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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 LaFe x Co 1- x O 3 ( x = 0.2, 0.3) perovskites. Regardless of the set of precursors, similar particle-size distributions ( d p = 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 La 3 (Fe x Co 1- x ) 3 O 8 brownmillerite or La 4 (Fe x Co 1- x ) 3 O 10 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 La 2 (Fe x Co 1- x )O 4 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/cm 2 current density (∼1.61 V vs reversible hydrogen electrode (RHE)).

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.

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 57 Fe 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/cm 2 decreases from 378 to 339 mV and the current density at 1.7 V vs RHE increases by twofold from 150 to 315 mA/cm 2 . 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., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Fe 3 O 4 /CoFe 2 O 4 nanorods were obtained via a simple seed-mediated synthesis. Nanorods were used as seeds to grow CoFe 2 O 4 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 Am 2 /kg. Complementarily recorded 57 Fe-Mössbauer spectra were consistent with the Fe 3 O 4 /CoFe 2 O 4 spinel structure and exhibited considerable signs of spin frustration, which was correlated to the internal and surface structure of the nanorods.

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 10 6 Hz, while field-dependent particle alignment has been cross-checked via magnetometry.

Nearly phase-pure bismuth ferrite particles were formed by thermolysis of the single-source precursor [Cp(CO)2FeBi(OAc)2] (1) in octadecene at 245 °C, followed by subsequent calcination at 600 °C for 3 h. In contrast, the slightly modified compound [Cp(CO)2FeBi(O2C(t)Bu)2] (2) yielded only mixtures of different bismuth oxide phases, revealing the distinctive influence of molecular design in material synthesis. The chemical composition, morphology, and crystallinity of the resulting materials were investigated by X-ray diffraction, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. In addition, the optical properties were investigated by Fourier transform infrared and UV-vis spectroscopies, showing a strong band gap absorption in the visible range at 590 nm (2.2 eV). The magnetic behavior was probed by vibrating-sample and superconducting quantum interference device magnetometry, as well as (57)Fe Mössbauer spectroscopy.

We demonstrate the ability of Mössbauer spectroscopy to simultaneously investigate Brownian motion and Néel relaxation in ferrofluidic samples. For this purpose, Mössbauer spectra of coated iron oxide nanoparticles with core diameters of 6.0-26.4 nm dissolved in 70 vol % glycerol solution were recorded in the temperature range of 234-287 K and compared to low-temperature spectra without Brownian motion. By comparison to theory, we were able to determine the particle coating thickness and the dynamic viscosity of the fluid from the broadening of the absorption lines (Brownian motion), as well as the state of Néel relaxation. Results from Mössbauer spectroscopy were crosschecked by AC-susceptometry at several temperatures for Brownian motion and in the high-frequency regime (100 Hz-1 MHz) for Néel relaxation.

To study the effects of different temperatures and particle sizes on the anharmonic cycloidal spin structure in BiFeO3 nanoparticles, Mössbauer spectroscopy was applied to three sets of particles with different mean diameters in the range of 54 nm to 1.6 μm at temperatures between 4.2 and 800 K. The paramagnetic transition showed a distinct broadening upon decreasing particle size with Néel temperatures decreasing from 652 to 631 K. The anharmonicity of the long-range cycloidal structure, calculated from experimental Mössbauer spectra, is revealed to decrease upon rising temperature, starting at 150-200 K and reaching the harmonic state at about 400 K.