Issue 2, 2022

Tailoring defects and nanocrystal transformation for optimal heating power in bimagnetic CoyFe1−yO@CoxFe3−xO4 particles

Abstract

The effects of cobalt incorporation in spherical heterostructured iron oxide nanocrystals (NCs) of sub-critical size have been explored by colloidal chemistry methods. Synchrotron X-ray total scattering methods suggest that cobalt (Co) substitution in rock salt iron oxide NCs tends to remedy their vacant iron sites, offering a higher degree of resistance to oxidative conversion. Self-passivation still creates a spinel-like shell, but with a higher volume fraction of the rock salt Co-containing phase in the core. The higher divalent metal stoichiometry in the rock salt phase, with increasing Co content, results in a population of unoccupied tetrahedral metal sites in the spinel part, likely through oxidative shell creation, involving an ordered defect-clustering mechanism, directly correlated to core stabilization. To shed light on the effects of Co-substitution and atomic-scale defects (vacant sites), Monte Carlo simulations suggest that the designed NCs, with desirable, enhanced magnetic properties (cf. exchange bias and coercivity), are developed with magnetocrystalline anisotropy which increases due to a relatively low content of Co ions in the lattice. The growth of optimally performing candidates combines also a strongly exchange-coupled system, secured through a high volumetric ratio rock salt phase, interfaced by a not so defective spinel shell. In view of these requirements, specific absorption rate (SAR) calculations demonstrate that the rock salt core sufficiently protected from oxidation and the heterostructure preserved over time, play a key role in magnetically mediated heating efficacies, for potential use of such NCs in magnetic hyperthermia applications.

Graphical abstract: Tailoring defects and nanocrystal transformation for optimal heating power in bimagnetic CoyFe1−yO@CoxFe3−xO4 particles

Supplementary files

Article information

Article type
Paper
Submitted
06 Aug. 2021
Accepted
30 Nov. 2021
First published
30 Nov. 2021
This article is Open Access
Creative Commons BY license

Nanoscale, 2022,14, 382-401

Tailoring defects and nanocrystal transformation for optimal heating power in bimagnetic CoyFe1−yO@CoxFe3−xO4 particles

G. Antonaropoulos, M. Vasilakaki, K. N. Trohidou, V. Iannotti, G. Ausanio, M. Abeykoon, E. S. Bozin and A. Lappas, Nanoscale, 2022, 14, 382 DOI: 10.1039/D1NR05172E

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