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Pronounced magnetocaloric effects are typically observed in materials that often contain expensive and rare elements and are therefore costly to mass produce. However, they can rather be exploited on a small scale for miniaturized devices such as magnetic micro coolers, thermal sensors, and magnetic micropumps. Herein, a method is developed to generate magnetocaloric microstructures from an equiatomic iron–rhodium (FeRh) bulk target through a stepwise process. First, paramagnetic near-to-equiatomic solid-solution FeRh nanoparticles (NPs) are generated through picosecond (ps)-pulsed laser ablation in ethanol, which are then transformed into a printable ink and patterned using a continuous wave laser. Laser patterning not only leads to sintering of the NP ink but also triggers the phase transformation of the initial γ- to B2-FeRh. At a laser fluence of 246 J cm−², a partial (52%) phase transformation from γ- to B2-FeRh is obtained, resulting in a magnetization increase of 35 Am² kg−¹ across the antiferromagnetic to ferromagnetic phase transition. This represents a ca. sixfold enhancement compared to previous furnace-annealed FeRh ink. Finally, herein, the ability is demonstrated to create FeRh 2D structures with different geometries using laser sintering of magnetocaloric inks, which offers advantages such as micrometric spatial resolution, in situ annealing, and structure design flexibility. in press

The paper addresses coupling of magnetic nanoparticles (MNPs) with the polymer matrix of temperature-sensitive microgels and their response to magnetic fields.

Aerobic cyclohexene oxidation and peroxide decomposition in the liquid phase were performed over a series of CoxFe3−xO4 spinel catalysts exhibiting a volcano plot for the catalytic activity with a maximum at x = 1.

Perovskites are interesting oxidation catalysts due to their chemical flexibility enabling the tuning of several properties. In this work, we synthesized LaFe1−xCoxO3 catalysts by co-precipitation and thermal decomposition, characterized them thoroughly and studied their 2-propanol oxidation activity under dry and wet conditions to bridge the knowledge gap between gas and liquid phase reactions. Transient tests showed a highly active, unstable low-temperature (LT) reaction channel in conversion profiles and a stable, less-active high-temperature (HT) channel. Cobalt incorporation had a positive effect on the activity. The effect of water was negative on the LT channel, whereas the HT channel activity was boosted for x > 0.15. The boost may originate from a slower deactivation rate of the Co3+ sites under wet conditions and a higher amount of hydroxide species on the surface comparing wet to dry feeds. Water addition resulted in a slower deactivation for Co-rich catalysts and higher activity in the HT channel state.

Sticking properties play an important role in the early phase of planet formation. In the protoplanetary disc, grains drift towards the star, being exposed to increasingly higher temperatures. Tensile strength measurements by means of the Brazilian test along with results from Mössbauer spectroscopy suggest that there is a spacial region that favours planetesimal formation between 900 K and 1300 K [1,2]. For the Brazilian test pieces of two meteorites, namely Sayh al Uhaymir 001 and Allende, were milled to micrometer dust, pressed into cylinders, and tempered at increasing temperatures up to 1400 K before the tensile strength measurement. The Sayh al Uhaymir is an L4/5 type chondrite that has undergone a slight thermal metamorphosis. The Allende however is classified as CV3. It is unequilibrated and therefore the closest to a realistic mix of minerals in the protoplanetary disc. Comparing sticking properties in terms of surface energies in relation to the heating temperature of the two different meteorite samples, they show no significant difference for heating under vacuum. Both datasets show a considerable increase in sticking around 1200 K by orders of magnitude. The new Allende data fits the older Sayh al Uhaymir data in this respect. This confirms the former found location in the warm inner disc that supports planetesimal formation best. The most abundant element in protoplanetary discs is gaseous hydrogen. To see how the presence of hydrogen might influence the results, we followed the same measurement procedure but tempering in a continuous hydrogen atmosphere. The heating chamber is flushed with hydrogen during the entire heating process. This also does not produce any significant change in the results. The relative surface energies still increase monotonously and rise by orders of magnitude around 1200 K. We see an influence of composition and atmosphere as well as water content, grain size and morphology on sticking properties. Overall, also our new results not only suggest subtle changes but imply a boost in surface energy for high-temperature dust. This continues to support the idea of a hot spot around 1200 K that favours aggregation and might trigger a high number of planetesimals and subsequently planets in the inner part of protoplanetary discs [in prep]. [1] Bogdan, T., Pillich, C., Landers, J., Wende, H., & Wurm, G. (2020). Drifting inwards in protoplanetary discs I: Sticking of chondritic dust at increasing temperatures. Astronomy & Astrophysics, 638, A151. [2] Pillich, C., Bogdan, T., Landers, J., Wurm, G. & Wende, H., (2021). Drifting inwards in protoplanetary discs II: The influence of water on sticking properties at increasing temperatures. Astronomy & Astrophysics, 652, A106.

The original version of this Article contained an error where Figures 3 and 4 were interchanged. The original Figures 3 and 4 and accompanying legends appear below. The original Article has been corrected. (Figure presented.). CA Gökce

Liquid crystal (LC) based magnetic materials consisting of LC hosts doped with functional magnetic nanoparticles enable optical switching of the mesogens at moderate magnetic field strengths and thereby open the pathway for the design of novel smart devices. A promising route for the fabrication of stable ferronematic phases is the attachment of a covalently bound LC polymer shell onto the surface of nanoparticles. With this approach, ferronematic phases based on magnetically blocked particles and the commercial LC 4-cyano-4′-pentylbiphenyl (5CB) liquid crystal were shown to have a sufficient magnetic sensitivity, but the mechanism of the magneto-nematic coupling is unidentified. To get deeper insight into the coupling modes present in these systems, we prepared ferronematic materials based on superparamagnetic particles, which respond to external fields with internal magnetic realignment instead of mechanical rotation. This aims at clarifying whether the hard coupling of the magnetization to the particle's orientation (magnetic blocking) is a necessary component of the magnetization-nematic director coupling mechanism. We herein report the fabrication of a ferronematic phase consisting of surface-functionalized superparamagnetic Fe3O4 particles and 5CB. We characterize the phase behavior and investigate the magneto-optical properties of the new ferronematic phase and compare it to the ferronematic system containing magnetically blocked CoFe2O4 particles to get information about the origin of the magneto-nematic coupling.

Iron oxide nanoparticles are presently considered as main work horses for various applications including targeted drug delivery and magnetic hyperthermia. Several questions remain unsolved regarding the effect of size onto their overall magnetic behavior. One aspect is the reduction of magnetization compared to bulk samples. A detailed understanding of the underlying mechanisms of this reduction could improve the particle performance in applications. Here we use a number of complementary experimental techniques including neutron scattering and synchrotron X-ray diffraction to arrive at a consistent conclusion. We confirm the observation from previous studies of a reduced saturation magnetization and argue that this reduction is mainly associated with the presence of antiphase boundaries, which are observed directly using high-resolution transmission electron microscopy and indirectly via an anisotropic peak broadening in X-ray diffraction patterns. Additionally small-angle neutron scattering with polarized neutrons revealed a small non-magnetic surface layer, that is, however, not sufficient to explain the observed loss in magnetization alone.

Doping complex polymer solutions with magnetic nanoparticles opens up a class of functional materials. However, a distinct decrease in the degree of magnetic in-field alignment of nanoparticles upo...

Fe3O4/CoFe2O4 nanorods were obtained via a simple seed-mediated synthesis. Nanorods were used as seeds to grow CoFe2O4 by thermal codecomposition of the cobalt(II) and iron(III) acetylacetonate precursors. The growth process was monitored by electron microscopy (SEM, TEM), and the resulting nanorods were characterized by powder X-ray diffraction analysis and IR and Raman spectroscopy. Magnetometry and AC susceptometry studies revealed a distribution of Neel relaxation times with an average blocking temperature of 140 K and a high-field magnetization of 42 Am2/kg. Complementarily recorded 57Fe-Mossbauer spectra were consistent with the Fe3O4/CoFe2O4 spinel structure and exhibited considerable signs of spin frustration, which was correlated to the internal and surface structure of the nanorods.

Iron ions are observed in a previously unobserved coordination environment in iron–nickel oxyhydroxide. Complementary characterization techniques suggest the environment sits atop the two-dimensional Ni(OH)2 sheets.

The implementation of anisotropy to functional materials is a key step towards future smart materials. In this work, we evaluate the influence of preorientation and sample architecture on the strain-induced anisotropy in hybrid elastomers containing covalently attached elongated magnetic filler particles. Accordingly, silica coated spindle-type hematite nanoparticles are incorporated into poly(dimethylsiloxane)-based elastomers, and two types of composite architectures are compared: on the one hand a conventional architecture of filled, covalently crosslinked elastomers, and on the other hybrid elastomers that are crosslinked exclusively by covalent attachment of the polymer chains to the particle surface. By the application of external strain and with magnetic fields, the orientational order of the elongated nanoparticles can be manipulated, and we investigate the interplay between strain, magnetic order, and orientational order of the particles by combining 2D small angle X-ray scattering experiments under strain and fields with Mossbauer spectroscopy under similar conditions, and supplementary angular-dependent magnetization experiments. The converging information is used to quantify the order in these interesting materials, while establishing a direct link between the magnetic properties and the spatial orientation of the embedded magnetic nanoparticles.

The development of new feedstock materials is a central prerequisite for advances in Additive Manufacturing (AM). To increase the breadth of potential applications for 3D and 4D printing of polymers, micro- and nano-additives incorporated into the feedstock material play an important role. In this context, magnetic materials are of great interest. Our study describes a way to fabricate polymer powders for laser powder bed fusion (PBF-LB) with a homogeneous, well-dispersed coating of iron oxide nanoparticles. Without the addition of chemical precursors, spherical superparamagnetic FeOx nanoparticles with monomodal size distribution below 10 nm are generated from FeOx micropowder by laser fragmentation in liquid. The adsorption of the nanoparticles on polyamide (PA12) powder is conducted directly in an aqueous dispersion after laser fragmentation, followed by drying, powder analysis and PBF-LB processing. Via Mossbauer spectroscopy and magnetometry, we determined that the saturation magnetization and structure of the iron oxide nanoparticles were not influenced by PBF-LB processing, and the magnetic properties were successfully transferred to the final 3D-printed magnetic part.

Perovskites are interesting oxidation catalysts due to their chemical flexibility enabling the tuning of several properties. In this work, we synthesized LaFe

Sticking properties are of great importance for planetesimal formation in protoplanetary disks. During the early phases of pebble growth, grains regularly travel from cold, water-rich regions to the warm inner part of the disk, experiencing ever higher temperatures. This drift leads to changes in composition, grain size, morphology, and water content. To follow the evolution that the dust might go through, we milled a meteorite to micrometer dust and tempered it under vacuum at increasing temperatures up to 1400 K. For each tempered sample we measured the splitting tensile strength of millimeter-sized dust aggregates using a well-established method known as the Brazilian test. To link the evolution of surface energy with temperature to compositional changes, we additionally measured the (ferric) composition of the samples by Mössbauer spectroscopy. At the low pressure of protoplanetary disks and at moderate temperatures, grains presumably hold only a monolayer of surface water and can thus be considered as dry. As the dust drifts further inwards towards higher temperature regions even this monolayer of water may evaporate completely and grains are super dry. In the laboratory, contacts between grains in cylinders are dry and remain dry for measurement if they are prepared for the Brazilian test before tempering. If cylinders are prepared after tempering but from the tempered dust, contacts are wet contacts but the influence of the composition can be traced. For wet samples, we measured an effective surface energy which monotonously decreases by a factor of 5 from room temperature to about 1300 K due to compositional changes [1]. This reduction of surface energy still holds for dry samples but with an increase in the sticking force by a factor of ~ 10 over the wet samples. Super dry samples deviate strongly from this starting at about 900 K. Above this temperature, the surface energy is boosted and increases exponentially up to another factor of ~ 100 at about 1200 K [2]. Exceeding temperatures of 1300 K, grain sizes microscopically change (increase) for all samples, leading to an instability of aggregates and therefore making growth challenging. Beyond 1400 K no classical collisional growth is possible. As consequence, there is a spatial region in protoplanetary disks with temperatures around 1200 K which favors aggregation and, therefore, will likely be a sweet spot for planetesimal formation as indicated in fig.1. [1] Bogdan, T., Pillich, C., Landers, J., Wende, H., & Wurm, G. (2020). Drifting inwards in protoplanetary discs I Sticking of chondritic dust at increasing temperatures. Astronomy & Astrophysics, 638, A151. [2] Pillich, C., Bogdan, T., Landers, J., Wurm, G., Wende, H. (2021). Drifting inwards in protoplanetary discs II The influence of water on sticking properties at increasing temperatures. Astronomy & Astrophysics, (accepted).

The development of magnetocaloric materials represents an approach to enable efficient and environmentally friendly refrigeration. It is envisioned as a key technology to reduce CO2 emissions of air conditioning and cooling systems. Fe-Rh has been shown to be one of the best-suited materials in terms of heat exchange per material volume. However, the Fe-Rh magnetocaloric response depends on its composition. Hence, the adaptation of material processing routes that preserve the Fe-Rh magnetocaloric response in the generated structures is a fundamental step towards the industrial development of this cooling technology. To address this challenge, the temperature-dependent properties of laser synthesized Fe-Rh nanoparticles and the laser printing of Fe-Rh nanoparticle inks are studied to generate 2D magnetocaloric structures that are potentially interesting for applications such as waste heat management of compact electrical appliances or thermal diodes, switches, and printable magnetocaloric media. The magnetization and temperature dependence of the ink’s γ-FeRh to B2-FeRh magnetic transition is analyzed throughout the complete process, finding a linear increase of the magnetization M (0.8 T, 300 K) up to 96 Am2/kg with ca. 90% of the γ-FeRh being transformed permanently into the B2-phase. In 2D structures, magnetization values of M (0.8 T, 300 K) ≈ 11 Am2/kg could be reached by laser sintering, yielding partial conversion to the B2-phase equivalent to long-time heating temperature of app. 600 K, via this treatment. Thus, the proposed procedure constitutes a robust route to achieve the generation of magnetocaloric structures.

By using the crystalline precursor decomposition approach and direct co-precipitation the composition and mesostructure of cobalt-based spinels can be controlled. A systematic substitution of cobalt with redox-active iron and redox-inactive magnesium and aluminum in a cobalt spinel with anisotropic particle morphology with a preferred 111 surface termination is presented, resulting in a substitution series including Co3 O4 , MgCo2 O4 , Co2 FeO4 , Co2 AlO4 and CoFe2 O4 . The role of redox pairs in the spinels is investigated in chemical water oxidation by using ceric ammonium nitrate (CAN test), electrochemical oxygen evolution reaction (OER) and H2 O2 decomposition. Studying the effect of dominant surface termination, isotropic Co3 O4 and CoFe2 O4 catalysts with more or less spherical particles are compared to their anisotropic analogues. For CAN-test and OER, Co3+ plays the major role for high activity. In H2 O2 decomposition, Co2+ reveals itself to be of major importance. Redox active cations in the structure enhance the catalytic activity in all reactions. A benefit of a predominant 111 surface termination depends on the cobalt oxidation state in the as-prepared catalysts and the investigated reaction.

Mössbauer spectroscopy is a well-known technique to study complex magnetic structures, due to its sensitivity to electronic and magnetic interactions of the probed nucleus with its electronic surrounding. It has also been applied to the emerging fields of magnetic hybrid materials as well as to ferrofluids, as information on the magnetic alignment and the velocity of the probed nucleus, i.e. of the particle it is embedded in, can be inferred from the spectra in addition to the above-mentioned quantities. Considering the wide range of preparation methods and sample properties, including fluids, particle powders, sintered pellets, polymer matrices and viscoelastic hydrogels, a considerable advantage of Mössbauer spectroscopy is the usage of γ-photons. This allows measurements on opaque samples, for which optical experiments are usually not feasible, also making the technique relatively independent of specific sample geometries or preparation. Using iron oxide nanoparticles in glycerol solution as an exemplary material here, the variety of system parameters simultaneously accessible via Mössbauer spectroscopy can be demonstrated: Spectra recorded for particles of different sizes provided information on the particles’ Brownian dynamics, including the effect of the shell thickness on their hydrodynamic diameter, the presence (or absence) and ballpark frequency of Néel superspin relaxation as well as the particles’ average magnetic orientation in external magnetic fields. For single-core particles, this resulted in the observation of standard Langevin-type alignment behavior. Mössbauer spectra additionally provide information on the absolute degree of spin alignment, also allowing the determination of the degree of surface spin canting, which limits the maximum magnetization of ferrofluid samples. Analyzing the alignment behavior of agglomerated particles for comparison, we found a completely different trend, in which spin alignment was further hindered by the competition of easy magnetic directions. More complex particle dynamics are observed when going from ferrofluids to hybrid materials, where the particle mobility and alignability depends not only on the particles’ shape and material, but also on the matrices’ inner structure and the acting force-transfer mechanism between particles and the surrounding medium. In ferrohydrogels for example, particle mobility in terms of Mössbauer spectroscopy was probed for different crosslinker concentrations, resulting in widely different mesh-sizes of the polymer network and different degrees of freedom. While a decrease in particle dynamics is clearly visible in Mössbauer spectroscopy upon rising crosslinker density, complementary AC-susceptometry experiments indicated no Brownian motion on the expected timescales. This apparent contradiction could, however, be explained by the different timescales of the experiments, probing either the relatively free Brownian motion on ultrashort timescales or the more bound state preventing extensive particle motion by interaction with the trapping mesh walls in the millisecond regime. However, it should also be considered that the effect of the surroundings on particle rotation in AC-susceptometry may also differ from the variation in translational motion, probed by Mössbauer spectroscopy. Being sensitive mainly to translational motion also results in a wide range of particles to be accessible for studies via Mössbauer spectroscopy, including larger agglomerates embedded in polymers, intended for remote-controlled heating. Despite the agglomerates’ wide distribution in effective diameters, information on particle motion was found to be in good agreement with AC-susceptometry experiments at ultralow frequencies in and above the polymer melting region, while additionally giving insight into Néel relaxation of the individual nanoparticles and their magnetic structure.

Sub-10 nm CoFe2O4 nanoparticles with different sizes and various compositions obtained by (partial) substitution of Co with Ni cations have been synthesized by using a one-pot method from organic solutions by the decomposition of metal acetylacetonates in the presence of oleylamine. The electrocatalytic activity of CoFe2O4 towards the oxygen evolution reaction (OER) is clearly enhanced with a smaller size (3.1 nm) of the CoFe2O4 nanoparticles (compared with 4.5 and 5.9 nm). In addition, the catalytic activity is improved by partial substitution of Co with Ni, which also leads to a higher degree of inversion of the spinel structure. Theoretical calculations attribute the positive catalytic effect of Ni owing to the lower binding energy differences between adsorbed O and OH compared with pure cobalt or nickel ferrites, resulting in higher OER activity. Co0.5Ni0.5Fe2O4 exhibited a low overpotential of approximately 340 mV at 10 mAcm-2, a smaller Tafel slope of 51 mVdec-1, and stability over 30 h. The unique tunability of these CoFe2O4 nanocrystals provides great potential for their application as an efficient and competitive anode material in the field of electrochemical water splitting as well as for systematic fundamental studies aiming at understanding the correlation of composition and structure with performance in electrocatalysis.

Sticking properties rule the early phases of pebble growth in protoplanetary discs in which grains regularly travel from cold, water-rich regions to the warm inner part. This drift affects composition, grain size, morphology, and water content as grains experience ever higher temperatures. In this study we tempered chondritic dust under vacuum up to 1400 K. Afterwards, we measured the splitting tensile strength of millimetre-sized dust aggregates. The deduced effective surface energy starts out asγe= 0.07 J m−2. This value is dominated by abundant iron-oxides as measured by Mössbauer spectroscopy. Up to 1250 K,γecontinuously decreases by up to a factor five. Olivines dominate at higher temperature. Beyond 1300 K dust grains significantly grow in size. Theγeno longer decreases but the large grain size restricts the capability of growing aggregates. Beyond 1400 K aggregation is no longer possible. Overall, under the conditions probed, the stability of dust pebbles would decrease towards the star. In view of a minimum aggregate size required to trigger drag instabilities it becomes increasingly harder to seed planetesimal formation closer to a star.

Fe

We report on the impact of magnetoelastic coupling on the magnetocaloric properties of ${\mathrm{LaFe}}_{11.4}{\mathrm{Si}}_{1.6}{\mathrm{H}}_{1.6}$ in terms of the vibrational (phonon) density of states (VDOS), which we determined with $^{57}\mathrm{Fe}$ nuclear resonant inelastic x-ray scattering (NRIXS) measurements and with density functional theory (DFT) based first-principles calculations in the ferromagnetic (FM) low-temperature and paramagnetic (PM) high-temperature phase. In experiments and calculations, we observe pronounced differences in the shape of the Fe-partial VDOS between nonhydrogenated and hydrogenated samples. This shows that hydrogen not only shifts the temperature of the first-order phase transition, but also affects the elastic response of the Fe subsystem significantly. In turn, the anomalous redshift of the Fe VDOS, observed by going to the low-volume PM phase, survives hydrogenation. As a consequence, the change in the Fe-specific vibrational entropy $\mathrm{\ensuremath{\Delta}}{S}_{\mathrm{lat}}$ across the phase transition has the same sign as the magnetic and electronic contribution. DFT calculations show that the same mechanism, which is a consequence of the itinerant electron metamagnetism associated with the Fe subsystem, is effective in both the hydrogenated and the hydrogen-free compounds. Although reduced by 50% as compared to the hydrogen-free system, the measured change $\mathrm{\ensuremath{\Delta}}{S}_{\mathrm{lat}}$ of $(3.2\ifmmode\pm\else\textpm\fi{}1.9)\phantom{\rule{0.16em}{0ex}}\frac{\mathrm{J}}{\mathrm{kg}\phantom{\rule{0.16em}{0ex}}\mathrm{K}}$ across the FM-to-PM transition contributes with $\ensuremath{\sim}35$% significantly and cooperatively to the total isothermal entropy change $\mathrm{\ensuremath{\Delta}}{S}_{\mathrm{iso}}$. Hydrogenation is observed to induce an overall blueshift of the Fe VDOS with respect to the H-free compound; this effect, together with the enhanced Debye temperature observed, is a fingerprint of the hardening of the Fe sublattice by hydrogen incorporation. In addition, the mean Debye velocity of sound of ${\mathrm{LaFe}}_{11.4}{\mathrm{Si}}_{1.6}{\mathrm{H}}_{1.6}$ was determined from the NRIXS and the DFT data.

By studying the response behavior of ferrofluids of 6-22 nm maghemite nanoparticles in glycerol solution exposed to external magnetic fields, we demonstrate the ability of Mossbauer spectroscopy to access a variety of particle dynamics and static magnetic particle characteristics at the same time, offering an extensive characterization of ferrofluids for in-field applications; field-dependent particle alignment and particle mobility in terms of Brownian motion have been extracted simultaneously from a series of Mossbauer spectra for single-core particles as well as for particle agglomerates. Additionally, information on Neel superspin relaxation and surface spin frustration could be directly inferred from this analysis. Parameters regarding Brownian particle dynamics, as well as Neel-type relaxation behavior, obtained via Mossbauer spectroscopy, have been verified by complementary AC-susceptometry experiments, modulating the AC-field amplitude, and using an extended frequency range of 10-1 to 106 Hz, while field-dependent particle alignment has been cross-checked via magnetometry.

Cation substitution in transition-metal oxides is an important approach to improve electrocatalysts by the optimization of their composition. Herein, we report on phase-pure spinel-type CoV2–xFexO4 nanoparticles with 0 ≤ x ≤ 2 as a new class of bifunctional catalysts for the oxygen evolution (OER) and oxygen reduction reactions (ORR). The mixed-metal oxide catalysts exhibit high catalytic activity for both OER and ORR that strongly depends on the V and Fe content. CoV2O4 is known to exhibit a high conductivity, while in CoFe2O4 the cobalt cation distribution is expected to change due to the inversion of the spinel structure. The optimized catalyst, CoV1.5Fe0.5O4, shows an overpotential for the OER of ∼300 mV for 10 mA cm–2 with a Tafel slope of 38 mV dec–1 in alkaline electrolyte. DFT+U+SOC calculations on cation ordering confirm the tendency toward the inverse spinel structure with increasing Fe concentration in CoV2–xFexO4 that starts to dominate already at low Fe contents. The theoretical results also show that the variations of oxidation states are related to the surface region, where the redox activity was found experimentally to be manifested in the transformation of V3+ → V2+. The high catalytic activity, facile synthesis, and low cost of the CoV2–xFexO4 nanoparticles render them very promising for application in bifunctional electrocatalysis.

Iron oxide nanoparticles (IONs) are being actively researched and experimented with as contrast agents for Magnetic Resonance Imaging (MRI), as well as image-directed delivery of therapeutics. The efficiency of an MRI contrast agent can be described by its longitudinal and transverse relaxivities, r(1) and r(2). gamma-Fe2O3 nanoparticles -doped with fluoride in a controlled manner and functionalised with citric acid showed a 3-fold increase in r(1) and a 17-fold increase in r(2) in a magnetic field of 3 T and almost 6-fold increase in r(1) and a 14-fold increase in r(2) at 11 T. Following fluorination, PXRD shows that the crystal structure of g-Fe2O3 is maintained, Mossbauer spectroscopy shows that the oxidation state of the Fe cation is unchanged and HREM shows that the particle size does not vary. However, magnetisation curves show a large increase in the coercive field, pointing towards a large increase in the magnetic anisotropy for the fluorinated nanoparticles compared to the un-doped g-Fe2O3 nanoparticles. Therefore, a chemically induced increase in magnetic anisotropy appears to be the most relevant parameter responsible for the large increase in relaxivity for gamma-Fe2O3 nanoparticles.

Monocrystalline, yet porous mosaic platelets of cobalt ferrite, CoFe2O4, can be synthesized from a layered double hydroxide (LDH) precursor by thermal decomposition. Using an equimolar mixture of Fe2+, Co2+, and Fe3+ during co-precipitation, a mixture of LDH, (FeIICoII)2/3FeIII1/3(OH)2(CO3)1/6·mH2O, and the target spinel CoFe2O4 can be obtained in the precursor. During calcination, the remaining FeII fraction of the LDH is oxidized to FeIII leading to an overall Co2+:Fe3+ ratio of 1:2 as required for spinel crystallization. This pre-adjustment of the spinel composition in the LDH precursor suggests a topotactic crystallization of cobalt ferrite and yields phase pure spinel in unusual anisotropic platelet morphology. The preferred topotactic relationship in most particles is [111]Spinel‖ [001]LDH. Due to the anion decomposition, holes are formed throughout the quasi monocrystalline platelets. This synthesis approach can be used for different ferrites and the unique microstructure leads to unusual chemical properties as shown by the application of the ex-LDH cobalt ferrite as catalyst in the selective oxidation of 2-propanol. Compared to commercial cobalt ferrite, which mainly catalyzes the oxidative dehydrogenation to acetone, the main reaction over the novel ex-LDH cobalt is dehydration to propene. Moreover, the oxygen evolution reaction (OER) activity of the ex-LDH catalyst was markedly higher compared to the commercial material.

In several upcoming rheological approaches, including methods of micro- and nanorheology, the measurement geometry is of critical impact on the interpretation of the results. The relative size of the probe objects employed (as compared to the intrinsic length scales of the sample to be investigated) becomes of crucial importance, and there is increasing interest to investigate the dynamic processes and mobility in nanostructured materials. A combination of different rheological approaches based on the rotation of magnetically blocked nanoprobes is used to systematically investigate the size-dependent diffusion behavior in aqueous poly(ethylene glycol) (PEG) solutions with special attention paid to the relation of probe size to characteristic length scales within the polymer solutions. We employ two types of probe particles: nickel rods of hydrodynamic length Lh between 200 nm and 650 nm, and cobalt ferrite spheres with diameter dh between 13 nm and 23 nm, and examine the influence of particle size and shape on the nanorheological information obtained in model polymer solutions based on two related, dynamic-magnetic approaches. The results confirm that as long as the investigated solutions are not entangled, and the particles are much larger than the macromolecular correlation length, a good accordance between macroscopic and nanoscopic results, whereas a strong size-dependent response is observed in cases where the particles are of similar size or smaller than the radius of gyration Rg or the correlation length ξ of the polymer solution.

International audience; Bismuth ferrite (BFO) is the drosophila of research in multiferroic materials due to its simultaneous magnetic and electric ordering at room temperature. The unfortunate detail is its antiferromagnetic ordering, which practically cancels magnetization and magnetoelectric coupling of the crystals. To induce finite coupling, dopants have been introduced with a certain success so far. Nanoparticles (NPs) can additionally constrain the formation of the magnetic cycloid in BFO due to size confinement. Doping nanoparticles can thus potentially provide a sizeable magnetization of BFO, making applications in computer memories and hyperthermia cancer treatment feasible. We show that the codoping of BFO NPs by Ba and Mn balances the electrochemical equilibrium, reduces the particle size, and shifts the magnetic phase transition to lower temperatures. The ferroelectric properties are retained and the remanent magnetization is increased by 1 order of magnitude: Bi0.95Ba0.05Fe0.95Mn0.05O3 possesses a remanent magnetization of 0.277 Am2/kg. Our Mössbauer studies reveal that two effects drive this increase: partial destruction of the spin cycloid due to Mn and increased spin canting due to Ba doping inducing local stress fields. This dopant combination and particular concentration improve the effective magnetization value exceptionally well.

Magnetic nanoparticle-mediated hyperthermia has shown great potential in cancer therapy. However, upscaling of the synthesis of iron oxide nanoparticle with the required narrow size distribution remains challenging. This paper describes the reproducible and scalable synthesis of citric acid-functionalized iron oxide nanoparticles optimized for hyperthermia treatment. Iron oxide nanoparticles were synthesized by a spray flame method, which is eco-friendly and cost-effective. To the best of our knowledge, this is the first study reporting spray-flame synthesis of small iron oxide nanoparticles (approx. 7 nm) with narrow size distribution (polydispersity index ≪ 0.1). The citric acid-coated iron oxide nanoparticles revealed a hydrodynamic size of approx. 37 nm and a high magnetic saturation of 69 Am2/kg at room temperature. The magnetic hyperthermia study showed a significantly enhanced value of the intrinsic loss power (4.8 nHm2/kg), which is 1.5-fold higher than the best commercially available equivalents. The improved heating efficiency and small hydrodynamic size of citric acid-coated iron oxide nanoparticles demonstrate that the system could potentially be used as a nanoplatform for hyperthermia treatment.

We report the first microporous cobalt imidazolate glass obtained from a meltable cobalt-based zeolitic imidazolate framework, ZIF-62(Co). Crystalline ZIF-62(Co) is constructed from Co2+ cations and two different imidazolate-type linkers, namely conventional imidazolate and benzimidazolate. The microporous framework melts at ∼430 °C and converts into a glass upon cooling to room temperature. X-Ray total scattering and Raman spectroscopy reveal that the local structure of the glass and the crystalline parent material are very similar. Magnetic measurements and X-ray diffraction uncover that ZIF-62(Co) partially decomposes upon melting and glass formation resulting in the reduction of ∼3% of the Co2+ ions to metallic cobalt. Most importantly, the ZIF glass retains almost 50% of the porosity of crystalline ZIF-62(Co). Our results pave the way for the realisation of metal–organic framework glasses containing open shell metal ions, as well as the application of these porous glasses in gas separation, energy storage and catalysis.

Magnetocaloric ${\mathrm{LaFe}}_{13\ensuremath{-}x}{\mathrm{Si}}_{x}$-based compounds belong to the outstanding materials with potential for efficient solid-state refrigeration. We have performed temperature-dependent $^{57}\mathrm{Fe}$ nuclear resonant inelastic x-ray scattering measurements (in a field ${\ensuremath{\mu}}_{0}H$ of $\ensuremath{\sim}0.7$ T) of the vibrational (phonon) density of states, VDOS, in ${\mathrm{LaFe}}_{11.6}{\mathrm{Si}}_{1.4}$ across the metamagnetic isostructural first-order phase transition at ${T}_{C}\ensuremath{\sim}192$ K from the low-temperature ferromagnetic (FM) to the high-temperature paramagnetic (PM) phase, in order to determine the change in thermodynamic properties of the Fe lattice at ${T}_{C}$. The experimental results are compared with density-functional-theory-based first-principles calculations using the fixed-spin moment approach. Our combined experimental and theoretical results reveal distinct and abrupt changes in the VDOS of the Fe sublattice across ${T}_{C}$, occurring within a small temperature interval of $\mathrm{\ensuremath{\Delta}}T\ensuremath{\le}12$ K around ${T}_{C}$. This indicates that strong magnetoelastic coupling (at the atomic scale) is present up to ${T}_{C}$, leading to a pronounced lattice softening (phonon redshift) in the PM phase. These changes originate from the itinerant electron magnetism associated with Fe and are correlated with distinct modifications in the Fe-partial electronic density of states $D({E}_{F}$) at the Fermi energy ${E}_{F}$. From the experimental VDOS we can infer an abrupt increase (jump) in the Fe-partial vibrational entropy $\mathrm{\ensuremath{\Delta}}{S}_{\mathrm{vib}}$ of $+6.9\ifmmode\pm\else\textpm\fi{}2.6$ J/(kg K) and in the vibrational specific heat $\mathrm{\ensuremath{\Delta}}{C}_{\mathrm{vib}}$ of $+2.7\ifmmode\pm\else\textpm\fi{}1.6$ J/(kg K) upon heating. The increase in magnitude of the vibrational entropy $|\mathrm{\ensuremath{\Delta}}{S}_{\mathrm{vib}}|=6.9$ J/(kg K) of the Fe sublattice at ${T}_{C}$ upon heating is substantial, if compared with the magnitude of the isothermal entropy change $|\mathrm{\ensuremath{\Delta}}{S}_{\mathrm{iso}}|$ of 14.2 J/(kg K) in a field change $\mathrm{\ensuremath{\Delta}}B$ from 0 to 1 T, as obtained from isothermal magnetization measurements on our sample and using the Maxwell relation. We demonstrate that $\mathrm{\ensuremath{\Delta}}{S}_{\mathrm{vib}}$ obtained by nuclear resonant inelastic x-ray scattering is a sizable quantity and contributes directly and cooperatively to the total entropy change $\mathrm{\ensuremath{\Delta}}{S}_{\mathrm{iso}}$ at the phase transition of ${\mathrm{LaFe}}_{13\ensuremath{-}x}{\mathrm{Si}}_{x}$.