Lattice solvent- and substituent-dependent spin-crossover in isomeric iron(II) complexes.

Spin-state switching in iron(II) complexes composed of ligands featuring moderate ligand-field strength-for example, 2,6-bi(1H-pyrazol-1-yl)pyridine (BPP)-is dependent on many factors. Herein, we show that spin-state switching in isomeric iron(II) complexes composed of BPP-based ligands-ethyl 2,6-bis(1H-pyrazol-1-yl)isonicotinate (BPP-COOEt, L1) and (2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)methylacetate (BPP-CH2OCOMe, L2)-is dependent on the nature of the substituent at the BPP skeleton. Bi-stable spin-state switching-with a thermal hysteresis width (ΔT1/2) of 44 K and switching temperature (T1/2) = 298 K in the first cycle-is observed for complex 1·CH3CN composed of L1 and BF4- counter anions. Conversely, the solvent-free isomeric counterpart of 1·CH3CN-complex 2a, composed of L2 and BF4- counter anions-was trapped in the high-spin (HS) state. For one of the polymorphs of complex 2b·CH3CN-2b·CH3CN-Y, Y denotes yellow colour of the crystals-composed of L2 and ClO4- counter anions, a gradual and non-hysteretic SCO is observed with T1/2 = 234 K. Complexes 1·CH3CN and 2b·CH3CN-Y also underwent light-induced spin-state switching at 5 K due to the light-induced excited spin-state trapping (LIESST) effect. Structures of the low-spin (LS) and HS forms of complex 1·CH3CN revealed that spin-state switching goes hand-in-hand with pronounced distortion of the trans-N{pyridyl}-Fe-N{pyridyl} angle (ϕ), whereas such distortion is not observed for 2b·CH3CN-Y. This observation points that distortion is one of the factors making the spin-state switching of 1·CH3CN hysteretic in the solid state. The observation of bi-stable spin-state switching with T1/2 centred at room temperature for 1·CH3CN indicates that technologically relevant spin-state switching profiles based on mononuclear iron(II) complexes can be obtained.

Optimization of Magnetic Cobalt Ferrite Nanoparticles for Magnetic Heating Applications in Biomedical Technology.

Using magnetic nanoparticles for extracorporeal magnetic heating applications in bio-medical technology allows higher external field amplitudes and thereby the utilization of particles with higher coercivities (HC). In this study, we report the synthesis and characterization of high coercivity cobalt ferrite nanoparticles following a wet co-precipitation method. Particles are characterized with magnetometry, X-ray diffraction, Mössbauer spectroscopy, transmission electron microscopy (TEM) and calorimetric measurements for the determination of their specific absorption rate (SAR). In the first series, CoxFe3-xO4 particles were synthesized with x = 1 and a structured variation of synthesis conditions, including those of the used atmosphere (O2 or N2). In the second series, particles with x = 0 to 1 were synthesized to study the influence of the cobalt fraction on the resulting magnetic and structural properties. Crystallite sizes of the resulting particles ranged between 10 and 18 nm, while maximum coercivities at room temperatures of 60 kA/m for synthesis with O2 and 37 kA/m for N2 were reached. Magnetization values at room temperature and 2 T (MRT,2T) up to 60 Am2/kg under N2 for x = 1 can be achieved. Synthesis parameters that lead to the formation of an additional phase when they exceed specific thresholds have been identified. Based on XRD findings, the direct correlation between high-field magnetization, the fraction of this antiferromagnetic byphase and the estimated transition temperature of this byphase, extracted from the Mössbauer spectroscopy series, we were able to attribute this contribution to akageneite. When varying the cobalt fraction x, a non-monotonous correlation of HC and x was found, with a linear increase of HC up to x = 0.8 and a decrease for x > 0.8, while magnetometry and in-field Mössbauer experiments demonstrated a moderate degree of spin canting for all x, yielding high magnetization. SAR values up to 480 W/g (@290 kHz, 69 mT) were measured for immobilized particles with x = 0.3, whit the external field amplitude being the limiting factor due to the high coercivities of our particles.

2-Propanol interacting with Co3O4(001): A combined vSFS and AIMD study.

The interaction of 2-propanol with Co3O4(001) was studied by vibrational sum frequency spectroscopy and ab initio molecular dynamics simulations of 2-propanol dissolved in a water film to gain an insight, at the molecular level, into the pathways of catalytic oxidation. The experimental study has been performed under near ambient conditions, where the presence of water vapor is unavoidable, resulting in a water film on the sample and, thereby, allowing us to mimic the solution-water interface. Both experiment and theory conclude that 2-propanol adsorbs molecularly. The lack of dissociation is attributed to the adsorption geometry of 2-propanol in which the O-H bond does not point toward the surface. Furthermore, the copresent water not only competitively adsorbs on the surface but also inhibits 2-propanol deprotonation. The calculations reveal that the presence of water deactivates the lattice oxygen, thereby reducing the surface activity. This finding sheds light on the multifaceted role of water at the interface for the electrochemical oxidation of 2-propanol in aqueous solution as recently reported [Falk et al., ChemCatChem 13, 2942-2951 (2021)]. At higher temperatures, 2-propanol remains molecularly adsorbed on Co3O4(001) until it desorbs with increasing surface temperature.

Spray-Flame Synthesis of LaFexCo1-xO3 (x = 0.2, 0.3) Perovskite Nanoparticles for Oxygen Evolution Reaction in Water Splitting: Effect of Precursor Chemistry (Acetates and Nitrates).

The product properties of mixed oxide nanoparticles generated via spray-flame synthesis depend on an intricate interplay of solvent and precursor chemistries in the processed solution. The effect of two different sets of metal precursors, acetates and nitrates, dissolved in a mixture of ethanol (35 Vol.%) and 2-ethylhexanoic acid (2-EHA, 65 Vol.%) was investigated for the synthesis of LaFexCo1-xO3 (x = 0.2, 0.3) perovskites. Regardless of the set of precursors, similar particle-size distributions (dp = 8-11 nm) were obtained and a few particles with sizes above 20 nm were identified with transmission electron microscopy (TEM) measurements. Using acetates as precursors, inhomogeneous La, Fe, and Co elemental distributions were obtained for all particle sizes according to energy dispersive X-ray (EDX) mappings, connected to the formation of multiple secondary phases such as oxygen-deficient La3(FexCo1-x)3O8 brownmillerite or La4(FexCo1-x)3O10 Ruddlesden-Popper (RP) structures besides the main trigonal perovskite phase. For samples synthesized from nitrates, inhomogeneous elemental distributions were observed for large particles only where La and Fe enrichment occurred in combination with the formation of a secondary La2(FexCo1-x)O4 RP phase. Such variations can be attributed to reactions in the solution prior to injection in the flame as well as precursor-dependent variations in in-flame reactions. Therefore, the precursor solutions were analyzed by temperature-dependent attenuated total reflection Fourier-transform infrared (ATR-FTIR) measurements. The acetate-based precursor solutions indicated the partial conversion of, mainly La and Fe, acetates to metal 2-ethylhexanoates. In the nitrate-based solutions, esterification of ethanol and 2-EHA played the most important role. The synthesized nanoparticle samples were characterized by BET (Brunauer, Emmett, Teller), FTIR, Mössbauer, and X-ray photoelectron spectroscopy (XPS). All samples were tested as oxygen evolution reaction (OER) catalysts, and similar electrocatalytic activities were recorded when evaluating the potential required to reach 10 mA/cm2 current density (∼1.61 V vs reversible hydrogen electrode (RHE)).

Solvent Influence on the Magnetization and Phase of Fe-Ni Alloy Nanoparticles Generated by Laser Ablation in Liquids.

The synthesis of bimetallic iron-nickel nanoparticles with control over the synthesized phases, particle size, surface chemistry, and oxidation level remains a challenge that limits the application of these nanoparticles. Pulsed laser ablation in liquid allows the properties tuning of the generated nanoparticles by changing the ablation solvent. Organic solvents such as acetone can minimize nanoparticle oxidation. Yet, economical laboratory and technical grade solvents that allow cost-effective production of FeNi nanoparticles contain water impurities, which are a potential source of oxidation. Here, we investigated the influence of water impurities in acetone on the properties of FeNi nanoparticles generated by pulsed laser ablation in liquids. To remove water impurities and produce "dried acetone", cost-effective and reusable molecular sieves (3 Å) are employed. The results show that the Fe50Ni50 nanoparticles' properties are influenced by the water content of the solvent. The metastable HCP FeNi phase is found in NPs prepared in acetone, while only the FCC phase is observed in NPs formed in water. Mössbauer spectroscopy revealed that the FeNi nanoparticles oxidation in dried acetone is reduced by 8% compared to acetone. The high-field magnetization of Fe50Ni50 nanoparticles in water is the highest, 68 Am2/kg, followed by the nanoparticles obtained after ablation in acetone without water impurities, 59 Am2/kg, and acetone, 52 Am2/kg. The core-shell structures formed in these three liquids are also distinctive, demonstrating that a core-shell structure with an outer oxide layer is formed in water, while carbon external layers are obtained in acetone without water impurity. The results confirm that the size, structure, phase, and oxidation of FeNi nanoparticles produced by pulsed laser ablation in liquids can be modified by changing the solvent or just reducing the water impurities in the organic solvent.

Rare-earth doped BiFe0.95Mn0.05O3 nanoparticles for potential hyperthermia applications.

Ionic engineering is exploited to substitute Bi cations in BiFe0.95Mn0.05O3 NPs (BFM) with rare-earth (RE) elements (Nd, Gd, and Dy). The sol-gel synthesized RE-NPs are tested for their magnetic hyperthermia potential. RE-dopants alter the morphology of BFM NPs from elliptical to rectangular to irregular hexagonal for Nd, Gd, and Dy doping, respectively. The RE-BFM NPs are ferroelectric and show larger piezoresponse than the pristine BFO NPs. There is an increase of the maximum magnetization at 300 K of BFM up to 550% by introducing Gd. In hyperthermia tests, 3 mg/ml dispersion of NPs in water and agar could increase the temperature of the dispersion up to ∼39°C under an applied AC magnetic field of 80 mT. Although Gd doping generates the highest increment in magnetization of BFM NPs, the Dy-BFM NPs show the best hyperthermia results. These findings show that RE-doped BFO NPs are promising for hyperthermia and other biomedical applications.

Spin-Polarized Photoemission from Chiral CuO Catalyst Thin Films.

The chirality-induced spin selectivity (CISS) effect facilitates a paradigm shift for controlling the outcome and efficiency of spin-dependent chemical reactions, for example, photoinduced water splitting. While the phenomenon is established in organic chiral molecules, its emergence in chiral but inorganic, nonmolecular materials is not yet understood. Nevertheless, inorganic spin-filtering materials offer favorable characteristics, such as thermal and chemical stability, over organic, molecular spin filters. Chiral cupric oxide (CuO) thin films can spin polarize (photo)electron currents, and this capability is linked to the occurrence of the CISS effect. In the present work, chiral CuO films, electrochemically deposited on partially UV-transparent polycrystalline gold substrates, were subjected to deep-UV laser pulses, and the average spin polarization of photoelectrons was measured in a Mott scattering apparatus. By energy resolving the photoelectrons and changing the photoexcitation geometry, the energy distribution and spin polarization of the photoelectrons originating from the Au substrate could be distinguished from those arising from the CuO film. The findings reveal that the spin polarization is energy dependent and, furthermore, indicate that the measured polarization values can be rationalized as a sum of an intrinsic spin polarization in the chiral oxide layer and a contribution via CISS-related spin filtering of electrons from the Au substrate. The results support efforts toward a rational design of further spin-selective catalytic oxide materials.

Laser Ablation of NiFe2O4 and CoFe2O4 Nanoparticles.

Pulsed laser ablation in liquids was utilized to prepare NiFe2O4 (NFO) and CoFe2O4 (CFO) nanoparticles from ceramic targets. The morphology, crystallinity, composition, and particle size distribution of the colloids were investigated. We were able to identify decomposition products formed during the laser ablation process in water. Attempts to fractionate the nanoparticles using the high-gradient magnetic separation method were performed. The nanoparticles with crystallite sizes in the range of 5-100 nm possess superparamagnetic behavior and approximately 20 Am2/kg magnetization at room temperature. Their ability to absorb light in the visible range makes them potential candidates for catalysis applications in chemical reactions and in biomedicine.

Phase Segregation in Cobalt Iron Oxide Nanowires toward Enhanced Oxygen Evolution Reaction Activity.

The impact of reduction post-treatment and phase segregation of cobalt iron oxide nanowires on their electrochemical oxygen evolution reaction (OER) activity is investigated. A series of cobalt iron oxide spinel nanowires are prepared via the nanocasting route using ordered mesoporous silica as a hard template. The replicated oxides are selectively reduced through a mild reduction that results in phase transformation as well as the formation of grain boundaries. The detailed structural analyses, including the 57Fe isotope-enriched Mössbauer study, validated the formation of iron oxide clusters supported by ordered mesoporous CoO nanowires after the reduction process. This affects the OER activity significantly, whereby the overpotential at 10 mA/cm2 decreases from 378 to 339 mV and the current density at 1.7 V vs RHE increases by twofold from 150 to 315 mA/cm2. In situ Raman microscopy revealed that the surfaces of reduced CoO were oxidized to cobalt with a higher oxidation state upon solvation in the KOH electrolyte. The implementation of external potential bias led to the formation of an oxyhydroxide intermediate and a disordered-spinel phase. The interactions of iron clusters with cobalt oxide at the phase boundaries were found to be beneficial to enhance the charge transfer of the cobalt oxide and boost the overall OER activity by reaching a Faradaic efficiency of up to 96%. All in all, the post-reduction and phase segregation of cobalt iron oxide play an important role as a precatalyst for the OER.

Ferrimagnetic Large Single Domain Iron Oxide Nanoparticles for Hyperthermia Applications.

This paper describes the preparation and obtained magnetic properties of large single domain iron oxide nanoparticles. Such ferrimagnetic particles are particularly interesting for diagnostic and therapeutic applications in medicine or (bio)technology. The particles were prepared by a modified oxidation method of non-magnetic precursors following the green rust synthesis and characterized regarding their structural and magnetic properties. For increasing preparation temperatures (5 to 85 °C), an increasing particle size in the range of 30 to 60 nm is observed. Magnetic measurements confirm a single domain ferrimagnetic behavior with a mean saturation magnetization of ca. 90 Am2/kg and a size-dependent coercivity in the range of 6 to 15 kA/m. The samples show a specific absorption rate (SAR) of up to 600 W/g, which is promising for magnetic hyperthermia application. For particle preparation temperatures above 45 °C, a non-magnetic impurity phase occurs besides the magnetic iron oxides that results in a reduced net saturation magnetization.

Magnetic response of CoFe2O4 nanoparticles confined in a PNIPAM microgel network.

The paper addresses coupling of magnetic nanoparticles (MNPs) with the polymer matrix of temperature-sensitive microgels and their response to magnetic fields. Therefore, CoFe2O4@CA (CA = citric acid) NPs are embedded within N-isopropylacrylamid (NIPAM) based microgels. The volume phase transition (VPT) of the magnetic microgels and the respective pure microgels is studied by dynamic light scattering and electrophoretic mobility measurements. The interaction between MNPs and microgel network is studied via magnetometry and AC-susceptometry using a superconducting quantum interference device (SQUID). The data show a significant change of the magnetic properties by crossing the VPT temperature (VPTT). The change is related to the increased confinement of the MNP due to the shrinking of the microgels. Modifying the microgel with hydrophobic allyl mercaptan (AM) affects the swelling ability and the magnetic response, i.e. the coupling of MNPs with the polymer matrix. Modeling the AC-susceptibility data results in an effective size distribution. This distribution represents the varying degree of constraint in MNP rotation and motion by the microgel network. These findings help to understand the interaction between MNPs and the microgel matrix to design multi responsive systems with tunable particle matrix coupling strength for future applications.

Structural Insights into Hysteretic Spin-Crossover in a Set of Iron(II)-2,6-bis(1H-Pyrazol-1-yl)Pyridine) Complexes.

Bistable spin-crossover (SCO) complexes that undergo abrupt and hysteretic (ΔT1/2 ) spin-state switching are desirable for molecule-based switching and memory applications. In this study, we report on structural facets governing hysteretic SCO in a set of iron(II)-2,6-bis(1H-pyrazol-1-yl)pyridine) (bpp) complexes - [Fe(bpp-COOEt)2 ](X)2 ⋅CH3 NO2 (X=ClO4 , 1; X=BF4 , 2). Stable spin-state switching - T1/2 =288 K; ΔT1/2 =62 K - is observed for 1, whereas 2 undergoes above-room-temperature lattice-solvent content-dependent SCO - T1/2 =331 K; ΔT1/2 =43 K. Variable-temperature single-crystal X-ray diffraction studies of the complexes revealed pronounced molecular reorganizations - from the Jahn-Teller-distorted HS state to the less distorted LS state - and conformation switching of the ethyl group of the COOEt substituent upon SCO. Consequently, we propose that the large structural reorganizations rendered SCO hysteretic in 1 and 2. Such insights shedding light on the molecular origin of thermal hysteresis might enable the design of technologically relevant molecule-based switching and memory elements.

The Roles of Composition and Mesostructure of Cobalt-Based Spinel Catalysts in Oxygen Evolution Reactions.

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.

The Effect of Water on the 2-Propanol Oxidation Activity of Co-Substituted LaFe1- Cox O3 Perovskites.

Perovskites are interesting oxidation catalysts due to their chemical flexibility enabling the tuning of several properties. In this work, we synthesized LaFe1-x Cox O3 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.

On the structure-property relationships of (Al, Ga, In)-doped spinel cobalt ferrite compounds: a combined experimental and DFT study.

We report a combined experimental and theoretical study of pure and doped cobalt ferrite where 25% of Fe3+ ions were replaced by Al3+, Ga3+, and In3+ ions, respectively, i.e., CoFe1.5X0.5O4 (X = Al, Ga, and In). The ferrite compositions were successfully synthesized using the solid-state reaction method. The X-ray powder diffraction method established that all ferrite samples had a spinel unit cell structure with the Fd3[combining macron]m (No. 227) space group. The lattice constants of ferrites increased from 8.382 Å (for undoped CoFe2O4) to 8.520 Å (for In-doped cobalt ferrite) in direct relation to the dopant ion size. The magnetic properties were obtained at 4.3 K and 300 K. At 4.3 K, the In-doped CoFe2O4 showed the highest saturation magnetic moment of 4.68 µB f.u.-1, while Al-doped CoFe2O4 showed the smallest value of 2.72 µB f.u.-1. The Fe3+ distribution among the spinel tetrahedral and octahedral sites was determined from the Mössbauer spectra. From ultraviolet-visible diffuse reflectance spectroscopy the direct optical bandgaps were determined, which have values between 1.20 eV and 1.28 eV for these ferrites. The ferrite compositions were also studied theoretically using plane-wave density functional theory using the CASTEP code where it was revealed that arrangements of the non-magnetic cations at the tetrahedral and octahedral sites strongly influence the electronic structure, the bandgap value, and the net magnetic moment per formula unit. Light Al3+ ions at the octahedral site give a low value of the net magnetic moment while the heavier Ga3+ and In3+ ions at the tetrahedral sites of the spinel give an enhanced magnetic moment. The magnetic moment values obtained from theoretical calculations match very well with the experimental values. Moreover, the theoretical calculations reveal that there exists a strong p-d hybridization among the oxygen and magnetic ions, which is affected by the non-magnetic dopant ions. The change in hybridization with the non-magnetic ion doping is responsible for the altered magnetic moments of the doped ferrites. Thus, our study provides a comprehensive investigation covering the synthesis and characterization of ferrites along with a good understanding of the phenomenon of how non-magnetic ion doping into spinel ferrites provides a method to tune the electronic and magnetic properties of the spinel ferrite.

Formation of Fe-Ni Nanoparticle Strands in Macroscopic Polymer Composites: Experiment and Simulation.

Magnetic-field-induced strand formation of ferromagnetic Fe-Ni nanoparticles in a PMMA-matrix is correlated with the intrinsic material parameters, such as magnetization, particle size, composition, and extrinsic parameters, including magnetic field strength and viscosity. Since various factors can influence strand formation, understanding the composite fabrication process that maintains the strand lengths of Fe-Ni in the generated structures is a fundamental step in predicting the resulting structures. Hence, the critical dimensions of the strands (length, width, spacing, and aspect ratio) are investigated in the experiments and simulated via different intrinsic and extrinsic parameters. Optimal parameters were found by optical microscopy measurements and finite-element simulations using COMSOL for strand formation of Fe50Ni50 nanoparticles. The anisotropic behavior of the aligned strands was successfully characterized through magnetometry measurements. Compared to the unaligned samples, the magnetically aligned strands exhibit enhanced conductivity, increasing the current by a factor of 1000.

Towards laser printing of magnetocaloric structures by inducing a magnetic phase transition in iron-rhodium nanoparticles.

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.

Magnetic Properties and Mössbauer Spectroscopy of Fe3O4/CoFe2O4 Nanorods.

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 Néel relaxation times with an average blocking temperature of 140 K and a high-field magnetization of 42 Am2/kg. Complementarily recorded 57Fe-Mössbauer 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.

In-Field Orientation and Dynamics of Ferrofluids Studied by Mössbauer Spectroscopy.

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 Mössbauer 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 Mössbauer spectra for single-core particles as well as for particle agglomerates. Additionally, information on Néel superspin relaxation and surface spin frustration could be directly inferred from this analysis. Parameters regarding Brownian particle dynamics, as well as Néel-type relaxation behavior, obtained via Mössbauer 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.