Octahedral Fe3 Research Articles

The potential of Gd doping as a promising approach for enhancing the adsorption properties of nickel-cobalt ferrites.

The study shows that the addition of gadolinium ions has a significant impact on the structure, morphology, and adsorption properties of Ni-Co spinel ferrite that was synthesized by the sol-gel auto-combustion method. The research also indicates that the higher the Gd content, the greater the increase in the lattice parameter, which suggests that Gd3+ ions uniformly replaced the octahedral Fe3+ ions. The morphology and chemical composition of Gd-doped Ni-Co ferrites have been studied using SEM and EDS. Gd adding to the NiCoFe matrix increases the BET surface area by 50% (from 48 to 72 m2/g) and promotes the formation of mesopores with an average radius from 3.9 to 4.9nm. The pHPZC values of Gd-doped ferrites are in the range of 7.22-7.39, which means that the ferrite surface will acquire a positive charge at natural pH, so this will promote the adsorption of Congo red anionic dye through electrostatic interaction forces. Langmuir, Freundlich, and Dubinin-Radushkevich models were used to explain the mechanism of CR adsorption on the Ni0.5Co0.5GdxFe2-xO4 adsorbent surface. The ionic-covalent parameter has been estimated to describe the surface acid-base properties. Overall, this study highlights the potential of Gd3+ doping as a promising approach for enhancing the adsorption properties of nickel-cobalt ferrites.

Mössbauer, optical and structural properties of [formula omitted] ion in borate glass

Lanthanum-bearing iron lithium borate glass is a quaternary system for oxide glasses and was prepared via the melt-quenching method. The present article correlates the structure, optical, ligand field and Mössbauer data on iron lithium borate glass containing La3+. The density was measured, while the molar volume was calculated. Other physical parameters are well-described. With increasing the La2O3 content within the glass network, infrared spectra analysis reveals structural modifications such as the increase in BO4 units and the decline in both BO3 units and NBO bonds content. Furthermore, optical absorption spectra were measured. The absorption spectra disclose a plethora of electronic transitions that are related to Fe3+ in tetrahedral and octahedral sites, however, Fe2+ phase is not observed in optical spectra, but it has a clear signature in Mössbauer spectra. Besides, the glass absorption edges undergo a clear blue shift, reflecting an increased band gap energy (1.96–2.28 eV). The decline in NBO bonds justifies this trend. Bewitchingly, the values of crystal field splitting are increased, while the values of Racah parameters are decreased. This trend is justified by the decline in NBO bonds and increases electron localization around Fe cations. Mössbauer spectra confirm the existence of Fe3+ in tetrahedral and octahedral sites, while Fe2+ exists in only a tetrahedral state. With increasing La2O3 content, the isomer shift of Fe3+ in tetrahedral sites changes to be 0.312–0.329 mm/s, while the isomer shift of octahedral Fe3+ is 0.424–0.456 mm/s. These findings coincide with optical data. While the isomer shift of tetrahedral Fe2+ is 0.902–0.911 mm/s. Our results of structural, optical and ligand field associated with Mössbauer spectra open more vistas toward the utility of these samples in the optics realm.

Regulating the distribution of iron active sites on γ-Fe2O3via Mn-modified α-Fe2O3 for NH3-SCR

Developing below 150 °C highly activity and broad reaction window catalysts has been challenging by using Fe-based catalysts for NH3-SCR. The octahedral Fe3+ (Fe3+Oh) sites exist in hematite (α-Fe2O3) and maghemite (γ-Fe2O3) are inactive for NH3-SCR due to the redox circle of Fe2+→Fe3+ reliance on the distribution of iron sites in crystal structure. Here we modified the α-Fe2O3 crystal structure by substituting part inactive Fe3+Oh sites with catalytically active Mn3+Oh sites, which promoted the formation of γ-Fe2O3 to generate the active tetrahedral Fe3+ (Fe3+Td) sites and enhanced the magnetism of the Fe1−yMnyOx. The strong Fe-O-Mn interaction established by crystal coordinative configurations not only boosted the formation of NO2 but also facilitated the Brønsted acid circle. Surprisingly, the Fe0.85Mn0.15Ox exhibited the superior low temperature NH3-SCR activity, with NOx conversion above 100% at 100–275 °C under a GHSV of 60000 h−1.

Er-driven incommensurate to commensurate magnetic phase transition of Fe in the spin-chain compound BaErFeO4

Magnetic phase transitions and structures of the spin-chain compound BaErFeO4 were investigated by measurements of magnetic properties (specific heat, magnetic susceptibility) and neutron diffraction. The lattice geometry of the orthorhombic crystal structure (space group ) of the BaRFeO4 compounds (R=Dy–Yb, Y) supports frustrations which lead to multiple magnetic phase transitions with complex magnetic structures. BaErFeO4 undergoes three successive magnetic phase transitions at TN1=49K, TN2=33.4K, and TN3=3.4K. In contrast with the previously investigated BaRFeO4 (R=Y, Tm, Yb) compounds, all with incommensurate magnetic propagation vectors k1=(0,0,kz), BaErFeO4 is the first member in this series that shows a phase transition from an incommensurate (k1 below TN1) to a commensurate magnetic structure with k2=(12,0,12) below TN2. In the crystal structure, all magnetic ions (Fe1, Fe2, Er1, and Er2) are part of chains propagating along the b axis. Below TN1, strong antiferromagnetic (AFM) Fe-Fe spin-exchange coupling between square pyramidal (Fe1) and octahedral (Fe2) centers generates a collinear AFM structure with a constant size of the ordered Fe moments and a constant magnetic phase inside each chain of Fe3+ cations. Exchange coupling between the Fe chains is much weaker. At TN2, 3d−4f exchange interactions induce an ordered moment at the Er3+ ions, which results in a change of the direction of the ordered Fe moments from the b direction (above TN2) to inside the ac plane (below TN2) and a change from an incommensurate (k1 above TN2) to a commensurate (k2 below TN2) AFM structure. Toward lower temperature, 4f−4f exchange interactions become stronger and create at TN3 a constant magnetic phase inside each chain of Er3+ cations. At TN2 and TN3, the magnetic susceptibility shows sharp decreases that coincide with large increases of the correlation length of the magnetic structure. The unique magnetic structures of BaErFeO4 are compared with those of other BaRFeO4 compounds by considering experimental and theoretical aspects. ©2024 American Physical Society 2024 American Physical Society

Effect of Al substitution at the Ga site on the structural and magnetic properties of GaFeO3

GaFeO3 compound figures among those orthoferrites that are potential candidates for multiferroics. However, GaFeO3 suffers from a relatively low Nèel temperature, TN ≈ 200 K, and magnetic moment. Based on the results of a detailed investigation of Raman-active modes, structural and magnetic properties of the Ga1-xAlxFeO3 (x = 0.0, 0.05, 0.10, 0.20, 0.30) samples, we show that Al substitution at the Ga sites remedies these shortcomings to a large extent. This work brings out clearly that Al preferentially occupies the tetrahedral (Ga1) sites rather than the octahedral (Ga2, Fe1 and Fe2) sites. The effect of Al substitution in Ga1-xAlxFeO3 is to (i) decrease the lattice parameters and cation-O bond lengths which results in a shift in the positions of Raman peaks towards higher wavenumbers, and (ii) increase (decrease) the cation-O-cation bond-angles such that the antiferromagnetic (ferromagnetic) superexchange interactions grow in strength. An enhancement in these interactions accounts for the observed increase in the Nèel temperature, TN, as well as in the saturation magnetization. The radically different temperature variations of the ‘zero-field-cooled’ and ‘field-cooled’ magnetizations below the irreversibility temperature can be qualitatively understood in terms of the Nèel molecular-field theory for ferrimagnetism. The temperature dependence of inverse susceptibility in the paramagnetic state provides evidence for the non-linear behavior at temperatures well above TN and hence for the persistence of short-range magnetic order to temperatures as high as 1.75 TN.

Synthesis, characterization, and enhanced sunlight-active photocatalytic property of single-site octahedral iron(III) oxide complex – Grafted graphene oxide

The reported study delves into the synthesis and analysis of an innovative composite material formed by grafting single-site octahedral iron(III) oxide complex onto graphene oxide (GO). The formation of the composite employs an innovative approach, utilizing a one-pot adsorption procedure to synthesize iron(III) oxide complex-modified graphene oxide (Fe-GO), with [Fe(bipy)Cl4][bipyH] serving as the precursor complex. Employing an array of analytical techniques including XRD, FTIR, DRS, PL, SEM, EDAX, XPS, and MB analyses, we meticulously uncover the intricate structural attributes of the resulting Fe-GO composite. Mössbauer spectroscopy confirms the presence of distorted octahedral Fe3+ single-sites grafted onto the GO surface, a crucial aspect firmly established in our synthesized specimen. This innovative approach not only enhances the photoactive properties of GO but also offers a resource-efficient avenue for such improvements. The photochemical efficacy of the synthesized samples is rigorously assessed by Rhodamine B degradation in water under authentic sunlight exposure. Remarkably, the Fe-GO composite outperforms pristine graphite, GO, and metal oxide photocatalysts (TiO2 and SnO2 based materials), underscoring its exceptional photocatalytic performance. The catalyst's durability and recyclability are thoroughly examined over five cycles, affirming its lasting effectiveness. Collectively, our findings highlight the substantial promise of iron-complex-decorated GO as an efficient solar-responsive photocatalyst, surpassing existing commercially available counterparts. This investigation opens a viable path towards the development of economically sustainable photocatalysts, tailored to meet the demands of various environmental applications reliant on solar-driven reactions.

Isomorphously Substituted [Fe,Al]ZSM-5 Catalysts for Methane Dehydroaromatization

Dehydroaromatization of methane (MDA) under non-oxidative conditions is a promising reaction for direct valorization of natural gas and biogas. Typically, Fe-modified ZSM-5 catalysts display low aromatic productivity and high coke selectivity in the MDA reaction. Herein, we show the benefit of starting from isomorphously substituted Fe-sites in [Fe,Al]ZSM-5 zeolites prepared by direct hydrothermal synthesis. Upon calcination, these samples contain predominantly isolated Fe3+ species, either atomically dispersed within the zeolite framework or anchored at exchange sites inside zeolite channels. In terms of the integral hydrocarbon productivity, [Fe,Al]ZSM-5 catalysts outperform Fe/ZSM-5, prepared by impregnation, as well as Mo/ZSM-5 catalysts with the same Si/Al ratio and molar metal loading. Operando X-ray absorption spectroscopy coupled with mass spectrometry (XANES-MS) demonstrates that the initial tetrahedral Fe3+ within the zeolite framework or at exchange sites are transformed into octahedral extraframework Fe2+ active sites during the MDA reaction and form small Fe2O3 clusters during oxidative regeneration. Combining activity measurements and operando thermogravimetry shows that the duration of the induction period, related to the formation of active hydrocarbon pool intermediates, strongly depends on the Fe dispersion and loading and can be used as a suitable descriptor for the MDA activity of [Fe,Al]ZSM-5. The shorter induction period of [Fe,Al]ZSM-5 in comparison to impregnated Fe/ZSM-5 can be linked to the higher methane conversion rate over highly dispersed Fe-sites and faster formation of active hydrocarbon pool intermediates.

Structural and Electrical Properties of Novel Cr/Fe Mixed Transition-Metal Phosphates.

The phosphate KCoCr(PO4)2 and iron-substituted variants KCoCr1-xFex(PO4)2 (x = 0.25, 0.5, and 0.75) were synthesized by a solid-state reaction route, while a high substitution level of Fe was achieved. Their structures were refined using powder X-ray diffraction and indexed in a monoclinic system with a P21/n space group. A 3D framework with six-sided tunnels parallel to the [101] direction was formed in which the K atoms are located. Mössbauer spectroscopy confirms the exclusive presence of octahedral paramagnetic Fe3+ ions, with isomer shifts increasing slightly with x substitution. Electron paramagnetic resonance spectroscopy confirmed the presence of paramagnetic Cr3+ ions. The activation energy, determined by dielectric measurements, shows that the iron-containing samples present higher ionic activity. Relative to the electrochemical activity of K, these materials could be good candidates for positive and/or negative electrode materials for energy storage applications.

Almandine jewelry garnet from the Kitelya deposit (Karelia): composition and spectroscopic properties

Research subject. The chemical composition and spectroscopic properties of almandine jewelry garnets from the Kite-lya deposit in the Northern Ladoga region (Karelia). Materials and methods. The chemical composition, impurity elements, mineral inclusions and spectroscopic properties of almandine jewelry crystals were studied using IR and Mössbauer spectroscopy. Results. Garnet crystals were found to exhibit a weakly pronounced zonal composition, varying from Alm75Pir15Sps7Grs3 in the center to Alm80Pir14Sps4Grs2 at their edges. Therefore, the Ca and Mn contents decrease towards the grain edges. This zonality of garnets is characteristic of the processes of progressive metamorphism of their host rocks. The garnet crystals feature small inclusions of quartz, chlorite, mica FACI (biotite), ilmenite, rutile, monazite, zircon and pyrrhotite. The composition of chlorite, biotite and zircon was established. The parameter of the cube unit cell ao = 11.522 ± 0.003 Å was calculated. The IR absorption spectra of 995, 966, 901, 878, 638, 568, 528, 476 and 455 cm–1 are characteristic of the pyrope-almandine difference. Mössbauer spectroscopy revealed an insignificant admixture of trivalent iron (Fe3+) in the structure of Kitelya garnets (≈1 % of the amount of isomorphic iron). The obtained optical absorption spectra of garnet plates in the visible light spectrum indicate that Fe2+ ions in dodecahedral positions, to a lesser extent dodecahedral Mn2+ ions, as well as possibly octahedral Fe3+ ions are responsible for the bright red-crimson color of pyrop-almandine from the Kitelya deposit. Conclusions. A “portrait” of typomorphic features (composition and properties) of the pyrope-almandine jewelry garnet from the Kitelya deposit was obtained. This portrait can be used when analyzing the historical finds of faceted or cabochonized differences of almandine in jewelry, church utensils in both Russia and Europe (where this jewelry material was exported during the 17th century). The preservation of garnet jewelry differences in the host rock is due to the presence of thin amorphous kelefite shells or soft minerals (sericite, chlorite, kaolinite etc.).

Substituting Chromium in Iron-Based Catalysts for the High-Temperature Water-Gas Shift Reaction.

A set of doped iron oxides (chromium, aluminum, gallium, indium, manganese, zinc, niobium) were prepared by a one-step coprecipitation/calcination approach evaluated for their WGS activity under industrially relevant conditions and characterized in detail. The WGS activity after ageing the doped catalyst for 4 days at 25 bar follows the order chromium ≈ aluminum > gallium > indium > manganese > zinc > niobium for copper-codoped catalysts. The activated catalysts predominantly consist of magnetite, irrespective of the dopant. Mössbauer spectra of aged catalysts showed that aluminum and zinc occupy both tetrahedral and octahedral sites of magnetite, while chromium, gallium, indium, manganese, and niobium preferentially substitute octahedral iron. The incorporation of trivalent metal ions of similar size to octahedral Fe3+ (i.e., chromium, aluminum, gallium) results in moderate to high CO conversion, irrespective of incorporation in tetrahedral or octahedral sites. The substitution of Fe2+ with Mn2+ results in an increased Fe3+/Fe2+ ratio. Incorporation of Zn2+ in tetrahedral sites (replacing Fe3+ ions) leads to a complex structure where the charge balance is compensated from the octahedral sites. Separate dopant metal oxide phases were observed in indium- and niobium-doped catalysts. XPS shows that copper is present as a separate phase in activated copper-codoped catalysts. Aluminum is identified as the most promising promoter for substituting chromium in commercial high-temperature WGS catalysts on the basis of their similar high CO conversion although incorporation of these dopants into the magnetite structure differed substantially.

Mo-Incorporated Magnetite Fe3 O4 Featuring Cationic Vacancies Enabling Fast Lithium Intercalation for Batteries.

Transition metal oxides (TMOs) as high-capacity electrodes have several drawbacks owing to their inherent poor electronic conductivity and structural instability during the multi-electron conversion reaction process. In this study, the authorsuse an intrinsic high-valent cation substitution approach to stabilize cation-deficient magnetite (Fe3 O4 ) and overcome the abovementioned issues. Herein, 5 at% of Mo4+ -ions are incorporated into the spinel structure to substitute octahedral Fe3+ -ions, featuring ≈1.7 at% cationic vacancies in the octahedral sites. This defective Fe2.93 ▫0.017 Mo0.053 O4 electrode shows significant improvements in the mitigation of capacity fade and the promotion of rate performance as compared to the pristine Fe3 O4 . Furthermore, physical-electrochemical analyses and theoretical calculations are performed to investigate the underlying mechanisms. In Fe2.93 ▫0.017 Mo0.053 O4 , the cationic vacancies provide active sites for storing Li+ and vacancy-mediated Li+ migration paths with lower energy barriers. The enlarged lattice and improved electronic conductivity induced by larger doped-Mo4+ yield this defective oxide capable of fast lithium intercalation. This is confirmed by a combined characterization including electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT) and density functional theory (DFT) calculation. This study provides a valuable strategy of vacancy-mediated reaction to intrinsically modulate the defective structure in TMOs for high-performance lithium-ion batteries.

Topotactic Oxygen Release and Incorporation in AFeO3 with Fe4+, AFeO2.5 with Fe3+, and AFeO2 with Fe2+ (A = Ca and Sr): Dedicated to the Occasion of the 100th Birthday of Prof. John B. Goodenough

Oxygen contents in perovskite-structure Fe oxides can change in accordance with the valence states of Fe, i.e., AFeO3 with Fe4+, AFeO2.5 with Fe3+, and AFeO2 with Fe2+ (A = Ca and Sr). AFeO3 has a fully oxygenated simple-perovskite structure, and the unusual high valence Fe4+ in AFeO3 is easily reduced to relatively stable Fe3+ by releasing oxygen. On the other hand, AFeO2 has an infinite-layer structure, and the unusual square-planar coordination of Fe2+ in AFeO2 changes to tetrahedral and octahedral Fe3+ by incorporating oxygen. Sample weight measurements by thermogravimetry and corresponding phase analysis with synchrotron X-ray diffraction data revealed that the difference in the A-site cation strongly influenced the oxygen release and incorporation behaviors. In ambient air, topotactic changes of AFe4+O3 → AFe3+O2.5 ← AFe2+O2 for both A = Ca and Sr can occur by releasing and incorporating oxygen in the perovskite structure frameworks. Nonstoichiometric phases with oxygen vacancies are present between SrFeO3 and SrFeO2.5.

Characterization of iron oxide waste scales obtained by rolling mill steel industry

Every year, the steelmaking industry produces millions of tons of slags resulting in pollution to the environment. Among the waste, secondary metals and scales rich in iron oxides are also thrown away. There is a need to treat the steel waste in a reasonably way to protect the environment and proposing new cheap technologies for producing advanced materials. In this study we report the morphological and structural characterization of waste scales generated during roll milling steel process at JSC “Arcelor Mittal Temirtau”. The raw slag and annealed at 1000 °C were measured by X-ray diffraction (XRD), scanning electron microscopy adapted with energy dispersive X-ray (SEM- EDX), magnetometry and Mössbauer Spectroscopy (MS). Fe and O were detected by EDX as main chemical elements and Si, S, Ca, Mg, C and Al as minimal elemental composition. XDR for the raw sample revealed α-Fe2O3 (hematite) and Fe3O4 (magnetite) as principal and secondary phase, respectively; whereas monophasic α-Fe2O3 is detected for the scales annealed at 1000 °C. Magnetometry measurements show the Verwey transition for the raw sample and the Morin transition for the annealed at 1000 °C; those are fingerprints for the presence of magnetite and hematite, respectively. MS measurements for the raw sample consist of 6 small peaks of absorption and a broad two-lines absorption peak in the central part. The doublets are associated to the hyperfine parameters belonging to wustite. Magnetite is related to the hyperfine parameters for two sextets in octahedral Fe2.5+ and tetrahedral Fe3+sites and a small sextet that resembles the Mössbauer parameters of α-Fe2O3. Only a well crystallized and weakly ferromagnetic sextet confirm the presence of α-Fe2O3 phase for the sample annealed at 1000 °C due to thermal oxidation.

Tin-bearing minerals at the Furong tin deposit, South China: Implications for tin mineralization

It remains poorly constrained whether remobilization of Sn from granites and prograde skarns plays an essential role in forming economic (skarn-type) tin mineralization. Using both electron probe microanalysis and laser ablation–inductively coupled plasma–mass spectrometry methods, in-situ Sn contents, as well as major elements, were analyzed for numerous silicates and magnetite from fresh granite, altered granite, and skarn at the large Furong Sn deposit (530,000 t Sn @ 0.8% Sn) in the Nanling Range, South China. Hornblende and biotite in fresh granite are the main Sn-bearing phases (Sn = 44–321 ppm), while plagioclase and K-feldspar are poor in Sn (< 5 ppm). In altered granite, tin is hosted mainly by hydrothermal muscovite (299–583 ppm) replacing plagioclase, but rarely by chlorite (mostly <10 ppm) replacing hornblende and biotite. In contrast, most silicates (garnet, diopside, vesuvianite, pargasite and epidote) and magnetite from tin skarn are Sn-rich (47–44,241 ppm), except for Sn-poor phlogopite and scapolite (< 10 ppm). In particular, garnet, pargasite, and epidote reach tin concentrations in the percent range. Tin generally enters the stannous silicates and magnetite through substitutions for octahedral Alvi and Fe3+. Comparisons of Sn contents between magmatic and hydrothermal minerals in granite, prograde and retrograde minerals related to tin skarn indicate that remobilization of Sn from granite and prograde skarn is not a pre-requisite to form tin mineralization.

Andradite titanium: Preparation, characterization and metallurgical performance

AbstractAndradite titanium (Ca3Fe2Si1.58Ti1.42O12, abbreviated as AT), which is a significant mineral phase in the sinter of titanium‐containing iron ore, was prepared via a solid‐state reaction with analytical reagents. The crystal structure, cold strength, and high‐temperature heat capacity were individually characterized, and the metallurgical performance, such as melting and reduction behavior, were measured. AT is a variant of andradite (Ca3Fe2Si3O12) formed by the Ti4+ substitution for Fe3+ in the octahedral sites and Fe3+ substitution for Si4+ in the tetrahedral sites. The compressive strength of AT was approximately 14.21 MPa, and its softening, melting, and flowing temperatures were 1453, 1483, and 1509 K, respectively. According to the differential scanning calorimetry measurements, the melting point was approximately 1502 K. The non‐isothermal reduction results revealed that AT was reduced to Fe, perovskite, and wollastonite in a single step, and the isothermal reduction test indicated that the reduction degree of AT was only 0.67 when reduced at 900°C for 150 min, and the order of reduction performance was Fe2O3 &gt; Fe3O4 &gt; CaO·2Fe2O3 &gt; CaO·Fe2O3 &gt; 2CaO·Fe2O3 &gt; AT. The high‐temperature heat capacity of AT as a function of temperature was also measured and modeled.

An efficient and low-cost magnetic heterogenous Fenton-like catalyst for degrading antibiotics in wastewater: Mechanism, pathway and stability

Metal-doped MgFe2O4 spinel ferrite synthesized from saprolite laterite nickel ore was verified as an efficient heterogeneous Fenton-like catalyst for degrading antibiotics including tetracycline (TC) and metronidazole (MNZ) in a “catalyst/oxalic acid (H2C2O4)/visible light (vis)” system. The degradation efficiencies reached over 95% and total organic carbon (TOC) removal efficiencies were nearly 50% of the two antibiotics within 210 min, under the optimal conditions, especially 90% catalytic activity of the fresh catalyst was maintained after five cycles, suggesting the ferrite possessed excellent degrading performance, cycling stability and applicability. Moreover, the degradation mechanism and pathway of TC were elucidated in detail. Results revealed that the [≡Fe(C2O4)3]3- complex ions formed by octahedral Fe3+ in spinel ferrite with oxalate ions on the surface of MgFe2O4, played the key role in production of ·OH radicals which decomposed antibiotic TC into small molecules even mineralized in three pathways. Cost-effective preparation, high catalytic performance and long cycle life may accelerate the practical application of the heterogeneous Fenton-like catalyst.

Exploring the structural, elastic, optical, dielectric and magnetic characteristics of Ca2+ incorporated superparamagnetic Zn0.5−xCa0.1Co0.4+xFe2O4 (x = 0.0, 0.05 & 0.1) nanoferrites

This work is aimed to understand influence of 10% Ca doping on the structural, optical, dielectric and magnetic behavior of half doped Zinc-Cobalt nanoferrites. Zn0.5−xCa0.1Co0.4+xFe2O4 (x = 0.0, 0.05 & 0.1) nanoferrites with crystallite size in 10–13 nm range were synthesized through a sol-gel auto-incinerated route. Rietveld profile refinement of PXRD patterns, observation of spinel ferrite type fcc Laue rings in SAED patterns, Raman modes (A1g,T2g & Eg) and metal-oxide (υ1 & υ2) bonds in 400–600 cm−1 IR range illustrated formation of single phase mixed valent spinel type fcc nanoferrites. In these nanoferrites Zn2+ ion resides at tetrahedral (TA) site, while Co2+ & Ca2+ ions preferentially fill the octahedral OB site and Fe3+ ion occupy both TA & OB sites. Moderate optical absorbance in blue color region and strong absorbance in the lower UV region is observed in these nanoferrites, which is owing to presence of mixed valent ions at the OB and TA sites respectively. 10% Ca doping in these half doped Zn-Co nanoferrites led to considerable decrement in the band gap energy (Eg) and turning them to semiconducting state (Eg in 2.5–2.3 eV range). In these nanoferrites hopping of electrons between divalent Fe2+, Ca2+, Zn2+, Co2+ & trivalent Fe3+ & Co3+ cations led to systematic decrease in the dielectric parameters with frequency. These nanoferrites exhibited superparamagnetism with a high magnetic moment (~ 2.9–3.0μB/f.u.) at room temperature. Systematic enhancements in saturation magnetization (Ms), coercivity (Hc), remanence (Mr) and squareness ratio at low temperatures revealed changing of superparamagnetic character to soft ferrimagnetic state of these nanoferrites. At 20K, highest value of Ms = 119 emu/g was observed for Zn0.5Ca0.1Co0.4Fe2O4 nanoferrite, while highest Hc = 2911 Oe & Mr = 61.0 emu/g were recorded for Zn0.4Ca0.1Co0.5Fe2O4 nanoferrite. Thus, a moderate 10% Ca2+ ion incorporation in Zn0.5−xCa0.1Co0.4+xFe2O4 (x = 0.0, 0.05 & 0.1) nanoferrites is emerged as an effective route for obtaining superparamagnetic nanoferrites with high magnetic moment and reduced band gap energy. Unique magneto-optical characteristics of Zn0.5−xCa0.1Co0.4+xFe2O4 (x = 0.0, 0.05 & 0.1) nanoferrites would project them as a good material for opto-magnetic, drug carrier, biomedical contrast agent and magnetic storage applications.

Is the mean value of the 3d-electron radius $$\langle r^{4} \rangle$$ in the equation of the crystal-field theory constant?

In the equation of the crystal-field theory $$\Delta = \frac{{Q \cdot \langle r^{4} \rangle }}{{\overline{R}{^5} }}$$ , where Δ is the crystal-field splitting, $$\overline{R}$$ is the mean metal–ligand distance in the 3dN-ion-centered coordination polyhedron and Q is constant, $$\langle r^{4} \rangle$$ , the mean value of the fourth power of the 3d-electron radius, is assumed to be also constant (Burns 1993). Here, this assumption is proved by means of high-pressure optical absorption spectroscopy on octahedral Fe2+ in siderite FeCO3 in combination with the data of X-ray diffraction structural refinement by Lavina et al. (2010). It is shown that in the pressure range 1·10–4 to 44.5 GPa or $$\overline{R}$$ ranging from 2.15 to 1.97 A, the value of Q $$\cdot \langle r^{4} \rangle$$ does not deviate more than ~ 4% from its average value.

Structural, surface and optical properties of nanoalumina produced by various ways

Start The compared study of the properties of liquid-phase and electric explosion alumina nanoparticles was made. The X-ray diffraction analysis demonstrated that these nanoparticles remain in amorphous and semi-amorphous states. The complete structural information of Al2O3 nanoparticles was obtained as a result of the full-profile refinement of their model phase parameters. The parameters of the unit cells, spatial distribution of atoms, and occupancy of nodes were also determined.The data of IR spectra of surface OH groups and adsorbed CO revealed that the surface imperfection of an electric explosive sample is lower than that obtained using the liquid-phase method. Using photoluminescent spectroscopy, impurities of Cr3+, Mn4+ and Ti3+ in the octahedral oxygen coordination and Fe3+ in the tetrahedral oxygen coordination were detected. It was observed that the concentration of these impurities was significantly higher in the electric explosion sample. Using UV-Vis DR spectroscopy, it was found that the liquid-phase sample was amorphous, and the electric explosive sample was well crystallized and most probably consisted of 2D and 3D nanostructures.

Spin reorientation, normal and inverse magnetocaloric effects in heavy rare-earth iron garnets

Experiments for heavy rare-earth iron garnets Ho3Fe5O12 and Er3Fe5O12 show a compensation effect characterized by a near zero magnetization at 134 K and 80 K, respectively. The magnetic entropy change calculated according to the Maxwell's relation is shown to be positive and negative, indicating both normal and inverse magnetocaloric effects exist in the sample. The critical temperature (134 K for Ho3Fe5O12, 80 K for Er3Fe5O12) of the two types of magnetocaloric effect occurs at almost the same temperature as the compensation point. However, the compensation effect is attributed to the multiple exchange interactions among the octahedral sites Fe3+, the tetrahedral sites Fe3+ and the dodecahedral sites R3+, while the reversal of the magnetocaloric effect is originated from the spin reorientation. The maximum magnetic entropy change of the normal magnetocaloric effect is 4.72 J kg−1 K−1 for Ho3Fe5O12 at 34 K and 4.94 J kg−1 K−1 for Er3Fe5O12 at 24 K, respectively. Moreover, all the positive slopes of basic Arrott plots suggest only the second-order phase transition existing in Ho3Fe5O12 and Er3Fe5O12.