Size-modulation of functionalized Fe3O4: nanoscopic customization to devise resolute piezoelectric nanocomposites

Abstract

Magnetite (Fe₃O₄), a representative relaxor multiferroic material, possesses fundamentally appealing multifaceted size-dependent properties. Herein, to evaluate a prototype spinel transition metal oxide (STMO), monodispersed and highly water-dispersible spherical magnetite nanoparticles (MNPs) with an enormous size range (3.7–242.8 nm) were synthesized via a facile microwave-assisted and polyol-mediated solvothermal approach at a controlled temperature and pressure using unique crystallite growth inhibitors. The excellent long-term colloidal stability of the MNPs in a polar environment and increase in their zeta potential confirmed the coordinative effect of the carboxylate groups derived from the covalent surface functionalization, which was also validated by FTIR spectroscopy, TGA and XPS analysis. The optical bandgap (E_g) between the crystal field split-off bands, which was calculated using the absorption spectra, increased gradually with a decrease in size of the MNPs within a broad UV-Vis range (1.59–4.92 eV). The red-shifting of the asymmetric Raman peaks with a smaller size and short-range electron–phonon coupling could be explained by the modified phonon confinement model (MPCM), whereas ferrimagnetic nature rejigged by superparamagnetism was verified from Mössbauer analysis. These stoichiometric, non-toxic, polar and magnetic nanocrystals are not only ideal for biomedical applications, but also suitable as electroactive porous host networks. Finally, the size-modulated MNPs were incorporated in poly(vinylidene fluoride) [PVDF]-based polytype nanogenerators as an electret filler to demonstrate their piezoelectric performance (V_OC ∼115.95 V and I_SC ∼1.04 μA), exhibiting substantial electromagnetic interference shielding.