results demonstrate the advantages of using a single-source precursor and solvothermal reaction conditions to achieve synthetic control over the structure of ternary spinel ferrite nanocrystals.
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spelling pubmed-94170872022-08-27 Controlling Cation Distribution and Morphology in Colloidal Zinc Ferrite Nanocrystals Sanchez-Lievanos, Karla R. Knowles, Kathryn E. Chem Mater [Image: see text] This paper describes the first synthetic method to achieve independent control over both the cation distribution (quantified by the inversion parameter x) and size of colloidal ZnFe(2)O(4) nanocrystals. Use of a heterobimetallic triangular complex of formula ZnFe(2)(μ(3)-O)(μ(2)-O(2)CCF(3))(6)(H(2)O)(3) as a single-source precursor, solvothermal reaction conditions, absence of hydroxyl groups from the reaction solvent, and the presence of oleylamine are required to achieve well-defined, crystalline, and monodisperse ZnFe(2)O(4) nanoparticles. The size of the ZnFe(2)O(4) nanocrystals increases as the ratio of oleic acid and oleylamine ligands to precursor increases. The inversion parameter increases with increasing solubility of the precursor in the reaction solvent, with the presence of oleic acid in the reaction mixture, and with decreasing reaction temperature. These results are consistent with a mechanism in which ligand exchange between oleic acid and carboxylate ligands bound to the precursor complex influences the degree to which the reaction produces a kinetically trapped or thermodynamically stable cation distribution. Importantly, these results indicate that preservation of the triangular Zn–O–Fe(2) core structure of the precursor in the reactive monomer species is crucial to the production of a phase-pure ZnFe(2)O(4) product and to the ability to tune the cation distribution. Overall, these results demonstrate the advantages of using a single-source precursor and solvothermal reaction conditions to achieve synthetic control over the structure of ternary spinel ferrite nanocrystals. American Chemical Society 2022-08-01 2022-08-23 /pmc/articles/PMC9417087/ /pubmed/36039100 http://dx.doi.org/10.1021/acs.chemmater.2c01568 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Sanchez-Lievanos, Karla R.
Knowles, Kathryn E.
Controlling Cation Distribution and Morphology in Colloidal Zinc Ferrite Nanocrystals
title Controlling Cation Distribution and Morphology in Colloidal Zinc Ferrite Nanocrystals
title_full Controlling Cation Distribution and Morphology in Colloidal Zinc Ferrite Nanocrystals
title_fullStr Controlling Cation Distribution and Morphology in Colloidal Zinc Ferrite Nanocrystals
title_full_unstemmed Controlling Cation Distribution and Morphology in Colloidal Zinc Ferrite Nanocrystals
title_short Controlling Cation Distribution and Morphology in Colloidal Zinc Ferrite Nanocrystals
title_sort controlling cation distribution and morphology in colloidal zinc ferrite nanocrystals
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9417087/
https://www.ncbi.nlm.nih.gov/pubmed/36039100
http://dx.doi.org/10.1021/acs.chemmater.2c01568
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