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Multifunctional nano-heterostructures (NHSs) with controlled morphology are cardinal in many applications, but the understanding of the nanoscale colloidal chemistry is yet to be fulfilled. The stability of the involved crystalline phases in different solvents at mid- and high-temperatures and reaction kinetics considerably affect the nucleation and growth of the materials and their final architecture. The formation mechanism of manganese ferrite-based core-shell NHSs is herein investigated. The effects of the core size (8, 10, and 11 nm), the shell nature (cobalt ferrite and spinel iron oxide) and the polarity of the solvent (toluene and octanol) on the dissolution phenomena of manganese ferrite are also studied. Noteworthily, the combined use of bulk (powder X-ray diffraction, 57Fe Mössbauer spectroscopy, and DC magnetometry) and nanoscale techniques (HRTEM and STEM-EDX) provides new insights into the manganese ferrite dissolution phenomena, the colloidal stability in an organic environment, and the critical size below which dissolution is complete. Moreover, the dissolved manganese and iron ions react further, leading to an inverted core-shell in the mother liquor solution, paving the way to novel synthetic pathways in nanocrystal design. The MnFe2O4@CoFe2O4 core-shell heterostructures were also employed as heat mediators, exploiting the magnetic coupling between a hard (CoFe2O4) and a soft phase (MnFe2O4).

Bismuth ferrite (BiFeO3, BFO) is one of the few single-phase crystalline compounds exhibiting strong multiferroic properties at room temperature, which makes it promising for use in various fields of science and technology. The remarkable characteristics of BFO at the nanoscale position it as a compelling candidate for enhancing the functionalities of polymeric nanocomposite materials. In this study, we explore the fabrication of polyvinylidene fluoride (PVDF) nanocomposites with a variable content of BFO nanopowders (0, 5, 10, 15, 20, and 25 wt%) by solution casting in the form of thin films with the thickness of ~60 µm. Our findings reveal that the presence of BFO nanoparticles slightly facilitates the formation of β- and γ-phases of PVDF, known for their enhanced piezoelectric properties, thereby potentially expanding the utility of PVDF-based materials in sensors, actuators, and energy harvesting devices. On the other hand, the increase in filler concentration leads to enlarged spherulite diameter and porosity of PVDF, as well as an increase in filler content above 20 wt% resulting in a decrease in the degree of crystallinity. The structural changes in the surface were found to increase the hydrophobicity of the nanocomposite surface. Magnetometry indicates that the magnetic properties of nanocomposite are influenced by the BFO nanoparticle content with the saturation magnetization at ~295 K ranging from ~0.08 emu/g to ~0.8 emu/g for samples with the lowest and higher BFO content, respectively. [ABSTRACT FROM AUTHOR]

Remanence magnetization plots (e.g., Henkel or δM plots) have been extensively used as a straightforward way to determine the presence and intensity of dipolar and exchange interactions in assemblies of magnetic nanoparticles or single domain grains. Their evaluation is particularly important in functional materials whose performance is strongly affected by the intensity of interparticle interactions, such as patterned recording media and nanostructured permanent magnets, as well as in applications such as hyperthermia and magnetic resonance imaging. Here, we demonstrate that δM plots may be misleading when the nanoparticles do not have a homogeneous internal magnetic configuration. Substantial dips in the M plots of γ-Fe2O3 nanoparticles isolated by thick SiO2 shells indicate the presence of demagnetizing interactions, usually identified as dipolar interactions. Our results, however, demonstrate that it is the inhomogeneous spin structure of the nanoparticles, as most clearly evidenced by Mössbauer measurements, that has a pronounced effect on the δM plots, leading to features remarkably similar to those produced by dipolar interactions. X-ray diffraction results combined with magnetic characterization indicate that this inhomogeneity is due to the presence of surface structural (and spin) disorder. Monte Carlo simulations unambiguously corroborate the critical role of the internal magnetic structure in the δM plots. Our findings constitute a cautionary tale on the widespread use of remanence plots to assess interparticle interactions as well as offer new perspectives in the use of Henkel and δM plots to quantify the rather elusive inhomogeneous magnetization states in nanoparticles.

Ti3C2Tx MXene is one of the most comprehensively studied 2D materials in terms of its adsorptive, transport, and catalytic properties, cytotoxic performance, etc. Still, conventional MXene synthesis approaches provide low single-flake MXene yield and frequently uncontrollable properties, demanding further post-processing. The MXene family also lacks magnetism, which is helpful for producing effective nanoadsorbents as their magnetic decantation is the cheapest and most convenient way to remove the spent adsorbent from water. Composite materials consisting of magnetic nanoparticles grown on top of MXene flakes are commonly used to provide magnetic properties to the resulting nanocomposite. In this paper, we study the possibility to delaminate multilayer Ti3C2Tx MXene sheets directly by growing iron oxide magnetic nanoparticles inside their interlayer spacing. We find out that, with a mass fraction of particles comparable or exceeding that of MXenes, their growth is accompanied by an effective enhancement of single-layer MXene yield and suitable magnetic properties of the resulting composite. The developed approach can be further used for simplifying synthesis protocols to obtain magnetic MXene-based nanoadsorbents with tunable properties. [ABSTRACT FROM AUTHOR]

The present work aimed at decorating halloysite nanotubes (HNT) with magnetic Fe3O4 nanoparticles through different synthetic routes (co-precipitation, hydrothermal, and sol-gel) to test the efficiency of three magnetic composites (HNT/Fe3O4) to remove the antibiotic ofloxacin (OFL) from waters. The chemical–physical features of the obtained materials were characterized through the application of diverse techniques (XRPD, FT-IR spectroscopy, SEM, EDS, and TEM microscopy, thermogravimetric analysis, and magnetization measurements), while ecotoxicity was assessed through a standard test on the freshwater organism Daphnia magna. Independently of the synthesis procedure, the magnetic composites were successfully obtained. The Fe3O4 is nanometric (about 10 nm) and the weight percentage is sample-dependent. It decorates the HNT's surface and also forms aggregates linking the nanotubes in Fe3O4-rich samples. Thermodynamic and kinetic experiments showed different adsorption capacities of OFL, ranging from 23 to 45 mg g−1. The kinetic process occurred within a few minutes, independently of the composite. The capability of the three HNT/Fe3O4 in removing the OFL was confirmed under realistic conditions, when OFL was added to tap, river, and effluent waters at µg L−1 concentration. No acute toxicity of the composites was observed on freshwater organisms. Despite the good results obtained for all the composites, the sample by co-precipitation is the most performant as it: (i) is easily magnetically separated from the media after the use; (ii) does not undergo any degradation after three adsorption cycles; (iii) is synthetized through a low-cost procedure. These features make this material an excellent candidate for removal of OFL from water. [ABSTRACT FROM AUTHOR]

Polymer-based multiferroics, combining magnetic and piezoelectric properties, are studied experimentally—from synthesis to multi-parameter characterization—in view of their prospects for fabricating biocompatible scaffolds. The main advantage of these systems is facile generation of mechanical deformations and electric signals in response to external magnetic fields. Herein, we address the composites based on PVDF-TrFE polymer matrices filled with a combination of piezoelectric (BaTiO3, BTO) and/or ferrimagnetic (Zn0.25Co0.75Fe2O4, ZCFO) particles. It is shown that the presence of BTO micron-size particles favors stripe-type structuring of the ZCFO filler and enhances the magnetoelectric response of the sample up to 18.6 mV/(cm∙Oe). Besides that, the admixing of BTO particles is crucial because the mechanical properties of the composite filled with only ZCFO is much less efficient in transforming magnetic excitations into the mechanical and electric responses. Attention is focused on the local surfacial mechanical properties since those, to a great extent, determine the fate of stem cells cultivated on these surfaces. The nano-indentation tests are accomplished with the aid of scanning probe microscopy technique. With their proven suitable mechanical properties, a high level of magnetoelectric conversion and also biocompatibility, the composites of the considered type are enticing as the materials for multiferroic-based polymer scaffolds. [ABSTRACT FROM AUTHOR]

Featured Application: Metallic nanoparticles with a high value of magnetization have potential interest for application in biomedicine, catalysis, composite permanent magnets, and other fields. Cobalt ferrite nanoparticles of different stoichiometries synthesized by a sol–gel autocombustion method were used as a starting material to obtain high-moment Fe50Co50 and Fe66Co34 metal nanoparticles by topochemical hydrogen reduction. Structural and magnetic investigations confirmed the formation of FeCo nanoparticles with crystallite sizes of about 30 nm and magnetization at 0.5 T of ~265 Am2/kg (0 K), which was larger than the expected bulk value, likely because of the incorporation in the body-centered cubic (bcc) FeCo structure of the residual C atoms present on the surface of the oxide particles. Temperature-dependent magnetization measurements in the H2 atmosphere were also performed to investigate in detail the reduction mechanism and the effect of an external magnetic field on the process efficiency. [ABSTRACT FROM AUTHOR]

The magnetic properties of SrFe12O19 (SFO) hard hexaferrites are governed by the complex relation to its microstructure, determining their relevance for permanent magnets´ applications. A set of SFO nanoparticles obtained by sol–gel self-combustion synthesis was selected for an in-depth structural X-Rays powder diffraction (XRPD) characterization by means of G(L) line-profile analysis. The obtained crystallites´ size distribution reveal a clear dependence of the size along the [001] direction on the synthesis approach, resulting in the formation of platelet-like crystallites. In addition, the size of the SFO nanoparticles was determined by transmission electron microscopy (TEM) analysis and the average number of crystallites within a particle was estimated. These results have been evaluated to illustrate the formation of single-domain state below a critical value, and the activation volume was derived from time dependent magnetization measurements, aiming to clarify the reversal magnetization process of hard magnetic materials. [ABSTRACT FROM AUTHOR]

Bi-magnetic core/shell nanoparticles were synthesized by a two-step high-temperature decomposition method of metal acetylacetonate salts. Transmission electron microscopy confirmed the formation of an ultrathin shell (~0.6 nm) of NiO and NiFe2O4 around the magnetically hard 8 nm CoFe2O4 core nanoparticle. Magnetization measurements showed an increase in the coercivity of the single-phase CoFe2O4 seed nanoparticles from ~1.2 T to ~1.5 T and to ~2.0 T for CoFe2O4/NiFe2O4 and CoFe2O4/NiO, respectively. The NiFe2O4 shell also increases the magnetic volume of particles and the dipolar interparticle interactions. In contrast, the NiO shell prevents such interactions and keeps the magnetic volume almost unchanged. [ABSTRACT FROM AUTHOR]