Chemical engineering of cationic distribution in spinel ferrite nanoparticles: the effect on the magnetic properties.

A set of ∼9 nm CoFe2O4 nanoparticles substituted with Zn2+ and Ni2+ was prepared by thermal decomposition of metallic acetylacetonate precursors to correlate the effects of replacement of Co2+ with the resulting magnetic properties. Due to the distinct selectivity of these cations for the spinel ferrite crystal sites, we show that it is possible to tailor the magnetic anisotropy, saturation magnetization, and interparticle interactions of the nanoparticles during the synthesis stage. This approach unlocks new possibilities for enhancing the performance of spinel ferrite nanoparticles in specific applications. Particularly, our study shows that the replacement of Co2+ by 48% of Zn2+ ions led to an increase in saturation magnetization of approximately 40% from ∼103 A m2 kg-1 to ∼143 A m2 kg-1, whereas the addition of Ni2+ at a similar percentage led to an ∼30% decrease in saturation magnetization to 68-72 A m2 kg-1. The results of calculations based on the two-sublattice Néel model of magnetization match the experimental findings, demonstrating the model's effectiveness in the strategic design of spinel ferrite nanoparticles with targeted magnetic properties through doping/inversion degree engineering.

Tunable particle-agglomeration and magnetic coupling in bi-magnetic nanocomposites.

A set of non-stoichiometric Zn-Co-ferrite nanoparticles (NPs) was prepared by thermal decomposition of metallic complexes, in the presence of oleic acid, and, after a ligand-exchange process, was coated by a hydrophilic surfactant: these NPs were used as seeds in a sol-gel self-combustion synthesis to prepare nanocomposites (NCs) with a fixed weight ratio. Our focus here is the development of an efficient synthetic approach to control the magnetic coupling between a hard-magnetic matrix (Sr-ferrite) and NPs. The physico-chemical synthetic conditions (temperature, pH, colloidal stability) were optimized in order to tune their effect on the final particles' agglomeration in the matrix. We demonstrate that our synthetic approach is a novel way to produce strongly magnetically coupled NCs, where the final extrinsic properties could be tuned by controlling (i) the agglomeration of seeds in the matrix and (ii) their elemental doping.

Advancements in polyol synthesis: expanding chemical horizons and Néel temperature tuning of CoO nanoparticles.

The polyol synthesis of CoO nanoparticles (NPs) is typically conducted by dissolving and heating cobalt acetate tetrahydrate and water in diethylene glycol (DEG). This process yields aggregates of approximately 100 nm made of partially aligned primary crystals. However, the synthesis demands careful temperature control to allow the nucleation of CoO while simultaneously preventing reduction, caused by the activity of DEG. This restriction hinders the flexibility to freely adjust synthesis conditions, impeding the ability to obtain particles with varied morpho-structural properties, which, in turn, directly impact chemical and physical attributes. In this context, the growth of CoO NPs in polyol was studied focusing on the effect of the polyol chain length and the synthesis temperature at two different water/cations ratios. During this investigation, we found that longer polyol chains remove the previous limits of the method, allowing the tuning of aggregate size (20-150 nm), shape (spherical-octahedral), and crystalline length (8-35 nm). Regarding the characterization, our focus revolved around investigating the magnetic properties inherent in the synthesized products. From this point of view, two pivotal findings emerged. Firstly, we identified small quantities of a layered hydroxide ferromagnetic intermediate, which acted as interference in our measurements. This intermediate exhibited magnetic properties consistent with features observed in other publications on CoO produced in systems compatible with the intermediate formation. Optimal synthetic conditions that prevent the impurity from forming were found. This resolution clarifies several ambiguities existing in literature about CoO low-temperature magnetic behavior. Secondly, a regular relationship of the NPs' TN with their crystallite size was found, allowing us to regulate TN over ~ 80 K. For the first time, a branching was found in this structure-dependent magnetic feature, with samples of spheroidal morphology consistently having lower magnetic temperatures, when compared to samples with faceted/octahedral shape, providing compelling evidence for a novel physical parameter influencing the TN of a material. These two findings contribute to the understanding of the fundamental properties of CoO and antiferromagnetic materials.

Green Synthesis of Co-Zn Spinel Ferrite Nanoparticles: Magnetic and Intrinsic Antimicrobial Properties.

Spinel ferrite magnetic nanoparticles have attracted considerable attention because of their high and flexible magnetic properties and biocompatibility. In this work, a set of magnetic nanoparticles of cobalt ferrite doped with zinc was synthesized via the eco-friendly sol-gel auto-combustion method. Obtained particles displayed a room-temperature ferromagnetic behavior with tuned by chemical composition values of saturation magnetization and coercivity. The maximal values of saturation magnetization ~74 Am2/kg were found in cobalt ferrite nanoparticles with a 15-35% molar fraction of cobalt replaced by zinc ions. At the same time, the coercivity exhibited a gradually diminishing trend from ~140 to ~5 mT whereas the concentration of zinc was increased from 0 to 100%. Consequently, nanoparticles produced by the proposed method possess highly adjustable magnetic properties to satisfy the requirement of a wide range of possible applications. Further prepared nanoparticles were tested with bacterial culture to display the influence of chemical composition and magnetic structure on nanoparticles-bacterial cell interaction.