Effects of Rhenium Substitution of Co and Fe in Spinel CoFe2O4 Ferrite Nanomaterials

Abstract

In this work, nanoparticles of Co1−xRexFe2O4 and CoFe2−xRexO4 (0 ≤ x ≤ 0.05) were synthesized by the sol-gel method. The Rietveld refinement analysis of XRD and Raman data revealed that all of the prepared samples were single phase with a cubic spinel-type structure. With the substitution of Re, the lattice parameters were slightly increased, and Raman spectra peak positions corresponding to the movement of the tetrahedral sublattice shifted to a higher energy position. Furthermore, Raman spectra showed the splitting of T2g mode into branches, indicating the presence of different cations at crystallographic A- and B-sites. The SEM micrograph confirms that surface Re exchange changes the coordination environment of metals and induces Fe-site structure distortion, thereby revealing more active sites for reactions and indicating the bulk sample’s porous and agglomerated morphology. The vibrating sample magnetometer (VSM) results demonstrated that the synthesized nanoparticles of all samples were ferromagnetic across the entire temperature range of 300–4 K. The estimated magnetic parameters, such as the saturation magnetization, remanent magnetization, coercivity, blocking temperature (TB), and magnetic anisotropy, were found to reduce for the Co-site doping with the increasing doping ratio of Re, while in the Fe site, they enhanced with the increasing doping ratio. The ZFC-FC magnetization curve revealed the presence of spin-glass-like behavior due to the strong dipole–dipole interactions in these ferrite nanoparticles over the whole temperature range. Finally, the dielectric constant (εr′) and dielectric loss (tanδ) were sharply enhanced at low frequencies, while the AC conductivity increased at high frequencies. The sharp increases at high temperatures are explained by enhancing the barrier for charge mobility at grain boundaries, suggesting that samples were highly resistive. Interestingly, these parameters (εr′, tanδ) were found to be higher for the Fe-site doping with the increasing Re doping ratio compared with the Co site.

Impact of the rhenium substitution on the oxygen evolution reaction of spinel CoFe2O4

“…67,68 In our previous work, we performed magnetic tests for all three samples and observed a higher saturation magnetization for the iron-doped samples, which further verified the enhanced cation migration in the Fe-doped sample. 31…”

“…A doping concentration as small as 0.05% has proven to vastly alter the host material's structural, electrical and magnetic properties. 31 We veried that the material's OER performance can also be improved with a similar doping concentration at the correct site. We further performed theoretical and experimental studies of the dopedmaterials using DFT, XPS and changing-temperature Raman for more in-depth explanation and to shed light on the direction of future improvements.…”