Mossbauer Spectroscopy Research Articles

Easily Water-Synthesisable Iron-Chloranilate Frameworks as High Energy and High-Power Cathodes for Sustainable Alkali-Ion Batteries.

Achieving high battery performance from low-cost, easily synthesisable electrode materials is crucial for advancing energy storage technologies. Metal organic frameworks (MOFs) combining inexpensive transition metals and organic ligands are promising candidates for high-capacity cathodes. Iron-chloranilate-water frameworks are herein reported to be produced in aqueous media under mild conditions. Removal of reticular water from known [Fe2(CAN)3(H2O)4]·4H2O yields a new supramolecular metal-organic framework (SMOF), [Fe2(CAN)3(H2O)4]. Removing coordination water, a new 2D honeycomb-like MOF forms, Fe2(CAN)3, stable without counterions and solvent. This MOF adopts the unusual ABC layer-stacking, as determined using a combination of ab initio random structure searching, electron diffraction, and Rietveld refinement of powder XRD data. Magnetometry, Mossbauer and Raman spectroscopy confirm that all three [Fe2(CAN)3(H2O)x]·yH2O phases contain HS-Fe3+ and CAN2-, with magnetic ordering temperatures increasing (5→20K) as the Fe-CAN connectivity increases. The SMOF and MOF show reversible (de)insertion of >4Li+/f.u. at average 2.59 V and 2.76 V vs Li+/Li, respectively. [Fe2(CAN)3] achieves 146 mAh/g at 1C, thus specific energy (563 Wh/kg) and power (446 W/kg) in Li half-cells competitive with conventional LiFePO4 (~580 Wh/kg and ~450 W/kg). Beyond Li, [Fe2(CAN)3] delivers 394 Wh/kg and 421 Wh/kg, for Na and K half-cells respectively, becoming a competitive cathode for sustainable batteries.

Structural Transformations in Duplex Stainless Steel CF8 Under Intensive Cold Plastic Deformation

The austenitic–martensitic transformation in austenitic–ferritic duplex stainless steel CF8 subjected to cold plastic deformation with a deformation degree ε = 10–95% is studied here using transmission Mössbauer spectroscopy (MS), conversion electron Mössbauer spectroscopy (CEMS), and X-ray diffraction (XRD) methods. It is assumed that the α′-martensite phase appeared at ε > 10%. The CEMS results showed that the formation of α′-martensite occurred most intensively in the near-surface layers of the steel, distributing in depth with the growth of the deformation degree. The volume fraction of the α′-martensite was determined based on the results of calculations carried out via the MS and XRD methods, and a good correlation was observed. A modified Olson–Cohen model was proposed to determine the dependence of the amount of α′-martensite on the deformation degree ε. The coefficients included in the Olson–Cohen expression were found.

Cerium doped superparamagnetic Mn-Zn ferrite as a promising material for self-regulated magnetic hyperthermia

Recently, cubic ferrites (CF) have been widely explored in biomedical applications, especially those that display superparamagnetism behavior due to the desirable absence of remanent field. In this study, we report the self-stabilization of the magnetic fluid hyperthermia (MFH) temperature in the cancer therapy range (42 - 48 ºC) by Ce3+ substitution in superparamagnetic Mn0.8Zn0.2Fe2-xCexO4 ferrite with x = 0.0; 0.015; 0.030; 0.050 and 0.100. A comprehensive characterization was performed in order to investigate the influence of this replacement on the magnetic and structural properties of the ferrite. The samples were synthesized by the sol-gel auto-combustion method and the properties were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), Raman spectroscopy (RS), Mössbauer spectroscopy (MS), vibrational sample magnetometry (VSM), and ferromagnetic resonance (FMR). Magnetic hyperthermia essays were used to obtain the heat induction curves and calculate energy dissipation. We refined the XRD data by the Rietveld method to determine the cation distribution and calculate interionic parameters. Magnetic characterization confirms the superparamagnetic behavior at 300 K, which is expected from the TEM results that show a narrow distribution of particle sizes, with a mean size of about 6.5 nm for all samples. The VSM results show a consistent decrease in magnetization saturation with cerium content that result in a weaker self-heating induction capacity for the cerium-doped samples. FMR results also show a smaller relaxation time T2 for these samples, suggesting a slower energy dissipation rate. These conclusions are confirmed by the heat induction curves and the values of the specific absorption rate (SAR), which are smaller for cerium-doped samples. For the a field with an amplitude of 35.33 kA/m and a frequency of 222 kHz, the temperature of the cerium-doped samples saturates in the optimum interval for cancer treatment, between 42 and 48 ºC. These results suggest that Ce3+ is a promising doping ion to optimize the heating rate behavior of Mn-Zn ferrite for cancer treatment by hyperthermia.

Challenges and Opportunities in Preparing Fe-N-C Layers Supported on Non-Carbon Supports

Global energy demand will be continuously rising in the foreseeable future. To mitigate the results of climate change it is necessary to reduce the emittance of greenhouse gases. One promising approach is to switch to hydrogen as energy carrier and use proton exchange membrane fuel cells (PEMFCs) to efficiently convert H2 into electric power. Here, hydrogen and oxygen/air are used to directly generate electrical energy with only water as byproduct. Both reactions need to happen efficiently at the same time. The oxygen reduction reaction (ORR), however, is a very sluggish four-electron-reaction and needs efficient catalysts.The state-of-the-art ORR catalyst in PEMFC is platinum but that is a very scarce and expensive metal. Hence, it is important to switch to precious-metal-group (PGM) free catalysts. In recent years, bio inspired iron-based FeNC catalysts have been shown to approach ORR activities that are competitive with those of platinum, even though they need a higher catalyst loading than Pt to reach the desired high current densities.1–3 Those catalysts feature single Fe atoms surrounded by four N atoms in graphitic carbon. The drawback of those materials is their lower stability compared to PGM materials. In a nutshell, the carbon matrix oxidizes during operation in PEMFCs, changing the morphology of the catalytic center and rendering it less active, or inactive, depending on the carbon oxidation extent. Direct demetallation phenomena are also possible, leaving a N4 cavity without metal cation center. It was shown recently by Wu et al.4 that it is possible to raise durability by adding an additional carbon layer on the catalyst. One alternative approach to reduce those degradations is to interface Fe-N4 sites with a carbon-free support. The targeted support material must be immune to corrosion in acid and withstand the typical ORR electrochemical potentials. It also has to be electrically conductive to facilitate electron transfers, both locally and on long scale.In this work, conductive ceramic metal oxide materials (Ta doped SnO2, TTO) was investigated as a possible alternative catalyst supports. This material is resistant to acid and can withstand prolonged potentials at operating conditions in PEMFCs.5 During the synthesis of the FeNC catalysts, high temperatures are generally applied. Such treatments can be detrimental to the conductivity of ceramics due to metal aggregation (in case of doped materials) and may also lead to morphological changes as well as the reduction of the ceramics to metallic materials. A robust method to synthesize FeNC catalysts is by mixing the separate Fe, N and C precursors and using optimized thermal treatment. In this study, the effect of the pyrolysis conditions as well as the ratio of FeNC precursors to TTO was investigated with various characterization methods, e.g. X-ray absorption spectroscopy, Mossbauer spectroscopy, and high resolution TEM. The characterization techniques confirm the presence of single atom Fe as well as different Sn species that might contribute to the activity. The resulting materials were electrochemically characterized with rotating disc electrode techniques and in PEM fuel cells for their ORR-activity and durability. It was shown that the activity of materials with a high FeNC precursor content relative to TTO can outperform a reference FeNC synthesized similarly but without TTO, in both RDE (Figure) and PEMFC.The presentation will report in detail the effects of pyrolysis conditions and FeNC precursor/TTO content on the structure, activity and stability of materials.(1) Mehmood, A. et al. High Loading of Single Atomic Iron Sites in Fe–NC Oxygen Reduction Catalysts for Proton Exchange Membrane Fuel Cells. Nat. Catal. 2022, 5 (4), 311–323. https://doi.org/10.1038/s41929-022-00772-9.(2) Gasteiger, H. A.; Marković, N. M. Just a Dream—or Future Reality? Science 2009, 324 (5923), 48–49. https://doi.org/10.1126/science.1172083.(3) Zion, N. et al.. Electrocatalysis of Oxygen Reduction Reaction in a Polymer Electrolyte Fuel Cell with a Covalent Framework of Iron Phthalocyanine Aerogel. ACS Appl. Energy Mater. 2022, 5 (7), 7997–8003. https://doi.org/10.1021/acsaem.2c00375.(4) Liu, S.et al. Atomically Dispersed Iron Sites with a Nitrogen–Carbon Coating as Highly Active and Durable Oxygen Reduction Catalysts for Fuel Cells. Nat. Energy 2022, 7 (7), 652–663. https://doi.org/10.1038/s41560-022-01062-1.(5) Jiménez-Morales, et al. Strong Interaction between Platinum Nanoparticles and Tantalum-Doped Tin Oxide Nanofibers and Its Activation and Stabilization Effects for Oxygen Reduction Reaction. ACS Catal. 2020, 10 (18), 10399–10411. https://doi.org/10.1021/acscatal.0c02220. Figure 1

Mössbauer analysis of (FeNiCrSiB) amorphous alloy ribbons

The fabrication of iron-based amorphous alloys was executed through the utilization of the melt-spinning technique, followed by a characterization employing X-ray diffraction (XRD), scanning electron microscopes (SEM) and transmission Mössbauer spectroscopy (MS). The studies were performed on Fe76-xNixCr4Si8B12 (where x = 0, 4, 12, and 30) metallic glasses in the form of ribbons. Mössbauer spectroscopy enables the exploration of the localized surroundings of iron (Fe) atoms within the glassy state, revealing alterations in the amorphous structure attributed to variations in the addition of Nickel (Ni). The broad lines in the Mössbauer spectra of ferromagnetic amorphous ribbons are a result of the distribution of non-equivalent iron sites and interatomic distances. The line intensity ratio suggests a preferential orientation of iron moments within the ribbon plane. The results derived from Mössbauer analysis indicate that the amorphous alloys feature bimodal distributions of the hyperfine fields. Changes in the nickel content within the alloys impact the disorder in the as-cast state and concurrently influence parameters such as the average hyperfine field <Hhyp>, the average radius R of the first coordination shell, and the number of nearest neighbor Fe atoms.

Spectrum is a picture: Feasibility study of two-dimensional convolutional neural networks in spectral processing

In chemometrics, a spectrum is usually represented in a form of numeric vector for further processing. The same approach has been used also for spectral data treatment by convolutional neural networks (CNN), initially purposed, however, for image processing. Analyzing spectral data as a two-dimensional picture rather than a one-dimensional vector potentially can improve the accuracy of regression and classification models. The purpose of this work was to test this assumption. As a first case study we have chosen one of the most difficult types of spectra to interpret – the Mössbauer spectral data. We explored the potential of 2D-CNN to predict Mössbauer spectral parameters numerically using image (.bmp) files with spectra. As a second case study, we address another challenging task – classification of biological tissues using their near-infrared spectra. In both cases, we compared the performance of CNN for two types of input data: spectra as pictures and as numeric vectors. It was found that in case of Mossbauer spectra, the use of 2D-CNN provides for better prediction of spectral parameters, while for NIR spectra of biological tissues the use of the traditional PLS-DA method turned out to be better for classification compared to the CNN approach.

Characterization of Kazakhstan’s Clays by Mössbauer Spectroscopy and X-ray Diffraction

Studies of the mineralogical composition were carried out, and the features of the clays from the deposits of Kazakhstan were established using Mössbauer spectroscopy (MS) and X-ray diffraction analysis (XRD). According to the XRD results, all the samples were mixed-layer clays of the kaolinite–illite type. The lattice parameters of the kaolinite were determined, and it was shown that its structure was disordered and contained a certain amount of impurity in some of the clay samples. A special feature of two of the samples was the additionally identified muscovite polytype 2M1. The spectra of the iron-containing clays were amenable to being resolved into separate components, with similar Mössbauer parameters of the kaolinite, muscovite, illite, and glauconite. The oxidation state of the iron was determined using MS. The predominant part of paramagnetic iron in most samples was in the trivalent state. The primary minerals contributing to Fe2+ were illite and muscovite. The results obtained during the study of the clay samples with complex mineralogical compositions using MS and XRD methods both complemented one another and were found to be in good agreement.

Complex defect formation in Fe doped γ-CuI: Enhancement of thermoelectric properties via band engineering

The doping effect of Fe atoms on CuI, a potential candidate for room temperature thermoelectric materials, was investigated due to the lack of studies for the aspect of band engineering. The addition of Fe atoms was observed to enhance the p-type performance of CuI, although Fe is more suitable as a donor material. Through Mossbauer spectroscopy and Density Functional Theory (DFT) calculations, it was determined that only about 5 % of the added Fe atoms simply substitute Cu sites, while most Fe atoms occupy interstitial sites, acting as defects and promoting Cu vacancies. Despite the trace amount of Fe only contribute to magnetic properties, it was found that multiple defects and deformation in the electronic band structure caused the effective mass to nearly double. As a result, electrical conductivity increased by an order of magnitude, while the decrease in the Seebeck coefficient was less than half, demonstrating a violation of the Pisarenko relation. Additionally, the incorporation of Fe atoms induced nano structuring behavior, increasing boundary scattering in CuI and significantly reducing thermal conductivity. Fe could be suggested as a suitable dopant for the "phonon-glass-electron-crystal" strategy.

Structure, magnetic properties and hyperthermia of Fe3-xCoxO4 nanoparticles obtained by wet high-energy ball milling

In this work, the methods of X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), Mössbauer spectroscopy (MS), magnetic properties measurements and specific loss measurements (hyperthermia) were used for the investigation of the structure and properties of Fe3-xCoxO4 nanoparticles. The Fe3-xCoxO4 nanoparticles were synthesized by using high-energy ball milling of Fe and Co mixed with water and surfactant additives. Co substitution increased the coercivity of the samples and changed the kinetics of oxidation process. The presence of cobalt ferrite was verified by MS. TEM images of synthesized samples demonstrated 5–50 nm particle size. Specific loss related heating effect depended mostly on the ratio between the samples coercivity and the amplitude of the high-frequency field. Specific loss power (SLP) and intrinsic loss power (ILP) values reached 164 W/g and 1.57 nH·m2/kg, respectively.

Preparation of magnetic composite sorbent based on exfoliated graphite with metallic iron, cobalt and nickel using melamine as a reducing agent

Known preparation methods of the magnetic sorbents based on exfoliated graphite (EG) with metallic phase take several hours and requires the use of a large amount of reducing gas at a high temperature, which is not technologically advanced. The aim of the work is to obtain EG modified with iron, cobalt, and nickel using new simple method. This method includes the thermal treatment in nitrogen atmosphere of the mixture of expandable graphite, Mn+ nitrates (Mn+ = Fe3+, Co2+, Ni2+) and melamine. The thermal decomposition of melamine leads to formation of ammonia, which reduces the products of the Mn+ nitrates decomposition (α-Fe2O3, Co3O4/CoO, NiO) to metallic iron, cobalt and nickel. The use of different amount of melamine as reducing agent leads to the formation of mixtures with different compositions containing iron oxides Fe3O4, FeO, metallic iron α-Fe, Fe-C alloy γ-(Fe,C) and iron carbide Fe3C, which were confirmed by Mossbauer spectroscopy. Metallic Co and Ni on the EG surface is formed in nitrogen atmosphere by reduction with carbon even without melamine. Obtained EG/Fe has the highest saturation magnetization of 54.7 emu/g. EG/Co and EG/Ni have lower saturation magnetization of 40.1 and 12.0 emu/g, which is due to lower saturation magnetization of the individual metals.

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Investigation of structural, electrical, and magnetic variations of Ni-Zn-Co ferrites by substituting rare earth Ho3+ for high-frequency applications

The investigation of structural, magnetic, and electrical properties of Ni0.6Zn0.3Co0.1HoxFe2−xO4 (NZCHF, 0 ≤ x ≤ 0.2) ferrites, synthesized through the sol–gel autocombustion method, has been undertaken. The refined x-ray diffraction (XRD) analysis was performed for XRD data analysis using Fullprof Suite software and it confirmed a single-phase cubic spinel structure, with the determination of crystallite size, refinement parameters and lattice constants. The bulk density of the samples consistently remained lower than the x-ray density, with densities increasing proportionally to the enhancement of Ho concentration. FTIR analysis corroborated the presence of metal-oxygen bonds within the ferrite possessing a spinel cubic structure. 57Fe Mossbauer spectroscopy showed that the hyperfine magnetic field of tetrahedral (A) and octahedral (B) sites decreased with the substitution of Ho3+ ions that preferentially occupy the B site. The impedance analyzer and vibrating sample magnetometer (VSM) were utilized to measure the real and imaginary parts of the complex permeability and magnetic properties of the samples, respectively. Complex impedance plots were scrutinized to discern the contributions of grain and grain boundary resistances, providing insights into the electrical behavior of the ferrite samples. Furthermore, the introduction of Ho concentration led to alterations in other key properties of the ferrites, including coercivity (H c ), retentivity (M r ), anisotropy constant (K), and magnetic moment (μ B ).The impact of the rare-earth content on the magnetic features of the prepared NiZnCo ferrite microspheres was investigated by analyzing magnetic-hysteresis (M-H) loops, which showed soft ferrimagnetism. Concurrently, the dielectric constant and dielectric loss tangent of the studied samples exhibited a decrease with the rise in Ho3+ concentration. The expected reduction in tan loss in the prepared samples is attributed to the increase in ac resistivity associated with the higher Ho3+ content.

Magnetically engineering enhanced EMA property through high entropy transition metal ions within all-inorganic perovskite

Addressing challenges such as signal interference and crosstalk requires the development of new materials capable of electromagnetic absorption (EMA). In this study, we explored magnetically high-entropy engineering by incorporating transition metal ions into the B sites of all-inorganic CsPbBr3 perovskite. This approach yielded excellent EMA properties, including a minimum reflection loss of 75 dB at 10.2 GHz with a thickness of 2.5 mm and an effective bandwidth of 8.8 GHz. Fe, Co, Ni, and Mn ions were successfully introduced into the CsPbBr3 lattice using high-energy ball milling and the combustion method. Through rigorous characterization techniques such as Rietveld refinement of X-ray diffraction and Grazing-Incidence Wide-Angle Scattering patterns, we confirmed the presence of high-entropy phases. Additionally, we conducted comprehensive studies using Vibrating-sample magnetometer, L2,3 edge XANES, and Mossbauer spectra to investigate the magnetic polarization, spin states, and dipolar exchanges of the transition metal ions. The observed synergistic effects among the magnetic permeability, polarization, and magnetic loss of these ions underscored their role in enhancing the EMA performance of CsPbBr3.

Adjusting the gas detection characteristics of NiFe2O4 spinel ferrite nanoparticles through the introduction of Zn doping

Nickel ferrite nanoparticles doped with zinc were synthesized at a lower reaction temperature of 180 °C. The research delved into their structural, optical, dielectric, and magnetic properties. These nanoparticles exhibited a distinct cubic spinel structure, with crystallite sizes ranging from 33 to 51 nm. FTIR analysis revealed metal oxide stretching vibrations between 400–600 nm. FESEM and HR-TEM examinations unveiled irregularly shaped nano-particles. XPS analysis disclosed the chemical states of Zn2+, Fe3+, and Ni2+ ions. Mossbauer spectra exhibited two sextet patterns related to tetrahedral (A) and octahedral (B) sites, plus a weak doublet pattern. Magnetic tests showed a decrease in saturation magnetization (Ms) but an increase in remanent magnetization (Mr) and coercivity (Hc) values upon doping.

Effect of sintering temperature on structural, elastic, and hyperfine features of nickel ferrite nanoparticles

Temperature is one of the key parameters in the synthesis of a system of magnetic nanoparticles and can affect considerably the arrangement of atoms in the crystal structure. Consequently, the magnetic, elastic, and structural properties are strongly impacted. In the magnetically soft NiFe1.8O4 spinel ferrite, the relative number of Ni and Fe ions in each of the two possible different geometries, tetrahedral (T) and octahedral (O), is of extreme importance. In this work, this material was studied on products of co-precipitation synthesis followed by a temperature dependent sintering. We performed 57Fe Mössbauer spectroscopy (MS), X-ray diffraction (XRD), scanning and transmission electron microscopies (SEM and TEM), X-ray absorption spectroscopy (XAS) using synchrotron radiation at Ni K- and L2-edge, and vibrating sample magnetometry (VSM) measurements. From XAS measurements it was found that Ni atoms prefer an octahedral coordination when the sintering temperature is increased. MS showed that the T-sites are more populated by Fe ions than the O-sites, a fact that can be explained by the presence of Fe ion vacancies in the O- sites. However, as the sintering temperature increases, we found that there is also a migration of Fe atom to the O-sites. Additionally, based on MS measurements in 78–292 K region, we estimated the Debye temperatures of the Fe ions in the tetra- and octahedral geometries and found that the recoiless f-factor depends on the sintering temperature of the nickel ferrite powders. The ratio fO/fT is about 0.98 and 0.95 at room temperature for the samples sintered at 1000 °C and 600 °C, respectively.

Polymer–Zeolite Composites: Synthesis, Characterization and Application

Although the potential of natural minerals for purification of liquid radioactive wastes (LRW) from radionuclides has been widely studied, the use of hybrid polymer composites made of zeolite is still rather scarce. This article reports on the preparation of zeolite-based hybrid polymer composites using the in situ polymerization technique in the body of mineral matrix and its intercalated with copper ferrocyanide (CuFC) forms. This hybrid polymer composites have shown unique and enhanced properties for the removal of micropollutants from wasted water as compared to the individual mineral. The change in conventional properties of two mixed minerals, such as zeolite and bentonite, and their intercalated with CuFC forms were probed using techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), Mössbauer spectroscopy (MS) and FT-IR analysis. The totality of analysis showed a coexistence of intercalated and percolated zeolite phases. The hybrid polymer composites exhibited both adsorption and ion-exchange properties in the removal of 134,137Cs+, 57,60Co2+ and 85Sr2+ radionuclides from LRW.

Exploring the effect of zinc substitution in nanocrystalline nickel ferrite for enhanced supercapacitor and gas sensing applications

A hydrothermal method was employed to synthesize Zn-substituted nickel ferrite nanoparticles at an optimized reaction temperature of 175 °C. X-ray diffraction analysis of as-synthesized nanoparticles exhibited a cubic spinel structure, and the average crystallite size decreased from 41 nm to 31 nm with increasing dopant concentration. Morphological study confirmed the cubic shape of the prepared nanoparticles. Raman spectra exhibited five Raman active modes (A1g + Eg + 3T2g), which are attributed to ferrite. The dielectric constant decreased and became constant with increasing frequency, whereas the AC conductivity demonstrated an increasing trend. The oxidation state and elemental composition of Zn2+, Ni2+ and Fe3+ in Zn-doped NiFe2O4 were confirmed by XPS measurements. Mossbauer spectra were recorded to determine the oxidation state of the iron. The coercivity increased with increasing Zn concentration. The Day plot analysis confirmed the pseudo-single-domain nature of the as-synthesized nanoparticles. Pseudocapacitive behavior was observed for all samples, whereas a high Csp value was achieved for ZNF3 (598 F/g). The LPG sensor made out of the synthesized nanoparticles demonstrated faster response and recovery times of 13 and 31 s, respectively, when exposed to a concentration of 10 ppm.

Structure and Activity-Durability Tradeoff of Coated Fe-N-C Catalysts for the Oxygen Reduction Reaction

Fe-based catalysts stand out for oxygen reduction reactions among the platinum group metal (PGM)-free catalysts for reducing the reliance on expensive and scarce platinum. With the endeavor of a PGM-free community, the state-of-the-art Fe-N-C catalysts have demonstrated encouraging initial activity in Proton Exchange Membrane Fuel Cell (PEMFC) 1-2. However, their long-term stability and durability remain a challenge, both in acidic liquid electrolyte cells and in single-cell PEMFCs3. Recently, a novel approach has demonstrated improved durability of Fe-N-C catalysts during ORR, which consisted of coating a pre-existing Fe-N-C with a thin carbon overlayer obtained via chemical vapor deposition of a metal-organic framework (ZIF-8), at 1100 °C4. However, the underlying mechanism for enhanced durability remains unclear. One of the keys to improved stability lies in the specific structure of the catalysts, including the coordination of the ORR-active iron atoms and the structure of the nitrogen-doped carbon matrix, especially the structure located at the top surface of catalysts. The CVD conditions that affect the structure of FeNC must be optimized, to achieve the optimal activity-durability trade-off.This presentation will report on the structure, activity, and durability trends of a suite of FeNC catalysts coated at different CVD conditions. The key parameters have been investigated, such as deposition temperature, overlayer thickness, and iron speciation on their ORR activity and durability. The coated Fe-N-C catalysts have been evaluated for their activity/durability (in oxygenated environments) both in liquid electrolyte cells and PEMFCs. The coated Fe-N-C demonstrated inferior initial activity and improved durability (Figure 1). The correlation between the structural information derived from multiple techniques (XRD, Mossbauer spectroscopy, TEM, Raman spectroscopy, N2 sorption, etc) and their electrochemical behaviors will be discussed.References Jiao, L.; Li, J.; Richard, L. L.; Sun, Q.; Stracensky, T.; Liu, E.; Sougrati, M. T.; Zhao, Z.; Yang, F.; Zhong, S.; Xu, H.; Mukerjee, S.; Huang, Y.; Cullen, D. A.; Park, J. H.; Ferrandon, M.; Myers, D. J.; Jaouen, F.; Jia, Q., Nature Materials 2021, 20 (10), 1385-1391.Mehmood, A.; Gong, M.; Jaouen, F.; Roy, A.; Zitolo, A.; Khan, A.; Sougrati, M.-T.; Primbs, M.; Bonastre, A. M.; Fongalland, D.; Drazic, G.; Strasser, P.; Kucernak, A., Nature Catalysis 2022, 5 (4), 311-323.Martinez, U.; Komini Babu, S.; Holby, E. F.; Zelenay, P., Current Opinion in Electrochemistry 2018, 9, 224-232.Liu, S.; Li, C.; Zachman, M. J.; Zeng, Y.; Yu, H.; Li, B.; Wang, M.; Braaten, J.; Liu, J.; Meyer, H. M.; Lucero, M.; Kropf, A. J.; Alp, E. E.; Gong, Q.; Shi, Q.; Feng, Z.; Xu, H.; Wang, G.; Myers, D. J.; Xie, J.; Cullen, D. A.; Litster, S.; Wu, G., Nature Energy 2022, 7 (7), 652-663. Figure 1

Structural transformation and magnetic properties of Fe-substituted nano CuCr2O4 spinel structure

Nanoparticles of CuCr2O4 and Fe substituted CuCr2O4 are synthesized using the sol-gel technique and characterized using XRD Raman and FeSEM to determine their structure and particle size. The XRD findings of CuCr2-xFexO4 showed the tetragonal phase for x = 0.0 and the cubic phase for the remaining compounds (x = 0.5,1.0 &1.5). With Fe substitution, the average crystalline size rose. At ambient temperature, the Raman spectra of the series' parent compounds and Fe-doped compounds were recorded. Raman modes for the compounds have been found, with one of the modes, A1g, shifting to a lower wavenumber owing to Fe substitution. When Fe was substituted, the energy band gap widened. With the use of FeSEM, particle shape was modified from irregular to regular (rectangular) for Fe replacement. The magnetic state and oxidation state of Fe in compounds was identified from the Mossbauer spectroscopy at room temepature. The magnetic data indicate that as Fe substitutes at the Cr site, the magnetic transition shifts to high temperature, from 122 K to 300 K. The saturation magnetization was raised, as well as the change of hard to soft magnetic nature for Fe replacement at the Cr site, which may be used for microwave frequency applications.

The iron oxidation state of Ryugu samples

AbstractThe Hayabusa2 mission sampled Ryugu, an asteroid that did not suffer extensive thermal metamorphism, and returned rocks to the Earth with no significant air exposure. It therefore offers a unique opportunity to study the redox state of carbonaceous Cb‐type asteroids and evaluate the overall redox state of the most primitive rocks of the solar system. An analytical framework was developed to investigate the iron mineralogy and valence state in extraterrestrial material at the micron scale by combining x‐ray diffraction, conventional Mössbauer (MS), and nuclear forward scattering (NFS) spectroscopies. An array of standard minerals was analyzed and cross‐calibrated between MS and NFS. Then, MS and NFS spectra on three Ryugu grains were collected at the bulk and the micron scales. In Ryugu samples, iron is essentially accommodated in magnetite, clay minerals (serpentine–smectite), and sulfides. Only a single set of Mössbauer parameters was necessary to account for the entire variability observed in MS and NFS spectra, at all spatial scales investigated. These parameters therefore make up a fully consistent iron mineralogical model for the Ryugu samples. As far as MS and NFS spectroscopies are concerned, Ryugu grains are overall similar to each other and share most of their mineralogical features with CI‐type chondrites. In detail however, no ferrihydrite is found in Ryugu particles even at the very sensitive scale of Mössbauer spectroscopy. The typical Fe3+/Fetot of clay minerals is much lower than typical redox ratios measured in CI chondrites (Fe3+/Fetot = 85%–90%). Furthermore, magnetite from Ryugu is stoichiometric with no significant maghemite component, whereas up to 12% of maghemite was previously identified in the Orgueil's so‐called magnetite. These differences suggest that most CI meteorites suffered terrestrial alteration and that the preterrestrial composition of these carbon‐rich samples was less oxidized than previously measured. However, it is not clear yet whether or not the parent bodies of CI chondrites were as reduced as Ryugu. Finally, the high spatial resolution of NFS allows to disentangle the redox state and the crystal chemistry of iron accommodated in serpentine and smectite. The most likely polytype of serpentine is lizardite, containing &lt;35% of Fe3+, a fraction of which being tetrahedrally coordinated. Smectite is more oxidized (Fe3+/Fetot &gt; 65%) and mainly contains octahedral ferric iron. This finding implies that these clays formed from highly alkaline fluids and the spatial variability highlighted here may suggest a temporal evolution or a spatial variability of the nature of this fluid.