Magnetic nanoparticles are being developed as structural and functional materials for use in diverse areas, including biomedical applications. Here, we report the synthesis of maghemite (γ-Fe 2 O 3 ) nanoparticles with distinct morphologies: single-core and multicore, including hollow spheres and nanoflowers, prepared by the polyol process. We have used sodium acetate to control the nucleation and assembly process to obtain the different particle morphologies. Moreover, from samples obtained at different time steps during the synthesis, we have elucidated the formation mechanism of the nanoflowers: the initial phases of the reaction present a lepidocrocite (γ-FeOOH) structure, which suffers a fast dehydroxylation, transforming to an intermediate “undescribed” phase, possibly a partly dehydroxylated lepidocrocite, which after some incubation time evolves to maghemite nanoflowers. Once the nanoflowers have been formed, a crystallization process takes place, where the γ-Fe 2 O 3 crystallites within the nanoflowers grow in size (from ∼11 to 23 nm), but the particle size of the flower remains essentially unchanged (∼60 nm). Samples with different morphologies were coated with citric acid and their heating capacity in an alternating magnetic field was evaluated. We observe that nanoflowers with large cores (23 nm, controlled by annealing) densely packed (tuned by low NaAc concentration) offer 5 times enhanced heating capacity compared to that of the nanoflowers with smaller core sizes (15 nm), 4 times enhanced heating effect compared to that of the hollow spheres, and 1.5 times enhanced heating effect compared to that of single-core nanoparticles (36 nm) used in this work.

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 δM plots of γ-Fe 2 O 3 nanoparticles isolated by thick SiO 2 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 magnetizations states in nanoparticles.Additional information on the δM and the in-field Mössbauer techniques, table with the complete results of the Mössbauer spectra fits, details of the Monte Carlo simulations, FC and ZFC magnetization curves of the VST series (Fig. S1a), Langevin scaling of M(H;T) data measured in VST45 (Fig. S1b), details on the estimate of the "magnetic size" from Langevin fits, δM plots of all the VST series and graphical analysis of the intraparticle and interparticle contributions to the dip (Fig. S2), example of hysteresis loops measured after ZFC and FC (for sample VST17, Fig. S3); X-ray diffraction patterns and lattice parameter across of the maghemite cores of different size (Fig. S4); complete results from Monte Carlo simulations showing the dependence of δM on core anisotropy (Fig. S5), surface anisotropy ( Fig. S6), exchange coupling constant ( Fig. S7) and disordered surface thickness (Fig. S8).

Applications based on aggregates of magnetic nanoparticles are becoming increasingly widespread, ranging from hyperthermia to magnetic recording. However, although some uses require a collective behavior, other need a more individual-like response, the conditions leading to either of these behaviors are still poorly understood. Here we use nanoscaleuniform binary random dense mixtures with different proportions of oxide magnetic nanoparticles with low/high anisotropy as a valuable tool to explore the crossover from individual to collective behavior. Two different anisotropy scenarios have been studied in two series of binary compacts: M1, comprising maghemite (-Fe2O3) nanoparticles of different sizes (9.0 nm / 11.5 nm) with barely a factor of 2 between their anisotropy energies and M2, mixing equally-sized pure maghemite (low-anisotropy) and Co-doped maghemite (high-anisotropy) nanoparticles with a large difference in anisotropy energy (ratio > 8).Interestingly, while the M1 series exhibits collective behavior typical of strongly-coupled dipolar systems, the M2 series presents a more complex scenario where different magnetic properties resemble either "individual-like" or "collective", crucially emphasizing that the collective character must be ascribed to specific properties and not to the system as a whole.The strong differences between the two series, offer new insight (systematically ratified by simulations) into the subtle interplay between dipolar interactions, local anisotropy and sample heterogeneity, to determine the behavior of dense assemblies of magnetic nanoparticles.peak temperature TMAX (Thalt  2· TMAX /3), then resumed to the lowest temperature (10 K).Subsequently, the M(T) curve is registered under exactly the same conditions as the reference ZFC curve. DCD (direct current demagnetization) remanence curves were measured by initially saturating the sample (in H = -50 kOe) and then measuring the moment after application and removal of progressively increasing reverse fields. 76 Finally, the temperature dependence of the ac susceptibility was recorded at 10 Hz using a field amplitude of 1 Oe.All the magnetic measurements were performed using a MPMS SQUID magnetometer from Quantum Design.Monte Carlo simulations. Monte Carlo simulations were carried out using the mesoscopic three-spins model 53 (see Supporting Information for details). [77][78][79]

While magnetic supports have been widely used to immobilize homogeneous catalysts in organic chemistry, this strategy has so far found very little application in photocatalysis. Indeed, magnetic supports are dark colored, and thus compete for photon absorption with photocatalysts themselves. We have developed a series of core–shell Fe(0)-silica nanoparticles as supports for immobilizing the photosensitizer Ru­(bpy)3 2+, featuring various silica shell thicknesses16–34 nm SiO2on 9 nm Fe cores. The supports and the resulting photocatalytic systems were studied for their magnetic, optical, and catalytic properties in the context of the photooxidation of citronellol, and we found that thicker silica shells lead to higher catalytic activity. We correlated this effect as well as Ru­(bpy)3 2+ fluorescence and singlet oxygen generation to the absorption properties of the supports. We were able to reuse our optimal system three times with minimal loss of activity and achieved turnover numbers largely surpassing the performance of homogeneous Ru­(bpy)3 2+. This work highlights the role of material design in the conception of new supports for applications in heterogeneous photocatalysis.